WO2011037072A1 - Cyclic compound, radiation-sensitive composition, and resist pattern formation method - Google Patents

Abstract

Disclosed is a cyclic compound represented by formula (1). (In the formula, L, R¹, R' and m are as defined in the description.) The cyclic compound represented by formula (1) is highly sensitive and enables the formation of a good resist pattern form, and is therefore useful as a component for a radiation-sensitive composition.

Description

Cyclic compound, radiation-sensitive composition, and resist pattern forming method

The present invention relates to a cyclic compound represented by a specific chemical structural formula, useful as an acid amplification type non-polymeric resist material, a radiation sensitive composition containing the same, and a resist pattern forming method using the composition.

Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, a resist thin film prepared by applying a solution of a polymer resist material such as polymethyl methacrylate, polyhydroxystyrene having an acid-dissociable reactive group or polyalkyl methacrylate on a substrate, ultraviolet rays, far ultraviolet rays, electron beams, extreme A line pattern of about 45 to 100 nm is formed by irradiating with ultraviolet rays (EUV), X-rays or the like.
However, polymer resists have a large molecular weight of about 10,000 to 100,000 and a wide molecular weight distribution. Therefore, in lithography using polymer resists, roughness is generated on the surface of fine patterns, making it difficult to control pattern dimensions. , Yield decreases. Therefore, there is a limit to miniaturization in conventional lithography using a polymer resist material. In order to produce finer patterns, various low molecular weight resist materials have been disclosed.
For example, an alkali developing negative radiation-sensitive composition (see Patent Document 1 and Patent Document 2) using a low molecular weight polynuclear polyphenol compound as a main component has been proposed. There is a drawback that the shape of the resist pattern to be obtained becomes worse.
As a candidate for a low molecular weight resist material, an alkali developing negative radiation-sensitive composition (see Patent Document 3 and Non-Patent Document 1) using a low molecular weight cyclic polyphenol compound as a main component has been proposed. Since these low molecular weight cyclic polyphenol compounds have a low molecular weight, it is expected to provide a resist pattern having a small molecular size, high resolution, and low roughness. Further, the low molecular weight cyclic polyphenol compound has a rigid cyclic structure in its skeleton, and thus provides high heat resistance despite its low molecular weight.
However, currently known low molecular weight cyclic polyphenol compounds have problems such as low solubility in safety solvents used in semiconductor manufacturing processes, low sensitivity, and poor resist pattern shape. Improvement of polyphenol compounds is desired.

JP 2005-326838 A JP 2008-145539 A JP 2009-173623 A

An object of the present invention is to provide a cyclic compound that gives a high-sensitivity and good resist pattern shape, a radiation-sensitive composition containing the same, and a resist pattern forming method using the radiation-sensitive composition. .

As a result of intensive studies to solve the above problems, the present inventors have found that a cyclic compound having a specific structure has a high solubility in safety solvent solubility, high sensitivity, and a good resist pattern shape. Invented.

That is, the present invention is as follows.
1. A cis cyclic compound represented by the following formula (1).

(In the formula (1), L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms. Group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ⁵ ) —C (═O) —, —N (R ⁵ ) —C (═O) O A divalent organic group selected from the group consisting of —, —S—, —SO—, —SO ₂ — and any combination thereof, and R ⁵ is hydrogen or an alkyl group having 1 to 10 carbon atoms. R ¹ is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cyano group, or a nitro group. Hydroxyl group, heterocyclic group, halogen, carboxyl group, acyl group having 2 to 20 carbon atoms, alkylsilyl having 1 to 20 carbon atoms Or a hydrogen atom, m is an integer of 0 to 4, R ′ is independently an alkyl group having 2 to 20 carbon atoms or the following formula

(Wherein R ⁴ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, A hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, or an alkylsilyl group having 1 to 20 carbon atoms, and p is an integer of 0 to 5)
Is an aryl group represented by: )

2. The cis cyclic compound according to item 1, represented by the following formula (2):

(In the formula (2), R ¹ , R ⁴ , p and m are the same as described above. X ₂ is a hydrogen or halogen atom, m ₅ is an integer of 0 to 3, and m + m ₅ = 4. .)

3. The cis cyclic compound according to item 2 represented by the following formula (3-1) or (3-2):

(In the formulas (3-1) and (3-2), R ¹ , R ⁴ , X ₂ , and p are the same as described above. M ₃ is 1 or 2, and m ₄ is 1. )

4). The cis cyclic compound of Claim 2 shown by following formula (4).

(In the formula (4), R ⁴ , X ₂ , m, m ₅ and p are the same as above.)

5. The cis cyclic compound according to item 4, represented by the following formula (5-1a) or (5-1b):

(In formulas (5-1a) and (5-1b), X ₂ , R ⁴ , m ₃ , m ₄ , and p are the same as described above.)

6). The cis cyclic compound according to item 5, represented by any one of the following formulas (6-1) to (6-4):

7. A radiation-sensitive composition comprising a cyclic compound comprising the cis cyclic compound according to any one of items 1 to 6 and a trans isomer thereof in a ratio of 80 to 100: 0 to 20 and a solvent.

8). The radiation-sensitive composition according to claim 7, comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent.

9. The radiation-sensitive composition according to claim 7 or 8, wherein the cyclic compound is 50 to 99.999% by weight of the total weight of the solid component.

10. The cyclic compound is at least one aldehyde compound (A1) having 2 to 59 carbon atoms having 1 to 4 formyl groups and at least one having 6 to 15 carbon atoms having 1 to 3 phenolic hydroxyl groups. The radiation-sensitive composition according to any one of items 7 to 9, which is synthesized by a condensation reaction with a phenol compound (A2) and has a molecular weight of 700 to 5,000.

11 The radiation-sensitive composition according to item 10, wherein the aldehyde compound (A1) is a benzaldehyde compound having 7 to 24 carbon atoms.

12 Acid is generated directly or indirectly by irradiation with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam, or heat. 12. The radiation sensitive composition according to any one of items 7 to 11, further comprising an acid generator (C).

13. The radiation-sensitive composition according to any one of items 7 to 12, further comprising an acid crosslinking agent (G).

14 14. The radiation sensitive composition according to any one of items 7 to 13, further comprising an acid diffusion controller (E).

15. 15. The radiation sensitive composition according to any one of items 7 to 14, wherein the cis cyclic compound is represented by the following formula (4).

(In the formula (4), R ⁴ , X ₂ , m, m ₅ and p are the same as above.)

16. 16. The radiation-sensitive composition according to item 15, wherein the cis cyclic compound is represented by the following formula (5-1a) or (5-1b).

(In the formulas (5-1a) and (5-1b), X ₂ , R ⁴ , m ₃ , m ₄ , and p are the same as described above.),

17. The radiation-sensitive composition according to item 16, wherein the cis-cyclic compound is represented by the following formula (5-2).

(In formula (5-2), R ⁴ and p are as defined above.)

18. The radiation-sensitive composition according to item 17, wherein the cis-cyclic compound is represented by any one of the following formulas (6-1) to (6-4).

19. The cyclic compound is obtained by a condensation reaction of two or more benzaldehyde compounds having 7 to 24 carbon atoms and two or more phenol compounds (A2) having 6 to 15 carbon atoms having 1 to 3 phenolic hydroxyl groups. The radiation-sensitive composition according to item 7.

20. The solid component is a cyclic compound / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) in a weight percentage of 50 to 99.99% based on the solid component. The radiation-sensitive composition according to item 8, which contains 4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49/0 to 49.

21. The radiation-sensitive composition according to item 7, wherein an amorphous film can be formed by spin coating.

22. The radiation-sensitive composition according to claim 21, wherein the dissolution rate of the amorphous film in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C is 10 Å / sec or more.

23. Dissolution rate of the amorphous film after irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or the amorphous film after heating at 20 to 250 ° C. in a 2.38 wt% tetramethylammonium hydroxide aqueous solution 22. The radiation sensitive composition according to item 21, wherein the composition is 5 kg / sec or less.

24. 24. A step of applying a radiation-sensitive composition according to any one of Items 7 to 23 on a substrate to form a resist film, a step of exposing the resist film, and a step of developing the exposed resist film Resist pattern forming method.

In the present invention, the cis isomer has a four-fold symmetry (C _4V ) represented by the following formulas (12-1) and (12-2), and is represented by cis-cis-cis (ccc). Shown is the structure of the bowl configuration.

(In the formulas (12-1) and (12-2), L, R ¹ , R ′ and m are the same as defined above. R ₇₆ represents the following formula:

L, R ¹ , and m are the same as described above. )

INDUSTRIAL APPLICABILITY According to the present invention, a cyclic compound that is highly soluble in a safe solvent, has high sensitivity, and gives a good resist pattern shape, a method for producing the same, a radiation-sensitive composition containing the same, and the radiation-sensitive composition are used. A resist pattern forming method can be provided.

Hereinafter, the present invention will be described in detail.
Cyclic Compound The cis cyclic compound of the present invention is represented by the following formula (1).

In the formula (1), L is independently a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms (preferably methylene, ethylene, propylene, butylene, pentylene, hexylene, methylmethylene, methyl Ethylene, dimethylmethylene, methylethylene), a cycloalkylene group having 3 to 20 carbon atoms (preferably cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene), an arylene group having 6 to 24 carbon atoms (preferably phenylene, naphthylene, Anthranylene, phenanthrylene), —O—, —OC (═O) —, —OC (═O) O—, —N (R ⁵ ) —C (═O) —, —N (R ⁵ ) —C (= O) a divalent organic group selected from the group consisting of O—, —S—, —SO—, —SO ₂ —, and any combination thereof. R ⁵ is hydrogen or an alkyl group having 1 to 10 carbon atoms (preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl).

R ¹ is independently an alkyl group having 1 to 20 carbon atoms (preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl), a cycloalkyl group having 3 to 20 carbon atoms (preferably cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl), aryl groups having 6 to 20 carbon atoms (preferably phenyl, naphthyl, anthranyl, phenanthryl), alkoxy groups having 1 to 20 carbon atoms (preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy) , T-butoxy), cyano group, nitro group, hydroxyl group, heterocyclic group (preferably pyridyl group, furyl group, thienyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, pyrazolyl group, benzofuranyl group, morpholinyl group) , Halogen (like Or fluorine, chlorine, bromine, iodine), carboxyl group, acyl group having 2 to 20 carbon atoms (preferably acetyl group, propionyl group, butyryl group), alkylsilyl group having 1 to 20 carbon atoms (preferably trimethylsilyl, triethyl). Silyl, tripropylsilyl, dimethylsilyl, diethylsilyl, dipropylsilyl, methylsilyl, ethylsilyl, propylsilyl) or a hydrogen atom.

R ′ is independently an alkyl group having 2 to 20 carbon atoms (preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, octyl, decyl, dodecyl, undecyl). Or the following formula

Is an aryl group represented by: R ⁴ is an alkyl group having 1 to 20 carbon atoms (preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl) or a cycloalkyl group having 3 to 20 carbon atoms (preferably cyclopropyl, cyclobutyl, cyclopentyl). Cyclohexyl), an aryl group having 6 to 20 carbon atoms (preferably phenyl, naphthyl, anthranyl, phenanthryl), an alkoxy group having 1 to 20 carbon atoms (preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t- Butoxy), cyano group, nitro group, hydroxyl group, heterocyclic group (preferably pyridyl group, furyl group, thienyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, pyrazolyl group, benzofuranyl group, morpholinyl group), halogen ( Preferably Element, chlorine, bromine, iodine), carboxyl group, or alkylsilyl group having 1 to 20 carbon atoms (preferably trimethylsilyl, triethylsilyl, tripropylsilyl, dimethylsilyl, diethylsilyl, dipropylsilyl, methylsilyl, ethylsilyl, propyl) Cyril). p is an integer of 0 to 5.

m is an integer of 0-4. -LR ¹ on different benzene rings may be the same or different, and when m is an integer of 2 to 4, 2 to 4 -LR ¹ on the same benzene ring may be the same or different. Good.

Preferred examples of the cis cyclic compound represented by the above formula (1) include the following compounds.

In the formulas (2) to (5-1b), R ¹ , R ⁴ , m, and p are the same as described above. X ₂ is hydrogen or a halogen atom (preferably fluorine, chlorine, bromine, iodine), m ₃ is 1 or 2, m ₄ is 1, m ₅ is an integer of 0 to 3, m + m ₅ = 4. )

The cis-cyclic compound of the present invention has high heat resistance and is amorphous so that it is excellent in film-forming properties, does not have sublimation properties, is excellent in alkali developability, etching resistance, etc. It is suitably used as a substrate.
In addition, in terms of production, various aldehydes including industrially produced aromatic aldehydes and phenols such as resorcinol and pyrogallol are subjected to a dehydration condensation reaction using a nonmetallic catalyst such as sulfuric acid, and then a column. Since it can be produced in a high yield by separation by a known method such as chromatography or preparative liquid chromatography, it is extremely excellent in practicality.

In the present invention, a cis cyclic compound represented by the following formula (5-2) is more preferable.

(In formula (5-2), R ⁴ and p are as defined above.)

In the present invention, cis cyclic compounds represented by the following formulas (6-1) to (6-4) are more preferable.

In the present invention, a cis cyclic compound represented by the above formula (6-3) is particularly preferred.

The molecular weight of the cyclic compound is 700 to 5000, preferably 800 to 2000, and more preferably 900 to 1500. Within the above range, the resolution is improved while maintaining the film formability required for the resist.

The radiation-sensitive composition of the present invention contains a cyclic compound mainly composed of a cis cyclic compound. The cyclic compound may contain a small amount of a trans cyclic compound. However, the resist component of the radiation-sensitive composition has only a cis cyclic compound, and the uniformity of the components in the resist film is high, and the pattern roughness is high. Since it reduces, it is more preferable. Moreover, since the sensitivity of a resist improves, it is more preferable. Therefore, the ratio of the cis cyclic compound to the trans cyclic compound in the cyclic compound is preferably 80 to 100: 0 to 20, more preferably 90 to 100: 0 to 10, and the cyclic compound is only the cis cyclic compound. It is further preferable that it contains.

The trans cyclic compound is a trans isomer of the cis cyclic compound of the formula (1) and is represented by the following formula (I).

(Wherein L, R ¹ , R ′ and m are the same as described above.)

A cyclic compound having only a cis cyclic compound can be obtained by a known method such as separation by column chromatography or preparative liquid chromatography, optimization of a reaction solvent and a reaction temperature during production, and the like.

For example, a cyclic compound having only the cis cyclic compound represented by the above formula (1) obtains a cis-trans mixture by a condensation reaction of one or more aldehyde compounds (A1) and one or more phenol compounds (A2). It is obtained by separating a cis-cyclic compound from the mixture by a known method such as column chromatography or preparative liquid chromatography.

More preferably, a cis-trans mixture is obtained by a condensation reaction of one or more aromatic aldehyde compounds (A1A) and one or more phenolic compounds (A2), and is obtained by a known method such as column chromatography or preparative liquid chromatography. It is obtained by separating the cis cyclic compound from the mixture.

The aldehyde compound (A1) has 2 to 59 carbon atoms, has 1 to 4 formyl groups, and is selected from an aromatic aldehyde compound (A1A) and an aliphatic aldehyde compound (A1B). The aromatic aldehyde compound (A1A) is a benzaldehyde compound having 7 to 24 carbon atoms, such as benzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, ethylmethylbenzaldehyde, isopropylmethylbenzaldehyde, diethylbenzaldehyde, Anisaldehyde, naphthaldehyde, anthraldehyde, cyclopropylbenzaldehyde, cyclobutylbenzaldehyde, cyclopentylbenzaldehyde, cyclohexylbenzaldehyde, phenylbenzaldehyde, naphthylbenzaldehyde, adamantylbenzaldehyde, norbornylbenzaldehyde, lactylbenzaldehyde, isopropylbenzal Examples include hydride, normal propyl benzaldehyde, bromo benzaldehyde, dimethylamino benzaldehyde, hydroxy benzaldehyde, dihydroxy benzaldehyde, trihydroxy benzaldehyde, etc., isopropyl benzaldehyde, normal propyl benzaldehyde, cyclohexyl benzaldehyde and phenyl benzaldehyde are preferable, 4-cyclohexyl benzaldehyde and 4-isopropyl aldehyde. Benzaldehyde is more preferred. The aromatic aldehyde compound (A1A) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired. The aromatic aldehyde compound (A1A) may be used alone or in combination of two or more.

The aliphatic aldehyde compound (A1B) is preferably a compound having 3 to 24 carbon atoms, such as ethanal, propanal, isopropanal, butanal, isobutanal, t-butanal, pentanal, isopentanal, neopentanal, hexanal. , Isohexanal, octanal, decanal, dodecanal, undecenal, cyclopropane carboxaldehyde, cyclobutane carboxaldehyde, cyclohexane carboxaldehyde and the like, isobutanal, t-butanal, pentanal, isopentanal, neopentanal, hexanal, isohexanal Octanal, decanal, dodecanal, cyclopropanecarboxaldehyde, cyclobutanecarboxaldehyde, cyclohexa Carboxaldehyde is preferred, octanal, decanal, dodecanal, cyclohexane carboxaldehyde more preferable. The aliphatic aldehyde compound (A1B) may have a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired. The aliphatic aldehyde compound (A1B) may be used alone or in combination of two or more.

The phenol compound (A2) preferably has 6 to 15 carbon atoms, and preferably has 1 to 3 phenolic hydroxyl groups. Examples of the phenol compound (A2) include phenol, catechol, resorcinol, hydroquinone, pyrogallol and the like, resorcinol and pyrogallol are preferable, and resorcinol is more preferable. The phenol compound (A2) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired. You may use a phenolic compound (A2) individually or in combination of 2 or more types.

The cis cyclic compound represented by the above formula (1) can be produced, for example, as follows. In the presence of an acid catalyst (hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, etc.) in an organic solvent such as methanol or ethanol, 0.1 to 10 mol of phenol compound (A2) is added to 1 mol of aldehyde compound (A1). The reaction is carried out at 60 to 150 ° C. for about 0.5 to 20 hours. Next, after filtration, washing with an alcohol such as methanol, washing with water, and separation by filtration, drying is performed to obtain a crude product (cis-trans mixture). By separating this crude product by column chromatography, preparative liquid chromatography, or the like, only a cis cyclic compound can be obtained. In place of the acid catalyst, a basic catalyst (sodium hydroxide, barium hydroxide, 1,8-diazabicyclo [5.4.0] undecene-7, etc.) is used, and cis cyclic reaction can be carried out in the same manner by reaction and separation. A compound is obtained. Furthermore, the cis cyclic compound is obtained by converting the aldehyde compound (A1) into a dihalide with hydrogen halide or halogen gas, reacting the isolated dihalide with the phenol compound (A2), and then separating only the cis cyclic compound. Can also be obtained.

More preferably, two or more aldehyde compounds (A1) and two or more phenol compounds (A2) are used. By using two or more aldehyde compounds (A1) and two or more phenol compounds (A2), the solubility of the resulting cyclic compound in a semiconductor safety solvent is improved.

In order to reduce the amount of residual metal in the cyclic compound, purification may be performed as necessary. Further, if the acid catalyst and the cocatalyst remain, generally, the storage stability of the radiation sensitive composition is lowered, or if the basic catalyst remains, generally the sensitivity of the radiation sensitive composition is lowered. The intended purification may be performed. Purification can be performed by a known method as long as the cyclic compound is not denatured, and is not particularly limited. For example, a method of washing with water, a method of washing with an acidic aqueous solution, a method of washing with a basic aqueous solution, or an ion exchange resin. The method of processing, the method of processing by silica gel column chromatography, etc. are mentioned. These purification methods are more preferably performed in combination of two or more. Acidic aqueous solution, basic aqueous solution, ion exchange resin, and silica gel column chromatography should be optimized depending on the metal to be removed, the amount and type of acidic compound and / or basic compound, the type of cyclic compound to be purified, etc. It is possible to select appropriately. For example, hydrochloric acid, nitric acid, acetic acid aqueous solution having a concentration of 0.01 to 10 mol / L as acidic aqueous solution, aqueous ammonia solution having a concentration of 0.01 to 10 mol / L as basic aqueous solution, cation exchange resin as ion exchange resin, For example, Amberlyst 15J-HG Dry made by Organo can be mentioned. You may dry after refinement | purification. Drying can be performed by a known method, and is not particularly limited. Examples thereof include vacuum drying and hot air drying under conditions where the cyclic compound is not denatured.

The cyclic compound can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process.

The cyclic compound is useful as a negative resist material that becomes a compound that is hardly soluble in an alkali developer by irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. By irradiating the cyclic compound with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, a condensation reaction between the compounds is induced and the compound becomes insoluble in an alkali developer. The resist pattern thus obtained has a very low LER.

The cyclic compound can be used as a main component of the negative radiation-sensitive composition, and can be added to the radiation-sensitive composition as an additive for improving sensitivity and etching resistance, for example. In this case, the cyclic compound is used at 1 to 49.999% by weight of the total weight of the solid component.

The glass transition temperature of the cyclic compound is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. When the glass transition temperature is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape and can provide performance such as high resolution.

The calorific value of crystallization determined by differential scanning calorimetry of the glass transition temperature of the cyclic compound is preferably less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the crystallization exotherm is less than 20 J / g, or (crystallization temperature) − (glass transition temperature) is within the above range, an amorphous film can be easily formed by spin coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.

In the present invention, the crystallization calorific value, crystallization temperature and glass transition temperature can be determined by differential scanning calorimetry using DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is put in an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 mL / min). After the rapid cooling, the temperature is raised again to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 mL / min). Further, after rapid cooling, the temperature is raised again to 400 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen gas stream (30 mL / min). The temperature at the midpoint of the step difference of the baseline that has changed in a step shape (where the specific heat has changed to half) is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature. The calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.

The cyclic compound preferably has a low sublimation property under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C. or lower, further preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower. Low sublimation means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, even more preferably 1% or less, particularly preferably Is preferably 0.1% or less. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Moreover, a favorable pattern shape can be given with low LER.

The cyclic compound preferably satisfies M <3.0 (M represents the total number of atoms / (total number of carbon atoms−total number of oxygen atoms)), and more preferably satisfies M <2.5. By satisfying the above conditions, the dry etching resistance is excellent.

Cyclic compounds include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate A solvent selected and having the highest solubility for the cyclic compound at 23 ° C., preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, particularly preferably A solvent selected from PGMEA, PGME, and CHN and having the highest solubility for the cyclic compound is at least 20% by weight at 23 ° C., particularly preferably at least 20% by weight at 23 ° C. with respect to PGMEA. Dissolve. By satisfying the above conditions, the semiconductor manufacturing process can be used in actual production.

A halogen atom may be introduced into the cyclic compound as long as the effect of the present invention is not impaired. The ratio of the number of halogen atoms to the total number of constituent atoms of the cyclic compound is preferably 0.1 to 60%, more preferably 0.1 to 40%, and more preferably 0.1 to 20%. More preferably, it is 0.1 to 10%, particularly preferably 1 to 5%. Within the above range, the film formability can be maintained while increasing the sensitivity to radiation. In addition, the solubility in a safe solvent can be improved.

Nitrogen atoms may be introduced into the cyclic compound as long as the effects of the present invention are not impaired. The ratio of the number of nitrogen atoms to the total number of constituent atoms of the cyclic compound is preferably 0.1 to 40%, more preferably 0.1 to 20%, and preferably 0.1 to 10%. Further preferred is 0.1 to 5%. Within the above range, the line edge roughness of the resulting resist pattern can be reduced. The introduced nitrogen atom is preferably a secondary or tertiary nitrogen atom, and more preferably a tertiary nitrogen atom.

As long as the effects of the present invention are not impaired, the cyclic compound is subjected to a crosslinking reaction by irradiation with visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, ion beam or chemical reaction induced thereby. A crosslinkable reactive group may be introduced. The introduction is performed, for example, by reacting a cyclic compound and a crosslinking reactive group introduction reagent in the presence of a base catalyst. Examples of the crosslinking reactive group include a carbon-carbon multiple bond, an epoxy group, an azide group, a halogenated phenyl group, and a chloromethyl group. Examples of the crosslinking reactive group introduction reagent include acids, acid chlorides, acid anhydrides, carboxylic acid derivatives such as dicarbonates and alkyl halides having such a crosslinking reactive group. A radiation-sensitive composition containing a cyclic compound having a crosslinking reactive group is also useful as a non-polymeric radiation-sensitive composition having high resolution, high heat resistance and solvent solubility.

A non-acid-dissociable functional group may be introduced into at least one phenolic hydroxyl group of the cyclic compound as long as the effect of the present invention is not impaired. The non-acid-dissociable functional group refers to a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group. For example, C1-20 alkyl group, C3-20 cycloalkyl group, C6-20 aryl group, C1-20 alkoxyl group, cyano group, nitro group, hydroxyl group, Examples thereof include a cyclic group, a halogen, a carboxyl group, a C1-20 alkylsilyl group, and a functional group selected from the group consisting of these derivatives.

A naphthoquinonediazide ester group may be introduced into at least one phenolic hydroxyl group of the cyclic compound as long as the effects of the present invention are not impaired. A compound in which a naphthoquinone diazide ester group is introduced into at least one phenolic hydroxyl group of a cyclic compound can be used as a main component of a negative radiation sensitive composition, and can be used as a main component of a positive radiation sensitive composition, It can add to a radiation sensitive composition as an acid generator and an additive.

In the range that does not impair the effect of the present invention, an acid-generating functional group that generates an acid upon irradiation with radiation may be introduced into at least one phenolic hydroxyl group of the cyclic compound. A cyclic polyphenol compound in which an acid-generating functional group that generates an acid upon irradiation with radiation is introduced into at least one phenolic hydroxyl group of the cyclic compound can be used as a main component of a negative radiation-sensitive composition. It can be used as a main component of the radiation-sensitive composition, or can be added to the radiation-sensitive composition as an acid generator or additive.

TECHNICAL FIELD The present invention relates to a radiation-sensitive composition comprising the aforementioned cyclic compound (a cis-cyclic compound and any trans-cyclic compound) and a solvent. The radiation-sensitive composition preferably comprises 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, and the cyclic compound is 50 to 99.999% by weight of the total weight of the solid component. Is preferred.

The radiation-sensitive composition of the present invention can form an amorphous film by spin coating. The dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present invention in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. is preferably 10 Å / sec or more, and preferably 10 to 10000 Å. / Sec is more preferable, and 100 to 1000 kg / sec is more preferable. It can melt | dissolve in an alkali developing solution as it is 10 tons / sec or more, and can be set as a resist. In addition, when the dissolution rate is 10000 kg / sec or less, the resolution may be improved. This is presumed to be due to the increase in the contrast of the interface between the unexposed portion dissolved in the alkali developer and the exposed portion not dissolved in the alkali developer due to the change in solubility of the cyclic compound before and after exposure. Further, there is an effect of reducing LER and reducing defects.

Dissolution of a portion exposed to radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray of an amorphous film formed by spin-coating the radiation-sensitive composition of the present invention in a 2.38 mass% TMAH aqueous solution at 23 ° C. The speed is preferably 5 K / sec or less, more preferably 0.05 to 5 K / sec, and further preferably 0.0005 to 5 K / sec. If it is 5 Å / sec or less, it is insoluble in an alkali developer and can be used as a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the cyclic compound is dissolved and LER is reduced. There is also an effect of reducing defects.

The radiation-sensitive composition of the present invention is preferably 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, more preferably 1 to 50% by weight of a solid component and 50 to 99% by weight of a solvent, and still more preferably. The solid component is 2 to 40% by weight and the solvent is 60 to 98% by weight, and particularly preferably the solid component is 2 to 10% by weight and the solvent is 90 to 98% by weight.

The amount of the cyclic compound is arbitrarily used such as the total weight of the solid component (cyclic compound, acid generator (C), acid crosslinking agent (G), acid diffusion controller (E), and other components (F). 50 to 99.4% by weight, preferably 55 to 90% by weight, more preferably 60 to 80% by weight, and particularly preferably 60 to 70% by weight of the total of the solid components. When the blending ratio is as described above, high resolution is obtained and the line edge roughness is reduced.

The composition of the present invention generates an acid directly or indirectly by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. It is preferable to include one or more acid generators (C). The amount of the acid generator used is preferably 0.001 to 49% by weight, more preferably 1 to 40% by weight, still more preferably 3 to 30% by weight, and particularly preferably 10 to 25% by weight based on the total weight of the solid components. By using within the above range, a pattern profile with high sensitivity and low edge roughness can be obtained. In the present invention, the acid generation method is not limited as long as an acid is generated in the system. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing is possible, and if high-energy rays are used, electron beam, extreme ultraviolet rays, X-rays, ion beam, further fine processing Is possible.

The acid generator (C) is preferably at least one selected from the group consisting of compounds represented by the following formulas (7-1) to (7-8).

(In formula (7-1), R ¹³ may be the same or different, and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. group, a hydroxyl group or a halogen atom; X ^- is an alkyl group, an aryl group, a sulfonic acid ion or halide ion having a halogen-substituted alkyl group or halogen-substituted aryl group).

The compound represented by the formula (7-1) includes triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n- Octane sulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenyl Sulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethane Sulfonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri ( 4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluene Sulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethyl Benzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-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-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate and cyclo (1,3-perfluoropropanedisulfone) at least selected from the group consisting of imidates It is preferred that one kind.

(In formula (7-2), R ^{14 s} may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. A group, a hydroxyl group or a halogen atom, X ⁻ is the same as defined above.)

The compound represented by the formula (7-2) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-tert-butylphenyl) iodonium, p-toluenesulfonate, bis (4-tert-butylphenyl) iodoniumbenzenesulfonate, bis (4-tert-butylphenyl) Iodonium-2-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis ( 4 t-butylphenyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octane Sulfonate, diphenyliodonium, p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4- Difluorobenzenesulfonate, diphe Ruiodonium hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium Perfluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium, p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate It is preferably at least one selected from the group consisting of

(In the formula (7-3), Q is an alkylene group, an arylene group or an alkoxylene group, and R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.)

The compound represented by the formula (7-3) includes 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-camphorsulfonyloxy) Succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-Dicarboximide, 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) naphthylimide, N- ( 2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- ( 4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Siimide, 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-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept Is preferably a 5-En 2,3-dicarboximide and N- at least one selected from the group consisting of (perfluoro--n- octane sulfonyloxy) naphthylimide.

(In formula (7-4), R ^{16 s} may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.)

The compound represented by the formula (7-4) is diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone. , Di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-trifluoromethylphenyl) disulfone It is preferable.

(In formula (7-5), R ^{17 s} may be the same or different, and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.)

The compound represented by the formula (7-5) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino). -Phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile And at least one selected from the group consisting of α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

In formula (7-6), R ¹⁸ 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.

In the formulas (7-7) and (7-8), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or cyclopentyl. A cycloalkyl group such as a cyclohexyl group, an alkoxyl group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group, or an aryl group such as a phenyl group, a toluyl group, and a naphthyl group, preferably 6 carbon atoms ~ 10 aryl groups. L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- Preferred examples include 1,2-quinonediazidosulfonyl groups such as a 6-sulfonyl group. In particular, 1,2-naphthoquinonediazido-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ¹⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (7-7-1), a carbonyl group, an ester group, an amide group or an ether group. Y ¹⁹ represents a hydrogen atom, an alkyl group or an aryl group, and X ²⁰ each independently represents a group represented by the following formula (7-8-1).

(In the formula (7-8-1), Z ²² each independently represents an alkyl group, a cycloalkyl group or an aryl group, R ²² represents an alkyl group, a cycloalkyl group or an alkoxyl group, and r represents 0-3. Is an integer.)

Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1, 4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6-bis (phenylsulfonylazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyl) Bissulfonyldiazomethanes such as zomethylsulfonyl) decane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4 Halogen-containing triazines such as 6- (bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) isocyanurate Derivatives and the like.

Of the acid generators, acid generators having an aromatic ring are preferable, and acid generators represented by formula (7-1) or (7-2) are more preferable. An acid generator having a sulfonate ion having X ^{− in} formula (7-1) or (7-2) having an aryl group or a halogen-substituted aryl group is more preferred, and an acid generator having a sulfonate ion having an aryl group Are particularly preferred, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are particularly preferred. LER can be reduced by using the acid generator. The acid generator (C) can be used alone or in combination of two or more.

The radiation-sensitive composition of the present invention preferably contains one or more acid crosslinking agents (G). The acid crosslinking agent (G) is a compound that can crosslink a cyclic compound within a molecule or between molecules in the presence of an acid generated from the acid generator (C). Examples of such an acid crosslinking agent (G) include compounds having one or more substituents (hereinafter referred to as “crosslinkable groups”) capable of crosslinking a cyclic compound.

Specific examples of such a crosslinkable group include (i) hydroxyalkyl groups such as hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group), acetoxy (C1-C6 alkyl group) and the like. Or a substituent derived therefrom; (ii) a carbonyl group such as formyl group, carboxy (C1-C6 alkyl group) or a substituent derived therefrom; (iii) a dimethylaminomethyl group, a diethylaminomethyl group, dimethylol Nitrogen-containing substituents such as aminomethyl group, diethylolaminomethyl group, morpholinomethyl group; (iv) glycidyl group-containing substituents such as glycidyl ether group, glycidyl ester group, glycidylamino group; (v) benzyloxymethyl Groups, benzoyloxymethyl groups, etc., C1-C6 allyloxy (C1-C6 Alkyl groups), substituents derived from aromatic groups such as C1-C6 aralkyloxy (C1-C6 alkyl groups); (vi) substituents containing polymerizable multiple bonds such as vinyl groups and isopropenyl groups. Can do. As the crosslinkable group of the acid crosslinking agent (G) of the present invention, a hydroxyalkyl group, an alkoxyalkyl group, and the like are preferable, and an alkoxymethyl group is particularly preferable.

Examples of the acid crosslinking agent (G) having a crosslinkable substituent include (i) a methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, a methylol group-containing glycoluril compound, and a methylol group-containing phenol compound. (Ii) alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds, etc. Containing compound; (iii) carboxymethyl group-containing melamine compound, carboxymethyl group-containing benzoguanamine compound, carboxymethyl group-containing urea compound, carboxymethyl group-containing Carboxymethyl group-containing compounds such as glycoluril compounds and carboxymethyl group-containing phenol compounds; (iv) Bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resole resin epoxy compounds And epoxy compounds such as poly (hydroxystyrene) -based epoxy compounds.

As the acid crosslinking agent (G), compounds having phenolic hydroxyl groups, and compounds and resins imparted with crosslinkability by introducing the crosslinkable group into acidic functional groups in the alkali-soluble resin can be used. . In this case, the introduction ratio of the crosslinkable group is usually 5 to 100 mol%, preferably 10 to 60 mol%, more preferably, based on the total acidic functional group in the compound having a phenolic hydroxyl group and the alkali-soluble resin. Is adjusted to 15-40 mol%. Within the above range, the cross-linking reaction occurs sufficiently, and a decrease in the remaining film ratio, a pattern swelling phenomenon, meandering, and the like can be avoided.

In the radiation-sensitive composition of the present invention, the acid crosslinking agent (G) is preferably an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycoluril compound or a resin thereof. Particularly preferred acid crosslinking agents (G) include compounds represented by the following formulas (8-1) to (8-3) and alkoxymethylated melamine compounds (acid crosslinking agent (G1)).

(In the above formula, R ⁷ each independently represents a hydrogen atom, an alkyl group, or an acyl group; R ⁸ to R ¹¹ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxyl group; X ² represents a single bond, a methylene group, or an oxygen atom.)

The alkyl group represented by R ⁷ preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The acyl group represented by R ⁷ preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and examples thereof include an acetyl group and a propionyl group. The alkyl group represented by R ⁸ to R ¹¹ preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkoxyl group represented by R ⁸ to R ¹¹ preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X ² is preferably a single bond or a methylene group. R ⁷ to R ¹¹ and X ² may be substituted with an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a hydroxyl group, or a halogen atom. The plurality of R ⁷ and R ⁸ to R ¹¹ may be the same or different.

Specific examples of the compound represented by the formula (8-1) include the compounds shown below.

Specific examples of the compound represented by the formula (8-2) include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril. N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) ) Glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, and the like. Of these, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.

Specific examples of the compound represented by the formula (8-3) include the compounds shown below.

Specific examples of alkoxymethylated melamine compounds include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (ethoxymethyl) melamine N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N, N, N, N, Examples thereof include N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like. Among these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable.
The acid crosslinking agent (G1) is obtained by, for example, condensing a urea compound or a glycoluril compound, and formalin to introduce a methylol group, and then ether with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol. Then, the reaction solution is cooled and the precipitated compound or its resin is recovered. The acid cross-linking agent (G1) can also be obtained as a commercial product such as CYMEL (trade name, manufactured by Mitsui Cyanamid) or Nicalac (manufactured by Sanwa Chemical Co., Ltd.).

Further, as other particularly preferred acid crosslinking agents (G), the molecule has 1 to 6 benzene rings, and has at least two hydroxyalkyl groups and / or alkoxyalkyl groups in the molecule. And / or a phenol derivative in which an alkoxyalkyl group is bonded to any one of the benzene rings (acid crosslinking agent (G2)). Preferably, the molecular weight is 1500 or less, the molecule has 1 to 6 benzene rings, and the hydroxyalkyl group and / or alkoxyalkyl group has 2 or more in total, and the hydroxyalkyl group and / or alkoxyalkyl group is the benzene ring. A phenol derivative formed by bonding to any one or a plurality of benzene rings can be given.

As the hydroxyalkyl group bonded to the benzene ring, those having 1 to 6 carbon atoms such as hydroxymethyl group, 2-hydroxyethyl group, and 2-hydroxy-1-propyl group are preferable. The alkoxyalkyl group bonded to the benzene ring is preferably one having 2 to 6 carbon atoms. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, 2-methoxyethyl And the 2-methoxy-1-propyl group is preferred.

Among these phenol derivatives, particularly preferable ones are listed below.

In the above formula, L ¹ to L ⁸ may be the same or different and each independently represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group. A phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ¹ to L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. it can. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, it can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.
A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like.

A phenol derivative having a hydroxymethyl group and / or an alkoxymethyl group synthesized in this manner is preferable in terms of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. preferable. The acid crosslinking agent (G2) may be used alone or in combination of two or more.

Another particularly preferable acid crosslinking agent (G) is a compound having at least one α-hydroxyisopropyl group (acid crosslinking agent (G3)). The structure is not particularly limited as long as it has an α-hydroxyisopropyl group. Further, the hydrogen atom of the hydroxyl group in the α-hydroxyisopropyl group is one or more acid dissociable groups (R—COO— group, R—SO ₂ — group, etc., R is a straight chain having 1 to 12 carbon atoms) From a hydrocarbon group having 3 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a 1-branched alkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms Which represents a substituent selected from the group consisting of: Examples of the compound having an α-hydroxyisopropyl group include one or two types such as a substituted or unsubstituted aromatic compound, diphenyl compound, naphthalene compound, and furan compound containing at least one α-hydroxyisopropyl group. The above is mentioned. Specifically, for example, a compound represented by the following general formula (9-1) (hereinafter referred to as “benzene compound (1)”), a compound represented by the following general formula (9-2) (hereinafter referred to as “benzene compound (1)”). , “Diphenyl compound (2)”), a compound represented by the following general formula (9-3) (hereinafter referred to as “naphthalene compound (3”)), and the following general formula (9-4): And the like (hereinafter referred to as “furan compound (4)”).

In the general formulas (9-1) to (9-4), each A ² independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A ² is an α-hydroxyisopropyl group. In the general formula (9-1), R ⁵¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkylcarbonyl group having 2 to 6 carbon atoms, or a linear or branched structure having 2 to 6 carbon atoms. The alkoxycarbonyl group of is shown. In the general formula (9-2), R ⁵² represents a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —CO—, or —COO—. In the general formula (9-4), R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

Specific examples of the benzene compound (1) include α-hydroxyisopropylbenzene, 1,3-bis (α-hydroxyisopropyl) benzene, 1,4-bis (α-hydroxyisopropyl) benzene, 1,2 Α-hydroxyisopropylbenzenes such as 1,4-tris (α-hydroxyisopropyl) benzene, 1,3,5-tris (α-hydroxyisopropyl) benzene; 3-α-hydroxyisopropylphenol, 4-α-hydroxyisopropylphenol Α-hydroxyisopropylphenols such as 3,5-bis (α-hydroxyisopropyl) phenol and 2,4,6-tris (α-hydroxyisopropyl) phenol; 3-α-hydroxyisopropylphenyl methyl ketone, 4-α -Hydroxyisopropyl Phenyl methyl ketone, 4-α-hydroxyisopropylphenyl ethyl ketone, 4-α-hydroxyisopropylphenyl n-propyl ketone, 4-α-hydroxyisopropylphenyl isopropyl ketone, 4-α-hydroxyisopropylphenyl n-butyl ketone, 4-α-hydroxyisopropylphenyl · t-butylketone, 4-α-hydroxyisopropylphenyl · n-pentylketone, 3,5-bis (α-hydroxyisopropyl) phenyl · methylketone, 3,5-bis (α-hydroxyisopropyl) ) Α-hydroxyisopropyl phenyl alkyl ketones such as phenyl ethyl ketone, 2,4,6-tris (α-hydroxyisopropyl) phenyl methyl ketone; 3-α-hydroxyisopropyl benzoic acid , Methyl 4-α-hydroxyisopropyl benzoate, ethyl 4-α-hydroxyisopropyl benzoate, n-propyl 4-α-hydroxyisopropyl benzoate, isopropyl 4-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl N-butyl benzoate, t-butyl 4-α-hydroxyisopropyl benzoate, n-pentyl 4-α-hydroxyisopropyl benzoate, methyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3,5-bis And alkyl 4-α-hydroxyisopropylbenzoate such as ethyl (α-hydroxyisopropyl) benzoate and methyl 2,4,6-tris (α-hydroxyisopropyl) benzoate.

Specific examples of the diphenyl compound (2) include 3-α-hydroxyisopropylbiphenyl, 4-α-hydroxyisopropylbiphenyl, 3,5-bis (α-hydroxyisopropyl) biphenyl, 3,3 ′. -Bis (α-hydroxyisopropyl) biphenyl, 3,4'-bis (α-hydroxyisopropyl) biphenyl, 4,4'-bis (α-hydroxyisopropyl) biphenyl, 2,4,6-tris (α-hydroxyisopropyl) ) Biphenyl, 3,3 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 3,4 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,6, -tetrakis (α-hydroxy) Isopropyl) biphenyl, 2,4,4 ′, 6, -tetrakis (α-hydroxyisopropyl) Biphenyl, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) biphenyl, 2,2 ′, 4,4 Α-hydroxyisopropylbiphenyls such as', 6,6'-hexakis (α-hydroxyisopropyl) biphenyl; 3-α-hydroxyisopropyldiphenylmethane, 4-α-hydroxyisopropyldiphenylmethane, 1- (4-α-hydroxyisopropylphenyl) ) -2-Phenylethane, 1- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 2- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 1- (4-α-hydroxyisopropyl) Phenyl) -3-phenylpropane, 1- (4-α-hydroxy) Sopropylphenyl) -4-phenylbutane, 1- (4-α-hydroxyisopropylphenyl) -5-phenylpentane, 3,5-bis (α-hydroxyisopropyldiphenylmethane, 3,3′-bis (α-hydroxyisopropyl) ) Diphenylmethane, 3,4′-bis (α-hydroxyisopropyl) diphenylmethane, 4,4′-bis (α-hydroxyisopropyl) diphenylmethane, 1,2-bis (4-α-hydroxyisopropylphenyl) ethane, 1,2 -Bis (4-α-hydroxypropylphenyl) propane, 2,2-bis (4-α-hydroxypropylphenyl) propane, 1,3-bis (4-α-hydroxypropylphenyl) propane, 2,4,6 -Tris (α-hydroxyisopropyl) diphenylmethane, 3,3 ', 5 Tris (α-hydroxyisopropyl) diphenylmethane, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) diphenylmethane, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenylmethane, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) diphenylmethane Α-hydroxyisopropyldiphenylalkanes such as 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenylmethane; 3-α-hydroxyisopropyldiphenyl ether, 4-α-hydroxyisopropyldiphenyl ether, 3,5-bis ( α-hydroxyisopropyl) diphenyl ether, 3,3′-bis (α-hydroxyisopropyl) diphenyl ether, 3,4′-bis (α-hydroxyisopropyl) diphenyl ether, 4,4′-bis (α-hydroxyisopropyl) diphenyl ether, 2 , 4,6-Tris (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ether, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenyl ether, 2,3 ′ , 4,6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenyl ether , Α-hydroxyisopropyl such as 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ether, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenyl ether Diphenyl ethers; 3-α-hydroxyisopropyl diphenyl ketone, 4-α-hydroxyisopropyl diphenyl ketone, 3,5-bis (α-hydroxyisopropyl) diphenyl ketone, 3,3′-bis (α-hydroxyisopropyl) diphenyl ketone, 3,4′-bis (α-hydroxyisopropyl) diphenyl ketone, 4,4′-bis (α-hydroxyisopropyl) diphenyl ketone, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ketone, 3,3 ′ , 5-Tris (α-hydroxyisopropyl) diph Phenyl ketone, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 2,4,4 ′, 6-tetrakis (α -Hydroxyisopropyl) diphenyl ketone, 3,3 ', 5,5'-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 2,3', 4,5 ', 6-pentakis (α-hydroxyisopropyl) diphenyl ketone, 2 , 2 ', 4,4', 6,6'-hexakis (α-hydroxyisopropyl) diphenylketone, etc .; α-hydroxyisopropyldiphenyl ketones; phenyl 3-α-hydroxyisopropylbenzoate, 4-α-hydroxyisopropylbenzoate Acid phenyl, benzoic acid 3-α-hydroxyisopropylphenyl, benzoic acid 4- -Hydroxyisopropylphenyl, phenyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3-α-hydroxyisopropylbenzoate 3-α-hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoate 4-α-hydroxyisopropyl Phenyl, 4-α-hydroxyisopropylbenzoate 3-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoate 4-α-hydroxyisopropylphenyl, benzoate 3,5-bis (α-hydroxyisopropyl) phenyl, 2 , 4,6-Tris (α-hydroxyisopropyl) benzoic acid phenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3-α-hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 4 α-hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoate 3,5-bis (α-hydroxyisopropyl) phenyl, 4-α-hydroxyisopropylbenzoate 3,5-bis (α-hydroxyisopropyl) phenyl, benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 3-α-hydroxyisopropylphenyl, 2,4,6-tris (α-hydroxyisopropyl) ) 4-α-hydroxyisopropylphenyl benzoate, 3,5-bis (α-hydroxyisopropyl) benzoate 3,5-bis (α-hydroxyisopropyl) phenyl benzoate, 3, α-hydroxyisopropyl benzoate 2,4,6 -Tris (α-hydroxyisopropyl) phenyl, 4 α-Hydroxyisopropylbenzoate 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoate 3,5-bis (α-hydroxyisopropyl) phenyl, 3 , 5-Bis (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 2,4,6-tris ( and α-hydroxyisopropyl benzoate phenyls such as α-hydroxyisopropyl) phenyl.

Further, specific examples of the naphthalene compound (3) include 1- (α-hydroxyisopropyl) naphthalene, 2- (α-hydroxyisopropyl) naphthalene, 1,3-bis (α-hydroxyisopropyl) naphthalene, 1,4-bis (α-hydroxyisopropyl) naphthalene, 1,5-bis (α-hydroxyisopropyl) naphthalene, 1,6-bis (α-hydroxyisopropyl) naphthalene, 1,7-bis (α-hydroxyisopropyl) Naphthalene, 2,6-bis (α-hydroxyisopropyl) naphthalene, 2,7-bis (α-hydroxyisopropyl) naphthalene, 1,3,5-tris (α-hydroxyisopropyl) naphthalene, 1,3,6-tris (Α-hydroxyisopropyl) naphthalene, 1,3,7-tris (α Hydroxyisopropyl) naphthalene, 1,4,6-tris (α-hydroxyisopropyl) naphthalene, 1,4,7-tris (α-hydroxyisopropyl) naphthalene, 1,3,5,7-tetrakis (α-hydroxyisopropyl) And naphthalene.

Specific examples of the furan compound (4) include 3- (α-hydroxyisopropyl) furan, 2-methyl-3- (α-hydroxyisopropyl) furan, 2-methyl-4- (α- Hydroxyisopropyl) furan, 2-ethyl-4- (α-hydroxyisopropyl) furan, 2-n-propyl-4- (α-hydroxyisopropyl) furan, 2-isopropyl-4- (α-hydroxyisopropyl) furan, 2 -N-butyl-4- (α-hydroxyisopropyl) furan, 2-t-butyl-4- (α-hydroxyisopropyl) furan, 2-n-pentyl-4- (α-hydroxyisopropyl) furan, 2,5 -Dimethyl-3- (α-hydroxyisopropyl) furan, 2,5-diethyl-3- (α-hydroxyisopropyl) fura 3,4-bis (α-hydroxyisopropyl) furan, 2,5-dimethyl-3,4-bis (α-hydroxyisopropyl) furan, 2,5-diethyl-3,4-bis (α-hydroxyisopropyl) ) Furan etc. can be mentioned.

The acid crosslinking agent (G3) is preferably a compound having two or more free α-hydroxyisopropyl groups, the benzene compound (1) having two or more α-hydroxyisopropyl groups, and two or more α-hydroxyisopropyl groups. More preferably, the diphenyl compound (2) having two or more α-hydroxyisopropyl groups, and the naphthalene compound (3) having two or more α-hydroxyisopropyl groups, α-hydroxyisopropylbiphenyls having two or more α-hydroxyisopropyl groups, α-hydroxy A naphthalene compound (3) having two or more isopropyl groups is particularly preferred.
The acid crosslinking agent (G3) is usually obtained by a method in which a acetyl group-containing compound such as 1,3-diacetylbenzene is reacted with a Grignard reagent such as CH ₃ MgBr for methylation, followed by hydrolysis. It can be obtained by a method in which an isopropyl group-containing compound such as diisopropylbenzene is oxidized with oxygen or the like to generate a peroxide and then reduced.

In the present invention, the amount of the acid crosslinking agent (G) used is preferably 0.5 to 49% by weight, more preferably 0.5 to 40% by weight, still more preferably 1 to 30% by weight, based on the total weight of the solid component. ˜20% by weight is particularly preferred. When the blending ratio of the acid crosslinking agent (G) is 0.5% by weight or more, the effect of suppressing the solubility of the resist film in an alkaline developer is improved, the remaining film ratio is decreased, and pattern swelling and meandering are caused. Since generation | occurrence | production can be suppressed, it is preferable, and on the other hand, when it is 49 weight% or less, since the fall of the heat resistance as a resist can be suppressed is preferable.

Further, the blending ratio of at least one compound selected from the acid crosslinking agent (G1), the acid crosslinking agent (G2), and the acid crosslinking agent (G3) in the acid crosslinking agent (G) is not particularly limited. Various ranges can be used depending on the type of substrate used when forming the pattern.

In the total acid crosslinking agent component, the alkoxymethylated melamine compound and / or the compounds represented by (9-1) to (9-3) are 50 to 99% by weight, preferably 60 to 99% by weight, more preferably 70%. It is preferable that the amount be ˜98 wt%, more preferably 80 to 97 wt%. It is preferable that the alkoxymethylated melamine compound and / or the compounds represented by (9-1) to (9-3) be 50% by weight or more of the total acid crosslinking agent component because the resolution can be improved. It is preferable to set the weight% or less because it is easy to obtain a rectangular cross-sectional shape as the pattern cross-sectional shape.

In the present invention, an acid diffusion control agent (E) having an action of controlling undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. You may mix | blend with a radiation sensitive composition. By using such an acid diffusion controller (E), the storage stability of the radiation-sensitive composition is improved. In addition, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before irradiation and the holding time after irradiation can be suppressed, and the process stability is extremely excellent. Examples of such an acid diffusion controller (E) include radiolytically decomposable basic compounds such as a nitrogen atom-containing basic compound, a basic sulfonium compound, and a basic iodonium compound. The acid diffusion controller can be used alone or in combination of two or more.

Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that are decomposed by exposure. Examples of the nitrogen-containing organic compound include the following general formula (10):

(Hereinafter referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (II)”), and a nitrogen atom. Examples thereof include polyamino compounds and polymers having three or more (hereinafter referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. In addition, an acid diffusion control agent (E) may be used individually by 1 type, and may use 2 or more types together.

In the general formula (10), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with a hydroxyl group or the like. Here, examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and specifically include methyl groups, ethyl groups, and n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group N-ethylhexyl group, n-nonyl group, n-decyl group and the like. Examples of the aryl group include those having 6 to 12 carbon atoms, and specific examples include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group. Furthermore, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

Specific examples of the nitrogen-containing compound (I) include mono (cyclohexanamine) such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, cyclohexylamine and the like. ) Alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine , Methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, dicyclohexylamine and other di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n- Pentylamine, tri-n-hexylamine, tri-n-heptylamine, Tri (cyclo) alkylamines such as ri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, Aromatic amines such as diphenylamine, triphenylamine and 1-naphthylamine can be exemplified.

Specific examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 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- Chiruechiru] benzene, and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.

Specific examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.
Specific examples of the amide group-containing compound include, for example, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methylpyrrolidone.

Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri- Examples thereof include n-butylthiourea.

Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, and 2-phenylbenzimidazole; pyridine, 2-methylpyridine 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline And pyridines such as acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2. ] Octane It can be mentioned.

Examples of the radiation-decomposable basic compound include the following general formula (11-1):

A sulfonium compound represented by the general formula (11-2):

The iodonium compound etc. which are represented by these can be mentioned.

In the general formulas (11-1) and (11-2), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. Represents an alkoxyl group, a hydroxyl group or a halogen atom of ˜6. Z ⁻ represents HO ⁻ , R—COO ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 11 carbon atoms, or an alkaryl group having 7 to 12 carbon atoms) or the following general formula (11-3):

An anion represented by

Specific examples of the radiolytic basic compound include, for example, triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenylsulfonium. Acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-tert-butylphenyl) iodonium hydroxide, bis (4-tert-butylphenyl) iodonium acetate, bis (4-tert-butylphenyl) iodonium hydroxide Bis (4-tert-butylphenyl) iodonium acetate, bis (4-tert-butylphenyl) iodonium salicylate, 4-tert-butylphenyl 4-hydroxyphenyl iodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyl iodonium acetate, include 4-t-butylphenyl-4-hydroxyphenyl iodonium salicylate and the like.

The blending amount of the acid diffusion controller (E) is preferably 0.001 to 49% by weight, more preferably 0.01 to 10% by weight, still more preferably 0.01 to 5% by weight, based on the total weight of the solid component. 0.01 to 3% by weight is particularly preferred. Within the above range, it is possible to prevent degradation in resolution, pattern shape, dimensional fidelity, and the like. Furthermore, even if the holding time from electron beam irradiation to heating after radiation irradiation becomes longer, the shape of the pattern upper layer portion does not deteriorate. Further, when the blending amount is 10% by weight or less, it is possible to prevent a decrease in sensitivity, developability of an unexposed portion, and the like. Further, by using such an acid diffusion control agent, the storage stability of the radiation-sensitive composition is improved, the resolution is improved, and the holding time before irradiation and the holding time after irradiation are reduced. Changes in the line width of the resist pattern due to fluctuations can be suppressed, and the process stability is extremely excellent.

The radiation-sensitive composition of the present invention includes, as necessary, other components (F) as long as the purpose of the present invention is not impaired, a dissolution accelerator, a dissolution controller, a sensitizer, a surfactant, One or more additives such as organic carboxylic acids or phosphorus oxo acids or derivatives thereof can be added.

(1) Solubility Accelerator A low molecular weight solubilizer enhances the solubility of a cyclic compound during development and moderately increases the dissolution rate of the cyclic compound when the solubility of the cyclic compound in an alkali or other developer is too low. It is a component having an action, and can be used within a range not impairing the effects of the present invention. Examples of the dissolution accelerator include low molecular weight phenol compounds, and examples thereof include bisphenols and tris (hydroxyphenyl) methane. These dissolution promoters can be used alone or in admixture of two or more.

The blending amount of the dissolution accelerator is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 49% by weight, more preferably 0 to 5% by weight, and more preferably 0 to 1% by weight based on the total weight of the solid component. Is more preferable, and 0% by weight is particularly preferable.

(2) Solubility control agent Solubility control agent is a component that acts to moderately reduce the dissolution rate during development by controlling its solubility when the cyclic compound is too soluble in an alkali or other developer. is there. As such a dissolution control agent, those that do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable. Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. These dissolution control agents can be used alone or in combination of two or more.

The blending amount of the dissolution control agent is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 49% by weight, more preferably 0 to 5% by weight, and more preferably 0 to 1% by weight based on the total weight of the solid component. Is more preferable, and 0% by weight is particularly preferable.

(3) Sensitizer The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (C), thereby increasing the amount of acid generated, and resist. It is a component that improves the apparent sensitivity. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more.

The blending amount of the sensitizer is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 49% by weight, more preferably 0 to 5% by weight, and more preferably 0 to 1% by weight based on the total weight of the solid component. Is more preferable, and 0% by weight is particularly preferable.

(4) Surfactant The surfactant is a component having an action of improving the coating property and striation of the radiation-sensitive composition of the present invention, the developability of the resist, and the like. Such a surfactant may be anionic, cationic, nonionic or amphoteric. A preferred surfactant is a nonionic surfactant. Nonionic surfactants have better affinity with the solvent used in the production of the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers and higher fatty acid diesters of polyethylene glycol, but are not particularly limited. Commercially available products have the following trade names: F-top (manufactured by Gemco), Mega-Fac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass), Examples include Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.)

The blending amount of the surfactant is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 49% by weight, more preferably 0 to 5% by weight, and more preferably 0 to 1% by weight based on the total weight of the solid component. Is more preferable, and 0% by weight is particularly preferable.

(5) Organic carboxylic acid or phosphorus oxo acid or derivative thereof For the purpose of preventing sensitivity deterioration or improving resist pattern shape, retention stability, etc., organic carboxylic acid or phosphorus oxo acid or derivative thereof is further included as an optional component. Can be contained. In addition, it can be used in combination with an acid diffusion controller, or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and the like, and derivatives such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester or derivatives thereof, phosphinic acid such as phosphinic acid, phenylphosphinic acid and derivatives such as esters thereof. Of these, phosphonic acid is particularly preferred. The organic carboxylic acid or phosphorus oxo acid or derivative thereof may be used alone or in combination of two or more.

The amount of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is appropriately adjusted according to the kind of the cyclic compound to be used, and is preferably 0 to 49% by weight, preferably 0 to 5% by weight based on the total weight of the solid component. More preferably, 0 to 1% by weight is further preferable, and 0% by weight is particularly preferable.

(6) The above-mentioned dissolution control agent, sensitizer, surfactant, and other additives other than organic carboxylic acid or phosphorus oxo acid or derivatives thereof. One or more additives other than the above-mentioned dissolution control agent, sensitizer, and surfactant can be blended as necessary within a range not inhibiting the purpose. Examples of such additives include dyes, pigments, and adhesion aids. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.

Formulation of the radiation-sensitive composition of the present invention (cyclic compound / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) is weight% based on solids so,
Preferably 50 to 99.4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49/0 to 49,
More preferably 55 to 90/1 to 40 / 0.5 to 40 / 0.01 to 10/0 to 5,
More preferably 60 to 80/3 to 30/1 to 30 / 0.01 to 5/0 to 1,
Particularly preferred is 60 to 70/10 to 25/2 to 20 / 0.01 to 3/0. The blending ratio of each component is selected from each range so that the sum is 100% by weight. When the above composition is used, the performance such as sensitivity, resolution and alkali developability is excellent.

The radiation-sensitive composition of the present invention is usually prepared by dissolving each component in a solvent at the time of use to make a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, if necessary. The

Examples of the solvent used in the preparation of the radiation-sensitive composition of the present invention include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n- Ethylene glycol monoalkyl ether acetates such as butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n- Propyl ether acetate, propylene glycol mono-n-butyl ether acetate, etc. Propylene glycol monoalkyl ether acetates; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; Lactic acid such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate and n-amyl lactate Esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybut Other esters such as rubacetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic carbonization such as toluene, xylene Hydrogens; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone; N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Amides; lactones such as γ-lactone can be mentioned, but are not particularly limited. These solvents can be used alone or in combination of two or more.

The radiation-sensitive composition of the present invention can contain a resin that is soluble in an alkaline aqueous solution as long as the object of the present invention is not impaired. Resins that are soluble in an alkaline aqueous solution include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and heavy polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units. A combination, or a derivative thereof may be used. The blending amount of the resin that is soluble in the alkaline aqueous solution is appropriately adjusted according to the type of the cyclic compound to be used, but is preferably 30 parts by weight or less, more preferably 10 parts by weight or less per 100 parts by weight of the cyclic compound. More preferably, it is 5 parts by weight or less, particularly preferably 0 part by weight.

The present invention relates to a method of forming a resist film on a substrate using the radiation-sensitive composition of the present invention, a step of exposing the resist film, and developing the resist film to form a resist pattern. The present invention relates to a method for forming a resist pattern including a step of forming. The resist pattern of the present invention can also be formed as an upper resist in a multilayer process.

In order to form a resist pattern, first, a resist film is formed by applying the radiation-sensitive composition of the present invention on a conventionally known substrate by a coating means such as spin coating, cast coating or roll coating. . The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon wafer, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. If necessary, an inorganic and / or organic film may be provided on the substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.

Next, the coated substrate is heated as necessary. The heating conditions vary depending on the composition of the radiation sensitive composition, but are preferably 20 to 250 ° C., more preferably 20 to 150 ° C. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. The heating conditions vary depending on the composition of the radiation sensitive composition, but are preferably 20 to 250 ° C., more preferably 20 to 150 ° C.

Next, a predetermined resist pattern is formed by developing the exposed resist film with an alkali developer. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline. An alkaline aqueous solution in which one or more compounds are dissolved in a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used. When the concentration of the alkaline aqueous solution is 10% by mass or less, it is preferable because the exposed portion can be prevented from being dissolved in the developer.

Also, an appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. This is preferable since the wettability of the developer with respect to the resist can be improved. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans with water after image development.

After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like. Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

The residual resist pattern after etching can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), etc. Examples of the strong alkaline aqueous solution include 1 to 20% by mass sodium hydroxide aqueous solution, A 1 to 20% by mass aqueous potassium hydroxide solution can be mentioned. Examples of the peeling method include a dipping method and a spray method. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

The wiring board obtained by the present invention can also be formed by a method of depositing a metal in a vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following synthesis examples and examples, the structures of the compounds were confirmed by ¹ H-NMR measurement.

Synthesis example 1
Synthesis of CR-1 A four-necked flask (1000 mL) equipped with a well-dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, and stirring blade was placed under a nitrogen stream under resorcinol (manufactured by Kanto Chemical Co., Ltd.). 22 g, 0.2 mol), 4-isopropylbenzaldehyde (29.6 g, 0.2 mol) and dehydrated ethanol (200 mL) were added to prepare an ethanol solution. This solution was heated to 85 ° C. with a mantle heater while stirring. Next, 75 mL of concentrated hydrochloric acid (35%) was added dropwise over 30 minutes using a dropping funnel, followed by stirring at 85 ° C. for 3 hours. After the completion of the reaction, the mixture was allowed to cool and allowed to reach room temperature, and then cooled in an ice bath. After standing for 1 hour, pale yellow target crude crystals were produced, which were filtered off. The crude crystals were washed twice with 500 ml of methanol, filtered and dried under vacuum to obtain 45.6 g of a compound. As a result of LC-MS analysis, this compound showed a molecular weight of 960 for the target compound. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in deuterated dimethyl sulfoxide solvent is 1.1 to 1.3 (m, 24H), 2.6 to 2.7, 2.7 to 2 .8 (m (trans isomer), m (cis isomer), 4H), 5.5, 5.6 (s (trans isomer), s (cis isomer), 4H), 6.0 to 6.9 (m , 24H), 8.4 to 8.5 (m, 8H).
The compound obtained from these results was identified as the objective compound (CR-1) (yield 95%). As a result of analysis by liquid chromatography, the production ratio of the cis form to the trans form was 29:71 (cis form: trans form).

Synthesis example 2
Synthesis of CR-2 Synthesis was performed in the same manner as in Synthesis Example 1 except that 4-isopropylbenzaldehyde was replaced with 4-cyclohexylbenzaldehyde (46.0 g, 0.2 mol) to obtain 50 g of a compound. As a result of analysis by LC-MS, this compound showed the molecular weight 1121 of the target compound. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in deuterated dimethyl sulfoxide solvent is 1.2 to 1.4 (m, 20H), 1.7 to 1.9 (m, 20H), 2.2 to 2.4 (m, 4H) 5.5, 5.6 (s (trans isomer), s (cis isomer), 4H), 6.0 to 6.8 (m, 24H), 8. 4 to 8.5 (m, 8H).
The compound obtained from these results was identified as the objective compound (CR-1) (yield 91%). As a result of analysis by liquid chromatography, the production ratio of cis form to trans form was 49:51 (cis form: trans form).

Preparative Example 1
Preparation of CR-1c CR-1 (1.5 g) was prepared by preparative HLC using ethyl acetate as a developing solvent. As a result, 0.11 g of a target cis product (hereinafter referred to as CR-1c) was obtained. The chemical shift value (δ ppm, TMS standard) of ¹ H-NMR in the heavy dimethyl sulfoxide solvent of the obtained compound is 1.1 to 1.2 (m, 24H), 2.6 to 2.7 (m, 4H), 5.5 (s, 4H), 6.0 (s, 2H), 6.1 (s, 2H), 6.3 (s, 2H), 6.4 (s, 2H), 6. 6, 6.6 (d, 8H), 6.8, 6.8 (d, 8H), 8.4 (s, 4H), 8.5 (s, 4H).

Preparative Example 2
Fractionation of CR-2c A cis-isomer product (hereinafter referred to as CR-2c) as a target product in the same manner as in Fractionation Example 1 except that CR-1 was replaced with CR-2 (1.5 g). 0.18 g was obtained. The chemical shift value (δppm, TMS standard) of ¹ H-NMR of the obtained compound in deuterated dimethyl sulfoxide solvent is 1.2 to 1.4 (m, 20H), 1.7 to 1.8 (m, 20H), 2.2 to 2.3 (m, 4H) 5.5 (s, 4H), 6.0 (s, 2H), 6.1 (s, 2H), 6.3 (s, 2H) , 6.4 (s, 2H), 6.6, 6.6 (d, 8H), 6.7, 6.7 (d, 8H), 8.4 (s, 4H), 8.5 (s , 4H).

Examples 1-3 and Comparative Examples 1-2
(1) Safety solvent solubility test The amount of the compound obtained in Synthesis Examples 1 and 2 and Preparative Examples 1 and 2 dissolved in propylene glycol monomethyl ether acetate (PGMEA) was evaluated. The solubility was calculated from the maximum amount of liquid that was visually confirmed to be completely dissolved after several kinds of liquids having different addition amounts were adjusted and irradiated with ultrasonic waves for 1 hour. The solubility results are shown in Table 1.
A: 3.0 wt% ≦ dissolved amount C: dissolved amount <3.0 wt%

Examples 4 to 6 and Comparative Examples 3 to 4
(2) Patterning test After preparing the components shown in Table 2 and preparing a uniform solution, the mixture was filtered through a Teflon membrane filter having a pore diameter of 0.1 μm to prepare a radiation-sensitive composition. went. The results are shown in Table 3.

(2-1) Resolution Evaluation After spin-coating a resist on a clean silicon wafer, pre-exposure baking (PB) was performed in an oven at 110 ° C. to form a resist film having a thickness of 60 nm. The resist film was irradiated with an electron beam with a line-and-space setting of 1: 1 at 50 nm intervals using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd.). After the irradiation, each film was heated at a predetermined temperature for 90 seconds and immersed in a 2.38 wt% TMAH aqueous solution for 60 seconds for development. Thereafter, it was washed with water for 30 seconds and dried to form a negative resist pattern. The obtained line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation). The dose amount (μC / cm ² ) at that time was defined as sensitivity.

(2-2) Evaluation of Pattern Shape The obtained cross-sectional photograph of 1: 1 line and space with an interval of 50 nm was observed and evaluated with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation).
A: Rectangular pattern (good pattern)
B: Almost rectangular pattern (almost good pattern)
C: Non-rectangular pattern (unfavorable pattern)

(3) Evaluation of Line Edge Roughness (LER) Hitachi Semiconductor's SEM Terminal PC V5 Offline Length Measurement Software at (300 points in the length direction (0.75 μm) of 1: 1 line and space at 50 nm intervals (( Using Hitachi Science Systems Co., Ltd.), the distance between the edge and the reference line was measured. The standard deviation (3σ) was calculated from the measurement result.
A: LER (3σ) ≦ 3.5 nm (good LER)
B: 3.5 nm <LER (3σ) ≦ 4.0 nm (almost good LER)
C: 4.0 nm <LER (3σ) (not good LER)

Compound CR-2cm: Mixed acid generator (C) of CR-2 and CR-2c in which the ratio of cis form to trans form is 93: 7
P-1: Triphenylbenzenesulfonium trifluoromethane sulfonate (Midori Chemical Co., Ltd.)
Acid crosslinking agent (G)
C-1: Nicarak MW-100LM (Sanwa Chemical Co., Ltd.)
C-2: Nicalak MX-270 (Sanwa Chemical Co., Ltd.)
Acid diffusion controller (E)
Q-1: Trioctylamine (Tokyo Chemical Industry Co., Ltd.)
Solvent S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)
S-2: Cyclohexanone (Tokyo Chemical Industry Co., Ltd.)

The present invention relates to a radiation-sensitive compound represented by a specific chemical structural formula, a radiation-sensitive composition containing the compound, and a resist pattern using the radiation-sensitive composition, which are useful as acid-amplified non-polymer resist materials. It is suitably used for the forming method.

Claims (24)

1. A cis cyclic compound represented by the following formula (1).
   

   

   (In the formula (1), L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms. Group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ⁵ ) —C (═O) —, —N (R ⁵ ) —C (═O) O A divalent organic group selected from the group consisting of —, —S—, —SO—, —SO ₂ — and any combination thereof, and R ⁵ is hydrogen or an alkyl group having 1 to 10 carbon atoms. R ¹ is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cyano group, or a nitro group. Hydroxyl group, heterocyclic group, halogen, carboxyl group, acyl group having 2 to 20 carbon atoms, alkylsilyl having 1 to 20 carbon atoms Or a hydrogen atom, m is an integer of 0 to 4, R ′ is independently an alkyl group having 2 to 20 carbon atoms, or the following formula
   

   

   (Wherein R ⁴ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, A hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, or an alkylsilyl group having 1 to 20 carbon atoms, and p is an integer of 0 to 5)
   Is an aryl group represented by: )
2. The cis cyclic compound of Claim 1 shown by following formula (2).
   

   

   (In the formula (2), R ¹ , R ⁴ , p and m are the same as described above. X ₂ is a hydrogen or halogen atom, m ₅ is an integer of 0 to 3, and m + m ₅ = 4. .)
3. The cis cyclic compound according to claim 2, which is represented by the following formula (3-1) or (3-2).
   

   

   (In the formulas (3-1) and (3-2), R ¹ , R ⁴ , X ₂ , and p are the same as described above. M ₃ is 1 or 2, and m ₄ is 1. )
4. The cis cyclic compound of Claim 2 shown by following formula (4).
   

   

   (In the formula (4), R ⁴ , X ₂ , m, m ₅ and p are the same as above.)
5. The cis-cyclic compound according to claim 4, which is represented by the following formula (5-1a) or (5-1b).
   

   

   (In formulas (5-1a) and (5-1b), X ₂ , R ⁴ , m ₃ , m ₄ , and p are the same as described above.)
6. The cis cyclic compound according to claim 5, which is represented by any one of the following formulas (6-1) to (6-4):
   

   
7. A radiation-sensitive composition comprising a cyclic compound comprising the cis-cyclic compound according to any one of claims 1 to 6 and a trans isomer thereof in a ratio of 80 to 100: 0 to 20 and a solvent.
8. The radiation-sensitive composition according to claim 7, comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent.
9. The radiation-sensitive composition according to claim 7 or 8, wherein the cyclic compound is 50 to 99.999% by weight of the total weight of the solid component.
10. The cyclic compound is at least one aldehyde compound (A1) having 2 to 59 carbon atoms having 1 to 4 formyl groups and at least one having 6 to 15 carbon atoms having 1 to 3 phenolic hydroxyl groups. The radiation-sensitive composition according to any one of claims 7 to 9, which is synthesized by a condensation reaction with a phenol compound (A2) and has a molecular weight of 700 to 5,000.
11. The radiation-sensitive composition according to claim 10, wherein the aldehyde compound (A1) is a benzaldehyde compound having 7 to 24 carbon atoms.
12. Acid that generates acid directly or indirectly by irradiation with radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam, or heat The radiation-sensitive composition according to any one of claims 7 to 11, further comprising a generator (C).
13. The radiation-sensitive composition according to any one of claims 7 to 12, further comprising an acid crosslinking agent (G).
14. The radiation-sensitive composition according to any one of claims 7 to 13, further comprising an acid diffusion controller (E).
15. The radiation-sensitive composition according to any one of claims 7 to 14, wherein the cis-cyclic compound is represented by the following formula (4).
    

    

    (In the formula (4), R ⁴ , X ₂ , m, m ₅ and p are the same as above.)
16. The radiation-sensitive composition according to claim 15, wherein the cis-cyclic compound is represented by the following formula (5-1a) or (5-1b).
    

    

    (In the formulas (5-1a) and (5-1b), X ₂ , R ⁴ , m ₃ , m ₄ , and p are the same as described above.),
17. The radiation-sensitive composition according to claim 16, wherein the cis-cyclic compound is represented by the following formula (5-2).
    

    

    (In formula (5-2), R ⁴ and p are as defined above.)
18. The radiation-sensitive composition according to claim 17, wherein the cis-cyclic compound is represented by any one of the following formulas (6-1) to (6-4).
    

    
19. The cyclic compound is obtained by a condensation reaction of two or more benzaldehyde compounds having 7 to 24 carbon atoms and two or more phenol compounds (A2) having 6 to 15 carbon atoms having 1 to 3 phenolic hydroxyl groups. The radiation sensitive composition of Claim 7.
20. The solid component is a cyclic compound / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F) in an amount of 50 to 99.4% by weight based on the solid component. The radiation-sensitive composition according to claim 8, comprising /0.001-49/0.5-49/0.001-49/0-49.
21. The radiation-sensitive composition according to any one of claims 7 to 20, wherein an amorphous film can be formed by spin coating.
22. The radiation-sensitive composition according to claim 21, wherein the dissolution rate of the amorphous film in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C is 10 Å / sec or more.
23. Dissolution rate of the amorphous film after irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or the amorphous film after heating at 20 to 250 ° C. in a 2.38 wt% tetramethylammonium hydroxide aqueous solution The radiation-sensitive composition according to claim 21, wherein is 5 Å / sec or less.
24. A step of applying a radiation-sensitive composition according to any one of claims 7 to 23 on a substrate to form a resist film, a step of exposing the resist film, and a step of developing the exposed resist film A resist pattern forming method.