JPH10121029A - Light absorber and chemically amplified positive resist material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chemically amplified positive resist material having no sublimability, very intense light absorption in the far-ultraviolet region and high resolution favorable for miniature processing by using a carboxylic acid derivative having a tricycle aromatic skeleton as the light absorber. SOLUTION: This absorber is represented by formula I or II [wherein R<1> to R<3> are each H, are alkyl, an alkoxyl, an alkenyl or an aryl; R<4> is an (oxygenous) aliphatic, alicyclic or aromatic hydrocarbon group or oxygen; h and R<5> is an acid/unstable group such as a group represented by formula III (wherein R<6> to R<8> are each H, an alkyl, an alkoxyl, an alkoxyalkyl or the like; and R<9> is an alkyl, an aryl or the like); p is 0 or 1; k, h and m are each 0-9; n is 1-10; and k+h+m+n<=10]. A chemically amplified positive resist material is sensitive to an actinic radiation and such high resolution as to be favorable for elaborate processing techniques. The mixing ratio is such that 150-700 pts.wt. organic solvent, 70-90 pts.wt. base resin, 0.5-15 pts.wt. acid generator and 0.01-10 pts.wt. light absorber are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for fine processing technology which has high sensitivity to high energy rays such as far ultraviolet rays, electron beams and X-rays and can form a pattern by developing with an alkaline aqueous solution. The present invention relates to a light absorber suitable as a component of a chemically amplified positive resist material and a chemically amplified positive resist material containing the same.

[0002]

2. Description of the Related Art LSI
With the demand for finer pattern rules in line with the higher integration and higher speed of light sources, light exposure, which is currently used as a general-purpose technology, is approaching the intrinsic resolution limit due to the wavelength of the light source. is there. In light exposure using a g-line (436 nm) or an i-line (365 nm) as a light source, a pattern rule of about 0.5 μm is limited, and the integration degree of an LSI manufactured using this is 16 Mbit DR.
AM equivalent. However, LSI prototypes have already been made at this stage, and there is an urgent need to develop further miniaturization techniques.

[0003] Against this background, far-ultraviolet lithography is expected as a next-generation microfabrication technology. The deep ultraviolet lithography can also process 0.3 to 0.4 μm, and when a resist material having low light absorption is used, a pattern having side walls nearly perpendicular to the substrate can be formed. 2. Description of the Related Art In recent years, a technique using a high-brightness KrF excimer laser as a light source of far ultraviolet light has attracted attention.

A recently developed acid-catalyzed chemically amplified positive resist material (Japanese Patent Publication No. 2-27660,
JP-A-3-27829) is a resist material that has high sensitivity, high resolution, and high dry etching resistance, and has excellent characteristics and is particularly promising for deep ultraviolet lithography.

By the way, when a chemically amplified positive resist material is used on a so-called high-reflection substrate (a substrate having a high light reflectance such as an aluminum substrate, a silicon substrate, or a chromium substrate for a photomask), there is a certain phenomenon. There are surf and halation. Here, the standing wave means that the light exposed to the positive resist film at the time of exposure on a flat high-reflection substrate is reflected on the substrate, and is further reflected on the surface of the resist film. Means that a standing wave (standing wave) is generated by light interference, and as a result, the side wall is wavy. On the other hand, halation refers to a phenomenon in which reflected light is obliquely reflected on a substrate having irregularities, such as a real device, and is exposed in a region that should not be exposed, resulting in a reduction in resolution and a reduction in pattern size. .

Generally, the means for solving these problems include:
A method of applying an antireflection film on a substrate or a resist film is used, but increasing the number of steps for this application is not preferable as a mass production technique.

As another means for suppressing the occurrence of standing waves and halation, there is a method using a resist material having a low transmittance. This is a technique for suppressing light interference by making the resist film itself high in absorbance instead of using an antireflection film. As an example, a resist composition to which a light-absorbing material such as oil yellow is added to reduce the light transmittance of a resist film (Japanese Patent Publication No. 51-37)
562).

However, when such a compound is used as a light-absorbing material, the compound volatilizes from the resist film due to pre-baking, and not only does the effect of preventing halation and standing waves become insufficient, but also Has the disadvantage of causing pinholes and impairing the adhesion between the resist film and the substrate.As a result, various characteristics such as sensitivity, pattern shape and resolution are impaired, and the overall performance as a resist material Was insufficient.

Further, a resist composition comprising a compound in which an electron-withdrawing group such as a cyano group, an ester group or a carboxyl group is bonded to the carbon at the β-position of the styrene-based compound (Japanese Patent Publication No.
69095 and JP-A-2-269346), but in this case, sensitivity, sublimability,
Although improvements in storage stability and the like were observed, characteristics such as resolution and depth of focus were not sufficient.

Therefore, none of the above methods can effectively prevent the occurrence of standing waves or halation.
Development of more effective technology is desired.

The present invention has been made in view of the above circumstances,
High resolution suitable for microfabrication technology, especially when used on highly reflective substrates, no standing wave or halation, high sensitivity to high energy rays, developed with alkaline aqueous solution It is an object of the present invention to provide a light-absorbing agent that provides a chemically amplified positive resist material capable of forming a pattern by performing the method, and a chemically amplified positive resist material containing the light absorbing agent.

[0012]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a tricyclic aromatic compound represented by the following general formula (1) or (2): Carboxylic acid derivatives having an aromatic skeleton have excellent properties as a light absorber, which is suitable as a component of a chemically amplified positive resist material having high resolution suitable for microfabrication technology, especially in deep ultraviolet lithography. I found that it can be very effective.

[0013]

Embedded image (Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, R ⁴ is a linear or branched alkenyl group or an aryl group, R ⁴ is a substituted or unsubstituted aliphatic hydrocarbon group which may contain an oxygen atom, a substituted or unsubstituted group which may contain an oxygen atom. An alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group which may contain an oxygen atom or an oxygen atom, R ⁵ is an acid labile group, and p is 0 or 1. k , H, and m are each an integer of 0 to 9, n is an integer of 1 to 10, and k + h + m + n
Satisfies ≦ 10. )

That is, when one or more of the compounds represented by the above formula (1) or (2) is used as the light absorber of the chemically amplified positive resist material, the light absorber is It has the following advantages (i) to (iii). (I) No sublimability. Therefore, there are no drawbacks such as an insufficient effect of preventing halation and standing waves, generation of pinholes, and loss of adhesion between the resist film and the substrate. (Ii) High energy rays such as deep ultraviolet rays, electron beams, and X-rays, particularly the wavelength of a KrF excimer laser beam, 24
It has an extremely large absorption around 8 nm. Therefore, when used for exposure with these high energy rays, a sufficient effect can be obtained with a small amount of addition as compared with a conventional light absorber. Supplementary to this, unexpectedly adverse effects may occur when a large amount of additives are added to the resist material. In fact, conventional light absorbers do not achieve the desired effect unless they are added in the same amount or more than the acid generators and dissolution inhibitors,
Film loss in unexposed areas, undissolved areas in exposed areas, or deterioration of pattern profiles such as rounding of the head and tailing, as well as deterioration of storage stability, etc. In many cases, it was inconsistent that deterioration occurred. On the other hand, if a sufficient effect can be obtained even with a small amount of addition, only a desired performance can be added by adding a small amount to a resist system having a certain degree of performance. In this sense, a small amount of the additive is a very important condition. (Iii) Since it is decomposed in the presence of an acid to release a carboxylic acid, the rate of dissolution in an aqueous alkali solution is greater than that of, for example, a phenol derivative. For this reason, no scum or bridges are generated, and the ratio of the alkali dissolution rate before and after exposure (dissolution contrast) is large, so that the resolution can be improved.

Therefore, a chemically amplified positive resist material containing a light absorber comprising one or more of the compounds represented by the above formulas (1) or (2) can be used for deep ultraviolet rays, electron beams and X rays.
When used in lithography (especially KrF excimer laser light) using high-energy rays such as rays, the pattern profile and the resolution do not deteriorate. Therefore, the light absorber of the above formula (1) or (2) of the present invention can exhibit excellent performance when used in a chemically amplified positive resist material, and has a high resolution and a wide depth of focus. The resist image can be obtained.

Accordingly, the present invention provides: [1] a light absorber comprising a carboxylic acid derivative having a tricyclic aromatic skeleton represented by the above general formula (1) or (2), [2] A light absorber according to the above [1], wherein the acid labile group R ^{5 in the} above formulas (1) and (2) has a structure of any of the following formulas (3a), (3b) or (3c); A) an organic solvent; (B) an alkali-insoluble or poorly soluble resin having an acidic functional group protected by an acid labile group, which is alkali-soluble when the acid labile group is dissociated. (D) a chemically amplified positive resist material comprising the light absorbing agent of [1] or [2]; [4] the chemically amplified positive resist material of [3]; (B) As a resin of the component, hydrogen atoms of some hydroxyl groups were substituted with acid labile groups. Weight average molecular weight 3,000-
A chemically amplified positive resist material using 300,000 polyhydroxystyrene; [5] a chemically amplified positive resist material according to the above [3] or [4] containing a dissolution controlling agent as the component (E); [6] (F) a chemically amplified positive resist material according to the above [3], [4] or [5] containing a basic compound as a component; [7] a group represented by ΔC-COOH in the molecule as the (G) component The above [3] containing an aromatic compound having
[4], the chemically amplified positive resist material of [5] or [6], [8] the above [3], [4], which contains a light absorbing agent other than the component (D) as the component (H). [5] A chemically amplified positive resist material according to [6] or [7].

[0017]

Embedded image (Wherein, R ^{6 to} R ⁸ are each independently a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl or aryl group, which may contain a carbonyl group in the chain, all of R ⁶ to R ⁸ must not be hydrogen atoms. in addition, the R ⁶ R ⁷ may combine with each other to form a ring, R ⁹ may be a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl group, or Aryl groups, and these groups may contain a carbonyl group in the chain, and R ⁹ may combine with R ⁶ to form a ring.)

Hereinafter, the present invention will be described in more detail. The carboxylic acid derivative having a tricyclic aromatic skeleton constituting the light absorber according to the present invention is represented by the following general formula (1):
This is shown in (2).

[0019]

Embedded image (Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, R ⁴ is a linear or branched alkenyl group or an aryl group, R ⁴ is a substituted or unsubstituted aliphatic hydrocarbon group which may contain an oxygen atom, a substituted or unsubstituted group which may contain an oxygen atom. An alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group which may contain an oxygen atom or an oxygen atom, R ⁵ is an acid labile group, and p is 0 or 1. k , H, and m are each an integer of 0 to 9, n is an integer of 1 to 10, and k + h + m + n
Satisfies ≦ 10. )

In the above formulas (1) and (2), R ^{1 to} R ³
Each independently represents a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl group, or an aryl group It is. Examples of the linear or branched alkyl group include a methyl group,
1 carbon atom such as ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hexyl group, cyclohexyl group and adamantyl group
Those of 10 to 10 are preferable, and among them, a methyl group, an ethyl group, an isopropyl group and a tert-butyl group are more preferably used. Examples of the linear or branched alkoxy group include carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hexyloxy, cyclohexyloxy and the like. Those having the formulas 1 to 8 are preferable, and among them, methoxy group, ethoxy group, isopropoxy group, te
An rt-butoxy group is more preferably used. As the straight-chain or branched alkoxyalkyl group, for example, those having 2 to 10 carbon atoms such as methoxymethyl group, ethoxypropyl group, propoxyethyl group, tert-butoxyethyl group are preferable, among which methoxymethyl group, A methoxyethyl group, an ethoxypropyl group, a propoxyethyl group and the like are preferred. As the linear or branched alkenyl group, those having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group and a butenyl group are preferred. As the aryl group, those having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, and a cumenyl group are preferable.

R ⁴ is a substituted or unsubstituted divalent aliphatic hydrocarbon group which may contain an oxygen atom, or a substituted or unsubstituted divalent alicyclic hydrocarbon group which may contain an oxygen atom. A substituted or unsubstituted divalent aromatic hydrocarbon group or an oxygen atom which may contain an oxygen atom. In the formula, p is 0 or 1, and when p is 0, -R ⁴
The bond is a single bond; Examples of the substituted or unsubstituted aliphatic hydrocarbon group which may contain an oxygen atom include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec-butylene group, and-
CH ₂ O—, —CH ₂ CH ₂ O—, and —CH ₂ OCH ₂ —
Preferred are those having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a —CH ₂ O— group, a —CH ₂ CH
_{The 2} O- group is more preferably used.

The substituted or unsubstituted alicyclic hydrocarbon group which may contain an oxygen atom includes 1,4-cyclohexylene, 2-oxacyclohexane-1,4-ylene, 2-thiacyclohexane- Those having 5 to 10 carbon atoms such as a 1,4-ylene group are exemplified.

Examples of the substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom include o-phenylene group, p-phenylene group, 1,2-xylene-3,6
An arylene alkylene group having 6 to 14 carbon atoms such as an -ylene group, a toluene-2,5-ylene group, or a 1-cumene-2,5-ylene group, or an allylalkylene group having 6 to 14 carbon atoms (the allylalkylene group referred to herein); -CH ₂ Ph- group is the group, -CH ₂ P
hCH ₂ — group, —OCH ₂ Ph— group, —OCH ₂ PhCH ₂
O-group and the like. Here, Ph is a phenylene group. ).

R ⁵ is an acid labile group. In this case, the acid labile group means a group obtained by substituting a carboxyl group with one or more functional groups capable of decomposing in the presence of an acid. Is not particularly limited as long as it decomposes in the presence of the compound to release a functional group exhibiting alkali solubility, and particularly preferred are groups represented by the following general formulas (3a), (3b) and (3c). .

[0025]

Embedded image (Wherein, R ^{6 to} R ⁸ are each independently a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl or aryl group, which may contain a carbonyl group in the chain, all of R ⁶ to R ⁸ must not be hydrogen atoms. in addition, the R ⁶ R ⁷ may combine with each other to form a ring, R ⁹ may be a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl group, or Aryl groups, and these groups may contain a carbonyl group in the chain, and R ⁹ may combine with R ⁶ to form a ring.)

In this case, the above-mentioned linear or branched alkyl group, linear or branched alkoxy group, linear or branched alkoxyalkyl group, linear or branched alkenyl group, aryl group Examples thereof include the same as those described above for R ^{1 to} R ³ .

In the formula (3a), the ring formed by bonding R ⁶ and R ⁷ to each other includes, for example, cyclohexylidene, cyclopentylidene, 3-oxocyclohexylidene, 3-oxo- 4 carbon atoms such as a 4-oxacyclohexylidene group and a 4-methylcyclohexylidene group
To 10 are mentioned.

In the formula (3b), the ring formed by bonding R ⁶ and R ⁷ to each other includes, for example, a 1-silacyclohexylidene group, a 1-silacyclopentylidene group,
Examples thereof include those having 3 to 9 carbon atoms such as -oxo-1-silacyclopentylidene group and 4-methyl-1-silacyclopentylidene group.

Further, in the formula (3c), the ring formed by bonding R ⁹ and R ⁶ to each other includes, for example, 2-oxacyclohexylidene group, 2-oxacyclopentylidene group, 2-oxa-4- Those having 4 to 10 carbon atoms such as a methylcyclohexylidene group are exemplified.

Examples of the group represented by the general formula (3a) include a tert-butyl group, a tert-amyl group,
In addition to tertiary alkyl groups having 4 to 10 carbon atoms such as 1,1-dimethylethyl group, 1,1-dimethylbutyl group, 1-ethyl-1-methylpropyl group, and 1,1-diethylpropyl group, 1 , 1-dimethyl-3-oxobutyl group, 3-
Oxocyclohexyl group, 1-methyl-3-oxo-4
A 3-oxoalkyl group such as -oxacyclohexyl group is preferred.

The group represented by the general formula (3b) includes
For example, a trimethylsilyl group, an ethyldimethylsilyl group,
Dimethylpropylsilyl group, diethylmethylsilyl group,
A trialkylsilyl group having 3 to 10 carbon atoms such as a triethylsilyl group is preferred.

The group represented by the general formula (3c) includes
For example, a 1-methoxymethyl group, a 1-methoxyethyl group,
1-ethoxyethyl group, 1-ethoxypropyl group, 1-
Ethoxyisobutyl group, 1-n-propoxyethyl group,
1-tert-butoxyethyl group, 1-n-butoxyethyl group, 1-i-butoxyethyl group, 1-tert-pentoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2′-n-butoxyethoxy) ) Ethyl group, 1
-(2'-ethylhexyl) oxyethyl group, 1-
(4′-acetoxymethylcyclohexylmethyloxy) ethyl group, 1- {4 ′-(tert-butoxycarbonyloxymethyl) cyclohexylmethyloxy} ethyl group, 2-methoxy-2-propyl group, 1-ethoxypropyl group, dimethoxy Those having 2 to 8 carbon atoms such as a methyl group, a diethoxymethyl group, a tetrahydrofuranyl group and a tetrahydropyranyl group are preferred.

In the above equations (1) and (2),
k, h, and m are each an integer of 0 to 9, and k + h + m + n
Satisfies ≦ 10.

Preferred specific examples of the compounds of the above formulas (1) and (2) include compounds represented by the following (4a) to (4j).

[0035]

Embedded image (In the formula, R ⁵ is an acid labile group.)

The compounds of the formulas (1) and (2) of the present invention can be easily and inexpensively prepared from carboxylic acid derivatives having a tricyclic aromatic skeleton represented by the following formulas (5) and (6) according to a conventional method. Can be synthesized.

[0037]

Embedded image (In the formula, R ^{1 to} R ⁴ , p, k, h, m, and n are the same as described above.)

In this case, there are various methods for synthesizing a compound having a group represented by the above general formula (3a) as an acid labile group, and the method is not particularly limited. There is a method of reacting carboxylic acid represented by 5) or 6) with trifluoroacetic anhydride and then reacting an alcohol represented by the following formula (7). This method is described in Org. Chem. , 30,92
7 (1965).

[0039]

Embedded image

In the above reaction, the amount of the trifluoroacetic anhydride and the alcohol used is 1 to 10 mol, preferably 1 to 10 mol, respectively, per 1 mol of the carboxyl group in the carboxylic acid represented by the formulas (5) and (6). It is preferable to add at a ratio of 5 mol. This reaction is preferably performed in an organic solvent such as methylene chloride and THF at a temperature in the range of -70 to 50C. The reaction time can be appropriately selected depending on the conditions,
It takes about 30 minutes to 4 hours.

Further, as the acid labile group, the above-mentioned general formula (3)
The method for synthesizing the compound having the group represented by b) includes various methods and is not particularly limited. Preferred examples include a method in which a carboxylic acid represented by the formula (5) or (6) is added to a carboxylic acid under a base catalyst. There is a method of reacting a silylalkyl halide represented by the following formula (8).

[0042]

Embedded image (In the formula, Z is a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, and R ^{6 to} R ⁸ are the same as described above.)

In the above reaction, the amount of the silylalkyl halide represented by the above formula (8) is 1 to 10 mol per 1 mol of the carboxyl group in the carboxylic acid represented by the above formula (5) or (6). In particular, it is desirable to add 1 to 5 mol.

The base used as the catalyst is not particularly limited, but specific examples include sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydride, potassium hydride, sodium methylate, Sodium ethylate, potassium tert
Alkali metal salts such as butyrate, triethylamine, diisopropylmethylamine, dimethylaniline,
Pyridine, 4-N, N-dimethylaminopyridine, 4-
Organic bases such as (1-piperidino) pyridine are exemplified. The amount of the base to be used is preferably 1 to 10 molar equivalents relative to the halogenated ester represented by the formula (8).

The reaction solvent used is not particularly limited, but specific examples thereof include ethers such as tetrahydrofuran, tetrahydropyran and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, benzene, Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and chloroform, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide, or the like. Among them, methylene chloride, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like are preferable.

The reaction temperature in this case is preferably from 0 to 100 ° C., particularly preferably from 20 to 70 ° C. Further, the reaction time can be appropriately selected, but is about 30 minutes to 4 hours.

There are various methods for synthesizing a compound having a group represented by the above general formula (3c) as an acid labile group, and the method is not particularly limited. Preferred examples include those represented by formulas (5) and (5c). There is a method of reacting a carboxylic acid represented by the formula (6) with a vinyl ether represented by the following formula (9) under an acid catalyst.

[0048]

Embedded image (In the formula, R ⁶ and R ⁹ are the same as described above, and R ¹⁰ is a divalent group obtained by removing one hydrogen atom from R ⁷ .
R ⁶ and R ⁹ may be bonded to each other to form a ring. )

In this case, the vinyl ethers of the above formula (9) are not particularly limited, but specific examples include methyl vinyl ether, ethyl vinyl ether and n.
-Propyl vinyl ether, tert-butyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, n-pentyl vinyl ether, cyclohexyl vinyl ether, 4-oxa-2-hexene, 3,4
-Dihydro-2H-pyran, 2,3-dihydrofuran and the like. The amount of the vinyl ether of the above formula (9) to be used is preferably 1 to 10 mol, particularly preferably 1 to 5 mol, per 1 mol of the carboxyl group in the carboxylic acid of the above formulas (5) and (6).

The acid catalyst used is not particularly limited, but specific examples include trifluoromethanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, pyridinium p-toluenesulfonate, pyridinium m-nitrobenzenesulfonate, And pyridinium sulfonate. The amount of the acid catalyst to be used is 0.1 to 1 mol of the carboxyl group in the carboxylic acid represented by the formulas (5) and (6).
It is preferred to add 001 to 1 mol.

The reaction solvent used is not particularly limited, but specific examples include ethers such as tetrahydrofuran, tetrahydropyran and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, benzene, Examples thereof include aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and chloroform, and mixtures thereof, among which tetrahydrofuran, tetrahydropyran, or methylene chloride and chloroform, among others. And the like, and mixtures of halogenated hydrocarbons.

The reaction can be carried out at a temperature ranging from 0 ° C. to the boiling point of the solvent. The reaction time can be appropriately selected depending on conditions, but the reaction is completed in about 30 minutes to 24 hours.

After completion of the reaction, the target compound can be obtained by neutralizing the acid of the catalyst with an alkali, washing and concentrating the solvent layer with water, and then performing recrystallization or column fractionation.

Further, an acid labile group represented by the above general formula (3)
As a second preferred example of a method for synthesizing a compound having a group represented by c), a haloalkoxyalkyl represented by the following formula (10) is added to a carboxylic acid represented by the formula (5) or (6) under a base catalyst. There is a method to make it react.

[0055]

Embedded image (In the formula, R ⁶ , R ⁷ , R ⁹ , and Z are the same as described above.)

In this case, the haloalkoxyalkyl of the above formula (10) is not particularly limited, but specific examples include methoxymethyl chloride, methoxymethyl bromide, methoxymethyl iodide, ethoxyethyl chloride, ethoxymethyl chloride. Ethoxymethyl bromide, methoxyethoxymethyl chloride, tetrahydrofuranyl chloride, tetrahydropyranyl chloride and the like. The amount of the haloalkoxyalkyl represented by the formula (10) is determined by the amount of the starting material represented by the formula (5),
1 to 1 for the carboxyl group of the carboxylic acid derivative of (6).
It is preferable to use 10 molar equivalents.

The base used as the catalyst is not particularly limited, but specific examples include sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydride, potassium hydride, sodium methylate, Sodium ethylate, potassium tert
Alkali metal salts such as -butyrate, or organic bases such as triethylamine, diisopropylmethylamine, dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 4- (1-piperidino) pyridine, and various correlation shifts Catalysts are also included. The amount of the base to be used is preferably in the range of 1 to 10 molar equivalents relative to the carboxyl group in the carboxylic acid represented by the formulas (5) and (6).

The reaction solvent used is not particularly limited, but specific examples include methanol, ethanol,
Propanol, 2-methylethanol, butanol, t
alcohols such as tert-butyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as methylene chloride and chloroform; Dimethylformamide,
Examples include aprotic polar solvents such as N, N-dimethylacetamide and dimethylsulfoxide, and mixed solvents thereof. Among them, acetone, N,
N-dimethylformamide, N, N-dimethylacetamide and the like are preferred. In the phase transfer reaction, a two-layer system of such an organic solvent and water may, for example, be mentioned.

The reaction can be carried out at a temperature ranging from 0 ° C. to the boiling point of the solvent. The reaction time can be appropriately selected depending on conditions, but the reaction is completed in about 30 minutes to 24 hours. After completion of the reaction, the reaction is stopped with water, the solvent layer is washed and concentrated, and then recrystallized or subjected to column fractionation to obtain the desired compound.

The light absorbing agent of the present invention comprises a carboxylic acid derivative having a tricyclic aromatic skeleton represented by the above formula (1) or (2). These may be used alone or in combination of two or more.

Further, in the present invention, the above formula (1) or (2)
A chemically amplified positive resist material containing a light absorber comprising a carboxylic acid derivative of the formula (1). The specific embodiment is as follows. [1] (A) Organic solvent (B) Alkali-insoluble or hardly soluble resin having an acidic functional group protected by an acid labile group, which becomes alkali-soluble when the acid labile group is dissociated. (C) Acid generator (D) A chemically amplified positive resist material containing a light absorber comprising a carboxylic acid derivative having a tricyclic aromatic skeleton represented by the above formula (1) or (2). [2] In the chemically amplified positive resist composition of the above [1], the resin as the component (B) has a weight average molecular weight of 3,000 or more in which some of the hydrogen atoms of the hydroxyl groups are substituted with acid labile groups.
A chemically amplified positive resist material using 300,000 polyhydroxystyrene. [3] The chemically amplified positive resist material according to [1] or [2], which comprises a dissolution controlling agent as the component (E). [4] The chemically amplified positive resist material according to the above [1], [2] or [3], which contains a basic compound as the component (F). [5] The above-mentioned [1], which contains, as a component (G), an aromatic compound having a group represented by ≡C-COOH in the molecule.
[2] The chemically amplified positive resist material according to [3] or [4]. (6) The chemically amplified positive resist material according to the above [1], [2], [3], [4] or [5], containing a light absorbing agent other than the component (D) as the component (H).

Here, as the organic solvent of the component (A),
For example, ketones such as cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, Alcohols such as ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol tert-butyl ether methyl ether (1 -Tert-butoxy-2-methoxyethane), ethylene glycol-tert-butyl ether ethyl ether (1-ter -Butoxy-2-ethoxyethane), propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl-3-methoxypropionate, ethyl-3-ethoxy Propionate, acetic acid ter
Esters such as t-butyl, tert-butyl propionate and methyl β-methoxyisobutyrate can be mentioned, and one of these can be used alone or two or more can be used in combination. Among them, 1-ethoxy-2-propanol, which has excellent solubility of resist components, or propylene glycol monomethyl ether acetate (regardless of α-type and β-type), which has excellent safety and solubility of resist components, is preferable. used.

The compounding amount of the organic solvent as the component (A) is preferably in a range where the resist film thickness can be adjusted to 0.4 to 2 μm, and specifically, 70 to 90 parts, particularly 75 to 85 parts of the component (B). 150 to 700 parts, especially 250 to 500 parts, is preferable. If the amount is less than 150 parts, the resist film thickness may be too thick to deteriorate the film formability, and if it exceeds 700 parts, the resist film thickness may be too thin. .

The resin which is an alkali-insoluble or hardly soluble resin having an acidic functional group protected by the acid labile group of the component (B) and becomes alkali-soluble when the acid labile group is dissociated is a base resin. The resin may be, for example, the following resins (I) and (II). (I) hydroxystyrene, hydroxy-α-methylstyrene, vinylbenzoic acid, carboxymethylstyrene,
Obtained by polymerizing or copolymerizing at least one monomer having an acidic functional group such as carboxymethoxystyrene, (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, and cinnamic acid. Obtained by protecting the acidic functional group of the resin produced by the addition polymerization with an acid labile group. (II) A resin produced by condensation polymerization typified by a novolak resin in which an acidic functional group is protected by an acid labile group.

In the case of the above (I), the resin may be composed only of a repeating unit in which a polymerizable multiple bond present in the monomer having an acidic functional group is cleaved, but if necessary, other resin may be used. A repeating unit may be further contained.

Examples of the monomer giving such another repeating unit include styrene, α-methylstyrene, methoxystyrene, t-butoxystyrene, acetoxystyrene, vinyltoluene, maleic anhydride, (meth) acrylonitrile, croton Nitrile, maleinile nitrile, fumalonitrile, mesacon nitrile, citraconitrile, itaconitrile, (meth) acrylamide,
Examples thereof include crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide, vinylaniline, vinylpyridine, vinyl-ε-caprolactam, vinylpyrrolidone, and vinylimidazole.

In the case of (II), the above resin may be composed of, for example, only a novolak resin unit.
If necessary, a unit formed by another condensation polymerization may be further contained. Such resins can be produced by polycondensation or copolycondensation of one or more phenols and one or more aldehydes, optionally with other polycondensation components, under an acidic catalyst.

Examples of the phenols include o-cresol, m-cresol, p-cresol, 2,3-
Xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-
Trimethylphenol and the like can be mentioned, and aldehydes include formaldehyde, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde and the like.

Among the above resins (I) and (II), those produced by addition polymerization of (I) are particularly preferred, and polyhydroxystyrene and its derivatives are particularly preferred.

In this case, polyhydroxystyrene and derivatives thereof are preferably those in which the hydrogen atom of the phenolic hydroxyl group, which is an acidic functional group, is partially substituted with one or more groups which are unstable to acids. Copolymers of polyhydroxystyrene can also be used. In the former case, examples of the acid-labile substituent include a tert-butyl group, te
tert-butoxycarbonyl group, substituents of tert-butyl derivatives such as tert-butoxycarbonylmethyl group,
1-ethoxyethyl group, 1-n-propoxyethyl group,
1-iso-propoxyethyl group, 1-n-butoxyethyl group, 1-i-butoxyethyl group, 1-sec-butoxyethyl group, 1-tert-butoxyethyl group, 1-
linear or branched acetal group such as tert-pentoxyethyl group, 1-ethoxy-n-propyl group, 1-cyclohexylethyl group, tetrahydrofuranyl group, tetrahydropyranyl group, 2-methoxy-tetrahydropyranyl group, etc. Are preferred. In addition, not only one kind but also two or more kinds may be used on the same polymer chain. For example, when two kinds of substituents are used on the same polymer chain, a combination of tert
-Butoxycarbonyl group and 1-ethoxyethyl group, te
rt-butoxycarbonyl group and 1-n-butoxyethyl group, tert-butoxycarbonyl group and 1-ethoxy-
An n-propyl group is preferred.

The latter polyhydroxystyrene copolymer includes a copolymer of hydroxystyrene and styrene, a copolymer of hydroxystyrene and tert-butyl acrylate, and a copolymer of hydroxystyrene and methacrylic acid.
Examples include a copolymer of tert-butyl, a copolymer of hydroxystyrene and maleic anhydride, and a copolymer of hydroxystyrene and ditert-butyl maleate.

The weight average molecular weight of the above polyhydroxystyrene or a derivative thereof is preferably 3,000 to 300,000.
Resolution may be inferior, and when it exceeds 300,000, resolution may be inferior.

Further, in the above base resin, when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer is present, and when a large amount of low molecular weight polymer is present, heat resistance may be reduced. When a large amount of a high molecular weight polymer is present, some of the high molecular weight polymers are difficult to dissolve in alkali, and may cause tailing after pattern formation.
Therefore, as the pattern rule becomes finer, the influence of such molecular weight and molecular weight distribution tends to increase. Therefore, in order to obtain a resist material suitably used for fine pattern dimensions, the molecular weight distribution of the base resin must be as follows. 0-1.
5, preferably a narrow dispersion of 1.0 to 1.3.

The blending amount of the base resin as the component (B) is 70
Preferred is from 90 to 90 parts, especially from 75 to 85 parts.

As the acid generator (C), known acid generators can be used, and for example, those represented by the following general formula (11) are preferred.

(R) _r MA (11) (wherein, R is the same or different aromatic hydrocarbon group or alkyl group. M is sulfonium or iodonium, A is p-toluenesulfonate, trifluoromethane A sulfonate, a nonafluorobutanesulfonate, a butanesulfonate or a straight chain having 1 to 20 carbon atoms,
A branched or cyclic alkyl sulfonate,
Is 2 or 3. )

In the above formula (11), the aromatic hydrocarbon group for R may be substituted or unsubstituted, for example, phenyl, tert-butoxyphenyl, tert
-Butylphenyl group, tert-butoxycarbonyloxyphenyl group, tert-butoxycarbonylmethoxyphenyl group, tert-butyldimethylsilyloxyphenyl group, tetrahydrofuranyloxyphenyl group,
Examples include a 1-ethoxyethoxyphenyl group, a 1-propoxyethoxyphenyl group, a 1-tert-butoxyethoxyphenyl group, and the like, and the alkyl group may be any linear, branched, or cyclic alkyl group. Examples include a methyl group, an ethyl group, a cyclohexyl group, and a 2-oxocyclohexyl group.

M is sulfonium or iodonium; A is p-toluenesulfonate, trifluoromethanesulfonate, nonafluorobutanesulfonate, butanesulfonate or a straight chain having 1 to 20 carbon atoms;
It is a branched or cyclic alkyl sulfonate.

Examples of the above-mentioned acid generator include diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, and p-toluenesulfonic acid (p-toluenesulfonic acid).
tert-butoxyphenyl) phenyliodonium,
Triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxy) trifluoromethanesulfonate Phenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, p-toluenesulfonate Tris (p-tert-butoxyphenyl) sulfonium acid, triphenylsulfonium nonafluorobutanesulfonate, butanesulfonic acid Li phenyl trifluoromethanesulfonate, trimethylsulfonium, p
-Trimethylsulfonium toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethyl p-toluenesulfonate Onium salts such as phenylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, and dicyclohexylphenylsulfonium p-toluenesulfonate; 2-cyclohexylcarbonyl-2
-(P-toluenesulfonyl) propane, 2-iso-
Propylcarbonyl-2- (p-toluenesulfonyl)
Β-ketosulfone derivatives such as propane, diazomethane derivatives such as bis (benzenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone, p-toluenesulfonic acid Nitrobenzylsulfonate derivatives such as 2,6-dinitrobenzyl and 2,4-dinitrobenzyl p-toluenesulfonate;
2,3-tris (methanesulfonyloxy) benzene,
Sulfonic acid ester derivatives such as 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate,
Examples thereof include imido-yl-sulfonate derivatives such as 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate. Examples thereof include triphenylsulfonium trifluoromethanesulfonate and trifluoromethanesulfonic acid (p-tert-butoxy). Phenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate,
triphenylsulfonium p-toluenesulfonate, p
The following compounds such as -toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium and tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types.

[0080]

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[0081]

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The compounding amount of the acid generator (C) is 0.5
If the amount is less than 0.5 part, the sensitivity may be reduced. If the amount is more than 15 parts, the resolution of the resist material is reduced due to a reduced alkali solubility rate. In some cases, the heat resistance may decrease due to an excessive amount of the monomer component.

In the present invention, a light absorber composed of a carboxylic acid derivative having a tricyclic aromatic skeleton represented by the above formula (1) or (2) is blended as the component (D). 01 to 10 parts, particularly preferably 0.1 to 5 parts,
If the amount is less than 0.01 part, sufficient effect of preventing standing waves and halation may not be obtained, and if it exceeds 10 parts, a remarkable decrease in sensitivity may appear.

As the dissolution controlling agent of the component (E), any one having at least one group decomposed by an acid in the molecule may be used.
Any of low molecular weight compounds and polymers may be used.

Examples of low molecular weight compounds include bisphenol A and the following polyphenol compounds in which the hydroxyl hydrogen atom is replaced with a tert-butyl derivative such as a tert-butoxy group, a tert-butoxycarbonyl group or a tert-butoxycarbonylmethyl group. Linear group such as a group, 1-ethoxyethyl group, 1-propoxyethyl group, 1-n-butoxyethyl group, 1-i-butoxyethyl group, 1-tert-butoxyethyl group, 1-tert-amyloxyethyl group Compounds substituted with a cyclic acetal group such as a cyclic or branched acetal group, a tetrahydrofuranyl group, a tetrahydropyranyl group, etc.

[0086]

Embedded image

Examples of the polymer dissolution controlling agent include a copolymer of p-butoxystyrene and tert-butyl acrylate and a copolymer of p-butoxystyrene and maleic anhydride. In this case, the weight average molecular weight is preferably from 500 to 10,000.

The compounding amount of the dissolution controlling agent of the component (E) is from 0 to
40 parts, preferably 1 to 40 parts, especially 5 to 25 parts are suitable.

As the basic compound to be blended as an additive of the component (F), a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By blending such a basic compound, the diffusion rate of the acid in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, the exposure margin and The pattern profile and the like can be improved.

As such a basic compound,
Primary, secondary, tertiary aliphatic amines, mixed amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples include a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine,
tert-butylamine, pentylamine, tert-
Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, and the like.Examples of the secondary aliphatic amines include: Dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-iso-butylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, Diheptylamine, dioctylamine,
Dinonylamine, didecylamine, didodecylamine,
Dicetylamine, N, N-dimethylmethylenediamine,
N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine and the like are exemplified. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, and triethylamine. -N-butylamine, tri-iso-butylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tri Dodecylamine, tricetylamine,
N, N, N ′, N′-tetramethylmethylenediamine,
N, N, N ', N'-tetramethylethylenediamine,
N, N, N ', N'-tetramethyltetraethylenepentamine and the like are exemplified.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine.

Specific examples of aromatic and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline,
N, N-dimethylaniline, 2-methylaniline, 3-
Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (for example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole Conductor (such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g. pyrroline, 2-methyl-1
-Pyrrolidine), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine,
Phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridinebutoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinipyridine, 1-methyl -4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives,
Piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, Purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10
-Phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine), and the like. Pyridinium p-toluenesulfonate and the like are exemplified, and a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, and an alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, triethanolamine, N-ethyldiethanolamine,
N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl)
Morpholine, 2- (2-hydroxyethyl) pyridine,
1- (2-hydroxyethyl) piperazine, 1- [2-
(2-Hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3
-Pyrrolidino-1,2-propanediol, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N-
(2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide and the like are exemplified.

The amide derivatives include formamide, N
-Methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-
Examples thereof include dimethylacetamide, propionamide, and benzamide. Examples of the imide derivative include phthalimide, succinimide, and maleimide. Particularly, triethylamine, N, N-dimethylaniline, N-methylpyrrolidone, pyridine, quinoline, nicotinic acid, triethanolamine, piperidineethanol, N, N-
Dimethylacetamide, succinimide and the like are preferred.
In addition, the said basic compound can be used individually by 1 type or in combination of 2 or more types.

The compounding amount of the basic compound to be compounded as the additive of the component (F) is preferably 0 to 2 parts, particularly preferably 0.01 to 1 part. When the compounding amount exceeds 2 parts, the sensitivity is excessively lowered. There are cases.

Specific examples of the aromatic compound having a group represented by −C—COOH in the molecule of the component (G) include 4-
Hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, 2-hydroxyphenylacetic acid, 3- (4-hydroxyphenyl) propionic acid, 3- (2-hydroxyphenyl) propionic acid, 2,5-dihydroxyphenylacetic acid, 3,4- Dihydroxyphenylacetic acid, 1,2-phenylene diacetate, 1,3-phenylene diacetate, 1,4-phenylene diacetate, 1,2-phenylenedioxy diacetate,
1,4-phenylenedipropanoic acid, benzoic acid, 4,4-
(4-hydroxyphenyl) valeric acid, 4-tert-butoxyphenylacetic acid, 4- (4-hydroxyphenyl)
Butyric acid, 3,4-dihydroxymandelic acid, 4-hydroxymandelic acid and the like.

The compounding amount of the aromatic compound having a group represented by ≡C-COOH in the molecule of the component (G) is from 0 to 15
Parts, preferably 0.1 to 15 parts, particularly preferably 1 to 10 parts.

The light absorbing agent other than the component (D) of the component (H) includes, for example, pentalene, indene, naphthalene, azulene, peptalene, biphenylene, indacene, fluorene, phenalene, phenanthrene, anthracene, fluoranthine, acetyrene Phenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, pleiadene, picene, perylene, pentaphen, pentacene, benzophenanthrene, anthraquinone, anthrone, benzantrone, 2,7-dimethoxynaphthalene, 2-ethyl-9, Condensed polycyclic hydrocarbon derivatives such as 10-dimethoxyanthracene, 9,10-dimethylanthracene, 9-ethoxyanthracene, 1,2-naphthoquinone, 9-fluorenone, theoxanthen-9-one, thia Tren, condensed heterocyclic derivatives such as dibenzothiophene, benzophenone, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 4,
Benzophenone derivatives such as 4'-dihydroxybenzophenone, 4,4'-bis (dimethylamino) benzophenone, square acid derivatives such as squaric acid and dimethyl squarate, bis (4-hydroxyphenyl) sulfoxide, bis (4-tert)
-Butoxyphenyl) sulfoxide, bis (4-ter
diarylsulfoxide derivatives such as t-butoxycarbonyloxyphenyl) sulfoxide, bis [4- (1-ethoxyethoxy) phenyl] sulfoxide, bis [4- (1-ethoxypropoxy) phenyl] sulfoxide, bis (4-hydroxyphenyl) Sulfone, bis (4-tert-butoxyphenyl) sulfone, bis (4-tert-butoxycarbonyloxyphenyl)
Sulfone, bis [4- (1-ethoxyethoxy) phenyl] sulfone, bis [4- (1-ethoxypropoxy)
Diphenyl sulfone derivatives such as phenyl) sulfone, benzoquinone diazide, naphthoquinone diazide, anthraquinone diazide, diazo compounds such as diazofluorene, diazotecharone, and diazophenanthrone; naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3, Quinone diazide group-containing compounds such as complete or partial ester compounds with 4-trihydroxybenzophenone, and complete or partial ester compounds of naphthoquinone-1,2-diazide-4-sulfonic acid chloride with 2,4,4'-trihydroxybenzophenone And the like.

The compounding amount of the light absorbing agent other than the component (D) of the component (H) is 0 to 10 parts, preferably 0.01 to 10 parts.
Parts, particularly preferably 0.1 to 5 parts.

A surfactant may be further added to the resist material to improve coating properties. Examples of the surfactant include fluorinated alkyl esters such as perfluoroalkylpolyoxyethylene ethanol, FC-430, and FC-31 (all manufactured by Sumitomo 3M Limited), perfluoroamine oxide, and perfluoroalkyl EO adducts. , X-70-092, X-70-0
93 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The method of using the resist material, the method of using light, and the like can be performed by using a known lithography technique. In particular, the resist material has a thickness of 254 to 193 nm.
It is most suitable for fine patterning by deep ultraviolet rays and electron beams.

[0103]

The compounds of the formulas (1) and (2) of the present invention
When used as a light absorber, it has no sublimability, has a very large light absorption in the far ultraviolet region, and further decomposes in the presence of an acid to liberate a carboxylic acid. Therefore, the chemically amplified positive resist material containing the same is sensitive to high energy rays such as far ultraviolet rays, electron beams and X-rays, particularly KrF excimer laser, and suppresses the appearance of standing waves and halation while dissolving. It has high resolution suitable for microfabrication technology without adversely affecting the characteristics and storage stability.

[0104]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples, Examples and Reference Examples, but the present invention is not limited to the following Synthesis Examples and Examples. All parts in each example are parts by weight.

[Synthesis Example 1] tert-butyl 9-anthracenecarboxylate (in the above formula (4a), R ⁵ = te
Synthesis of 9-anthracenecarboxylic acid (compound of the above formula (4a) where R ⁵ = H) 11.1 g (0.05 mol) of T-butyl
Dissolved in 50 g of HF. While maintaining the temperature at 5 ° C. or less under ice cooling, 42.0 g of trifluoroacetic anhydride (0.2 mol
l) was added dropwise over 10 minutes. After stirring at 0 to 5 ° C for 2 hours, the mixture was aged at room temperature for another 2 hours. Cool this again on ice,
Tert-butyl alcohol while maintaining the temperature at 5 ° C. or lower
6 g (0.4 mol) was added dropwise. After completion of the dropwise addition, the mixture was aged at room temperature for 2 hours. After completion of the reaction, 203 g of a 10% aqueous sodium hydroxide solution was added to the reaction solution to neutralize the acid, and extracted with 215 g of diethyl ether. The organic layer was washed twice with water, dried over magnesium sulfate, and purified by recrystallization from a THF-hexane solvent. Yield 6.7 g (yield 48
%), Purity 98.0%.

The obtained 9-anthracenecarboxylic acid te
The results of nuclear magnetic resonance spectrum (NMR), infrared spectrum (IR), and elemental analysis of rt-butyl are shown below.

[0107]

Embedded image < ¹ H-NMR: CDCl ₃ , δ (ppm)> (a) 1.80 singlet 9H (b) 7.26 to 7.58 multiplet 4H (c) 8.00 to 8.11 multiplet 4H (D) 8.48 singlet 1H <IR: (cm ⁻¹ )> 3081, 3052, 2973, 2933, 2867,
1714, 1625, 1560, 1523, 1486,
1473, 1457, 1456, 1444, 1413,
1392, 1367, 1319, 1290, 1265,
1236, 1160, 1145, 1014, 997, 9
52, 887, 850, 788, 728, 669, 64
0,619,601,551,528,462 <Elemental analysis _{(%): C 20 H 20} O 2> theory C: 82.0 H: 6.5 Found C: 82.0 H: 6.5

Synthesis Example 2 Synthesis of methoxymethyl 9-anthracenecarboxylate (compound of formula (4a) wherein R ⁵ = methoxymethyl group) 6.65 g of 9-anthracenecarboxylic acid (0.03 mol)
l) and 4.9 g (0.05 mol) of triethylamine were dissolved in 30 g of N, N-dimethylformamide. After stirring at room temperature for 30 minutes, 3.1 g (0.04 mol) of chloromethyl methyl ether was added dropwise while stirring was continued. After further stirring for 1 hour, the mixture was aged at 40 ° C. for 2 hours.
The reaction was stopped by adding 102 g of water to the reaction solution, and extracted with 114 g of dichloromethane. The organic layer was washed with a sodium hydroxide solution, further washed with water, and the solvent was distilled off under reduced pressure to obtain crystals. Yield 6.6 g (83% yield), 98% purity.

The results of nuclear magnetic resonance spectrum (NMR), infrared spectrum (IR), and elemental analysis of the obtained methoxymethyl 9-anthracenecarboxylate are shown below.

[0110]

Embedded image < ¹ H-NMR: CDCl ₃ , δ (ppm)> (a) 3.66 singlet 3H (b) 5.75 singlet 2H (c) 7.26 to 7.59 multiplet 4H (d) 8.01 to 8.13 Multiplet 4H (e) 8.54 Singlet 1H <IR: (cm ⁻¹ )> 3056, 2993, 2956, 2827, 1720,
1627, 1560, 1523, 1473, 1452,
1446, 1438, 1415, 1351, 1290,
1265, 1220, 1195, 1164, 1162,
1145, 1093, 1016, 970, 935, 92
7, 902, 854, 850, 790, 761, 73
2,669,638,603,566,551,51
4, 457, 426 <Elemental analysis value (%): C ₁₇ H ₁₄ O ₃ > Theoretical value C: 76.7 H: 5.3 Actual value C: 76.9 H: 5.3

Synthesis Example 3 Synthesis of ethoxyethyl 9-anthracenecarboxylate (compound of formula (4a) wherein R ^{5 is an} ethoxyethyl group) Instead of chloromethyl methyl ether used in Synthesis Example 2, 1-chloroethyl When the reaction was carried out in the same manner as in Synthesis Example 2 except that ethyl ether was used, ethoxyethyl 9-anthracenecarboxylate was obtained with a purity of 97% and a yield of 77%. The results of nuclear magnetic resonance spectrum (NMR) and elemental analysis of the obtained ethoxyethyl 9-anthracenecarboxylate are shown below.

[0112]

Embedded image < ¹ H-NMR: DMSO, δ (ppm)> (a) 1.15 to 1.20 triplet 3H (b) 1.47 to 1.57 doublet 3H (c) 3.58 to 3.5. 80 multiplet 2H (d) 6.11 to 6.18 quadruplet 1H (e) 7.47 to 7.80 multiplet 4H (f) 8.22 to 8.34 multiplet 4H (g) 8.75 Singlet 1H <Elemental analysis value (%): C ₁₉ H ₁₈ O ₃ > Theoretical value C: 77.5 H: 6.2 Actual value C: 77.6 H: 6.2

[Synthesis Example 4] Tetrahydropyranyl 9-anthracenecarboxylate (in the above formula (4a), R ⁵ =
Synthesis of tetrahydropyranyl group compound) 9-anthracenecarboxylic acid (11.1 g, 0.05 mol) was dissolved in a mixed solvent of THF (156 g) and dichloromethane (155 g). While stirring under ice-cooling, 21.0 g (0.25 mol) of 3,4-dihydro-2Hpyran was added dropwise.
After further stirring for 20 minutes, 0.138 g (0.0008 mol) of dehydrated p-toluenesulfonic acid was added and dissolved. After stirring at 0 ° C. for 1 hour and at room temperature for 1 hour, the reaction solution was ice-cooled and 5% aqueous sodium hydrogen carbonate solution was added.
g was added to neutralize the acid and terminate the reaction. The solvent was distilled off from the separated organic layer under reduced pressure to obtain an oil. The oil was purified by silica gel chromatography (elution solvent: ethyl acetate-hexane) to isolate tetrahydropyranyl 9-anthracenecarboxylate (see the following structural formula). Yield 10.8 g (yield 71%), purity 99
%.

Nuclear magnetic resonance spectrum (NMR) of the obtained tetrahydropyranyl 9-anthracenecarboxylate,
The results of infrared spectrum (IR) and elemental analysis are shown below.

[0115]

Embedded image < ¹ H-NMR: CDCl ₃ , δ (ppm)> (a) 1.88 to 2.09 multiplet 4H (b) 2.27 to 2.32 multiplet 2H (c) 4.11 to 4.29 7. Two multiplets 2H (d) 6.93 to 6.95 Triplets 1H (e) 7.54 to 7.87 Multiplets 4H (f) 8.30 to 8.33 Doublets 2H (g) 39-8.42 Doublet 2H (h) 8.81 Singlet 1H ¹ H <IR: (cm ⁻¹ )> 3399, 3054, 2977, 2944, 2883,
1716, 1625, 1523, 1454, 1446,
1390, 1357, 1321, 1286, 1265,
1222, 1197, 1168, 1153, 1128,
1118, 1056, 1022, 991, 937, 90
0, 896, 869, 854, 819, 792, 73
2,684,620,603,555,520,44
5,424 <Elemental analysis _{(%): C 17 H 14} O 3> theory C: 78.4 H: 5.9 Found C: 78.3 H: 5.9

[Synthesis Example 5] Tetrahydrofuranyl 9-anthracenecarboxylate (in the above formula (4a), R ⁵ =
Synthesis of tetrahydrofuranyl group compound) Reaction was carried out in the same manner as in Synthesis Example 4 except that dihydrofuran was used instead of 3,4-dihydro-2Hpyran used in Synthesis Example 4, and tetrahydrofuranyl 9-anthracenecarboxylate was obtained. Was obtained with a purity of 98% and a yield of 72%.

[Synthesis Example 6] n-propoxyethyl 9-anthracenecarboxylate (in the above formula (4a), R ⁵ =
Synthesis of n-propoxyethyl group compound) Reaction was carried out in the same manner as in Synthesis Example 4 except that n-propyl vinyl ether was used instead of 3,4-dihydro-2Hpyran used in Synthesis Example 4, and 9-anthracene was obtained. N-Propoxyethyl carboxylate has a purity of 97% and a yield of 68%
Was obtained.

[Synthesis Example 7] tert-butoxyethyl 9-anthracenecarboxylate (in the above formula (4a), R
Synthesis of ⁵ = tert-butoxyethyl group) The reaction was carried out in the same manner as in Synthesis Example 4 except that tert-butyl vinyl ether was used instead of 3,4-dihydro-2Hpyran used in Synthesis Example 4. Tert-Butoxyethyl anthracenecarboxylate was obtained with a purity of 98% and a yield of 70%.

[Synthesis Example 8] N-butoxyethyl 9-anthracenecarboxylate (in the above formula (4a), R ⁵ = n
-Synthesis of -butoxyethyl group compound) Synthesis Example 4 except that n-butyl vinyl ether was used instead of 3,4-dihydro-2Hpyran used in Synthesis Example 4.
As a result, n-butoxyethyl 9-anthracenecarboxylate was obtained with a purity of 98% and a yield of 65%.

[Synthesis Example 9] iso-butoxyethyl 9-anthracenecarboxylate (in the above formula (4a), R ⁵
= Iso-butoxyethyl group) Synthesis of isocyanate instead of ethyl vinyl ether used in Synthesis Example 4
The reaction was conducted in the same manner as in Synthesis Example 4 except that o-butyl vinyl ether was used. As a result, iso-butoxyethyl 9-anthracenecarboxylate was obtained with a purity of 98% and a yield of 75%.

[Synthesis Example 10] Synthesis of ethoxypropyl 9-anthracenecarboxylate (compound of formula (4a) wherein R ^{5 is an} ethoxypropyl group) Instead of ethyl vinyl ether used in Synthesis Example 4, 4-
When the reaction was carried out in the same manner as in Synthesis Example 4 except that oxa-2-hexene was used, ethoxypropyl 9-anthracenecarboxylate was obtained with a purity of 99% and a yield of 66%.

Synthesis Example 11 Synthesis of trimethylsilyl 9-anthracenecarboxylate (compound of formula (4a) wherein R ⁵ = trimethylsilyl group) Except that trimethylsilyl chloride was used instead of chloromethyl methyl ether used in Synthesis Example 2 When the reaction was carried out in the same manner as in Synthesis Example 2, trimethylsilyl 9-anthracenecarboxylate was obtained with a purity of 97% and a yield of 85%.

[Synthesis Example 12] The 9-anthracenecarboxylic acid used in Synthesis Example 1 (in the above formula (4a), R ⁵ = H
In the same manner as in Synthesis Example 1 except that 1-anthracenecarboxylic acid (compound of formula (4b) where R ⁵ = H) is used instead of tert-amyl alcohol and tert-butyl alcohol is used instead of tert-amyl alcohol. After the reaction, the following compound was obtained.

Tert-Butyl 1-anthracenecarboxylate (compound of the above formula (4b) wherein R ⁵ = tert-butyl group) Purity 99%, Yield 46% [Synthesis Examples 13 to 22] 9-anthracenecarboxylic acid (in the formula (4a), R ⁵ ＝ H
The compounds were reacted in the same manner as in Synthesis Examples 2 to 11 except that 1-anthracenecarboxylic acid (the compound of the above formula (4b), in which R ⁵ = H) was used instead of the compound of the formula (4b), to obtain the following compounds, respectively. Was done. <Synthesis Example 13> 98% purity and 80% yield of methoxymethyl 1-anthracenecarboxylate (compound of R ⁵ = methoxymethyl group in the above formula (4b)) <Synthesis Example 14> ethoxyethyl 1-anthracenecarboxylate (the above-mentioned compound) Compound of the formula (4b) wherein R ⁵ = ethoxyethyl group) Purity 97%, Yield 77% <Synthesis Example 15> Tetrahydropyranyl 1-anthracenecarboxylate (in the above formula (4b), R ⁵ = tetrahydropyranyl group Compound) Purity 97%, Yield 66% <Synthesis Example 16> Tetrahydrofuranyl 1-anthracenecarboxylate (compound of R ⁵ = tetrahydrofuranyl group in the above formula (4b)) Purity 99%, Yield 69% <Synthesis Example 17> N-propoxyethyl 1-anthracenecarboxylate (in the formula (4b), R ⁵ = n-propoxyethyl group) Compound) 99% purity, 75% yield <Synthesis Example 18> 1-anthracenecarboxylic acid tert-
Butoxyethyl (in the above formula (4b), R ⁵ = ter
Compound of t-butoxyethyl group) Purity 97%, Yield 60
<Synthesis Example 19> n-butoxyethyl 1-anthracenecarboxylate (compound of R ⁵ = n-butoxyethyl group in the above formula (4b)) purity 98%, yield 64% <synthesis example 20> 1-anthracenecarboxylic acid Iso-butoxyethyl acid (in the formula (4b), R ⁵ = iso-
Compound of butoxyethyl group) Purity 98%, yield 60% <Synthesis Example 21> Ethoxypropyl 1-anthracenecarboxylate (compound of R ⁵ = ethoxypropyl group in the above formula (4b)) Purity 98%, Yield 55% <Synthesis Example 22> Trimethylsilyl 1-anthracenecarboxylate (compound of R ⁵ = trimethylsilyl group in the above formula (4b)) Purity 98%, yield 82%

[Synthesis Examples 23 to 33] Instead of 1-anthracenecarboxylic acid used in Synthesis Examples 12 to 22, 2-anthracenecarboxylic acid (in the above formula (4c), R ⁵ = H
The compounds were reacted in the same manner as in Synthesis Examples 12 to 22 except that Compound (1) was used, and the following compounds were obtained, respectively. <Synthesis Example 23> 2-anthracenecarboxylic acid tert-
Butyl (compound of R ⁵ = tert-butyl group in the formula (4c)) Purity 99%, yield 46% <Synthesis Example 24> Methoxymethyl 2-anthracenecarboxylate (R ⁵ = methoxymethyl in the formula (4c) Compound of the group) Purity 98%, Yield 80% <Synthesis Example 25> Ethoxyethyl 2-anthracenecarboxylate (compound of R ⁵ = ethoxyethyl group in the above formula (4c)) Purity 97%, Yield 77% <Synthesis Example 26> Tetrahydropyranyl 2-anthracenecarboxylate (compound of R ⁵ = tetrahydropyranyl group in the above formula (4c)) Purity 97%, yield 66% <Synthesis Example 27> Tetrahydrofuranyl 2-anthracenecarboxylate (the above-mentioned compound) R ⁵ = compound of tetrahydrofuranyl group) of 99% purity in the formula (4c), 69% yield <synthesis example 28> 2-Ant Sen carboxylic acid n- propoxyethyl (Formula (R ⁵ = n- compounds of propoxyethyl group in 4c)) 99% purity, 75% yield <Synthesis Example 29> 2-anthracene carboxylic acid tert-
Butoxyethyl (in the above formula (4c), R ⁵ = ter
Compound of t-butoxyethyl group) Purity 97%, Yield 60
<Synthesis Example 30> n-butoxyethyl 2-anthracenecarboxylate (compound of R ⁵ = n-butoxyethyl group in the above formula (4c)) purity 98%, yield 64% <synthesis example 31> 2-anthracenecarboxylic acid Iso-butoxyethyl acid (in the formula (4c), R ⁵ = iso-
Compound of butoxyethyl group) Purity 98%, yield 60% <Synthesis Example 32> Ethoxypropyl 2-anthracenecarboxylate (compound of R ⁵ = ethoxypropyl group in the above formula (4c)) Purity 98%, yield 60% <Synthesis Example 33> Trimethylsilyl 2-anthracenecarboxylate (compound of R ⁵ = trimethylsilyl group in the above formula (4c)) Purity 99%, yield 86%

[Synthesis Example 34] tert-butyl 9-anthracene methoxyacetate (In the above formula (4e), R ⁵ =
Synthesis of tert-butyl group compound) 6.7 g (0.17 mol) of 60% sodium hydride was washed with 60 g of hexane, and 306 g of THF and 9-g of 9-
29.1 g of hydroxymethylanthracene (0.14 m
ol) and stirred. After stirring at room temperature for 20 minutes and stirring at 65 ° C. for 1 hour under reflux, the reaction solution was cooled and 28.0 g (0.17 mol) of ethyl bromoacetate and THF2 under ice-cooling.
3 g of the mixture were added dropwise over 10 minutes. This reaction solution was aged at room temperature for 1 hour and further at 65 ° C. for 1 hour, cooled, and stopped with a 0.4% aqueous ammonium chloride solution. The organic layer extracted with 200 g of ether was washed with water and the solvent was distilled off to obtain a mixture of crystals and an oil. This was dissolved again in ether, the insolubles were filtered off, dried over magnesium sulfate, and the solvent was distilled off.

The brown oil obtained was chromatographed on silica gel (eluent: ethyl acetate-hexane 1: 1).
Purification by 0) yielded ethyl 9-anthracene methoxyacetate (compound of formula (4e) wherein R ⁵ = ethyl group) as white crystals. Yield 14.2 g (yield 34.
5%), 95% pure.

To 14.2 g of the obtained ethyl 9-anthracene methoxyacetate, 145 g of methanol was added and dissolved by heating at 50 ° C., and 100 g of a 3% aqueous sodium hydroxide solution was added dropwise. After refluxing at 75 ° C. for 30 minutes, the reaction solution was cooled and the solvent was distilled off. 200 g of ether in the solid residue
And 300 g of water, and the solution was made acidic with concentrated hydrochloric acid, whereby crystals precipitated at the interface. This was separated by filtration, dissolved in a mixed solvent of THF-ether, washed with water, and recrystallized from ethanol to obtain ethyl 9-anthracenemethoxyacetate (compound of the above formula (4e) where R ⁵ = H) as white crystals. Was. Yield 6.9 g (53% yield), purity 9
7%.

The reaction was carried out in the same manner as in Synthesis Example 12 except that the obtained 9-anthracene methoxyacetic acid was used instead of 1-anthracene carboxylic acid used in Synthesis Example 12, to obtain tert-butyl 9-anthracene methoxyacetate. Was done. Purity 99%, yield 51%.

[Synthesis Examples 35 to 44] Instead of 1-anthracenecarboxylic acid used in Synthesis Examples 13 to 22, 9-anthracenemethoxyacetic acid (in the above formula (4e), R ⁵ =
(Compound H) except that Compound (H) was used, and the following reaction was obtained in the same manner as in Synthesis Examples 12 to 20, respectively. <Synthesis Example 35> Methoxymethyl 9-anthracene methoxyacetate (compound of R ⁵ = methoxymethyl group in the above formula (4e)) Purity 98%, yield 76% <Synthesis Example 36> Ethoxyethyl 9-anthracene methoxyacetate (the above Compound of the formula (4e) wherein R ⁵ = ethoxyethyl group) Purity 96%, yield 61% <Synthesis Example 37> 9-anthracenemethoxyacetic acid tetrahydropyranyl (in the above formula (4e), R ⁵ = tetrahydropyranyl group Compound) Purity 98%, Yield 59% <Synthesis Example 38> Tetrahydrofuranyl 9-anthracenemethoxyacetate (compound of R ⁵ = tetrahydrofuranyl group in the above formula (4e)) 98% purity, yield 72% <Synthesis Example 39 > 9-anthracene methoxyacetate n-propoxyethyl (in the above formula (4e), R ⁵ = n-propoxy) Compound of a siethyl group) Purity 98%, Yield 68% <Synthesis Example 40> 9-anthracenemethoxyacetic acid tert
-Butoxyethyl (in the above formula (4e), R ⁵ = te
rt-butoxyethyl group compound) purity 97%, yield 6
0% <Synthesis Example 41> 9-anthracene methoxyacetate n-butoxyethyl methoxyacetate (compound of R ⁵ = n-butoxyethyl group in the above formula (4e)) 98% purity, yield 69% <Synthesis Example 42> 9-anthracene Methoxyacetic acid iso-
Butoxyethyl (in the formula (4e), R ⁵ = iso)
-Butoxyethyl group compound) Purity 98%, yield 66% <Synthesis Example 43> Ethoxypropyl 9-anthracene methoxyacetate (compound of the above formula (4e), wherein R ⁵ = ethoxypropyl group) 98% purity, yield 66 <Synthesis Example 44> Trimethylsilyl 9-anthracene methoxyacetate (compound of R ⁵ = trimethylsilyl group in the above formula (4e)) Purity 98%, Yield 75%

[Synthesis Examples 45 to 56] Instead of 9-hydroxycarbonylmethoxymethylanthracene used in Synthesis Examples 34 to 44, 1,2,10- (6-methylanthracene) trioxyacetic acid (in the above formula (4f) R ⁵ = H
The same reaction as in Synthesis Examples 34 to 44 was carried out except that Compound (A) was used, and the following compounds were obtained, respectively. (R ⁵ = tert- compound of butyl in the formula (4f)) <Synthesis Example 45> 1,2,10- (6-methyl anthracene) Three oxy acid tert- butyl 99
%, Yield 51%. <Synthesis Example 46> 1,2,10- (6-methyl anthracene) Three oxy acid methoxymethyl (Formula (compound of R ⁵ = methoxymethyl group in 4f)) 98% pure, 76% yield <Synthesis Example 47 > Ethoxyethyl 1,2,10- (6-methylanthracene) trioxyacetate (compound of R ⁵ = ethoxyethyl group in the above formula (4f)) 96% purity, 61% yield <Synthesis Example 48> , 10- (6-Methylanthracene) tetrahydropyranyl trioxyacetate (the formula (4)
In f), a compound in which R ⁵ = tetrahydropyranyl group)
Purity 98%, Yield 59% Synthesis Example 49 Tetrahydrofuranyl 1,2,10- (6-methylanthracene) trioxyacetate (the formula (4)
In f), a compound in which R ⁵ = tetrahydrofuranyl group)
Purity 98%, Yield 72% <Synthesis Example 50> n-propoxyethyl 1,2,10- (6-methylanthracene) trioxyacetate (the formula (4)
In f) R ⁵ = compound of n-propoxyethyl group)
Purity 98%, Yield 68% <Synthesis Example 51> tert-Butoxyethyl 1,2,10- (6-methylanthracene) trioxyacetate (R ⁵ = tert-butoxyethyl group compound in the above formula (4f)) Purity 97%, Yield 60% <Synthesis Example 52> n-butoxyethyl 1,2,10- (6-methylanthracene) trioxyacetate (the above formula (4f)
R ⁵ = compound of n-butoxyethyl group) purity 9
<Synthesis Example 53> iso-butoxyethyl 1,2,10- (6-methylanthracene) trioxyacetate (formula (4)
f) R ⁵ = iso-butoxyethyl group compound) 98% purity, 66% yield <Synthesis Example 54> ethoxypropyl 1,2,10- (6-methylanthracene) trioxyacetate (the above formula (4f) R ⁵ = compound of ethoxypropyl group) purity 98
<Synthesis Example 55> Trimethylsilyl 1,2,10- (6-methylanthracene) trioxyacetate (compound of R ⁵ = trimethylsilyl group in the above formula (4f)) Purity 98
%, Yield 79%

[Synthesis Examples 56 to 66] Instead of 1-anthracenecarboxylic acid used in Synthesis Examples 12 to 22, 4-phenanthrenecarboxylic acid (in the above formula (4g), R ⁵ =
(Compound of H), except that Compound (H) was used. The reaction was carried out in the same manner as in Synthesis Examples 12 to 22, and the following compounds were obtained. <Synthesis Example 56> 4-phenanthrenecarboxylic acid tert
-Butyl (compound of R ⁵ = tert-butyl group in the above formula (4g)) purity 99%, yield 46% <Synthesis Example 57> methoxymethyl 4-phenanthrenecarboxylate (R ⁵ = methoxy in the above formula (4g) <Compound of methyl group) Purity 98%, Yield 80% <Synthesis Example 58> Ethoxyethyl 4-phenanthrenecarboxylate (compound of R ⁵ = ethoxyethyl group in the above formula (4g)) Purity 97%, Yield 77% < Synthesis Example 59> Tetrahydropyranyl 4-phenanthrenecarboxylate (compound of R ⁵ = tetrahydropyranyl group in the above formula (4g)) Purity 97%, Yield 66% <Synthesis Example 60> Tetrahydrofuranyl 4-phenanthrenecarboxylate ( formula R ⁵ = compound of tetrahydrofuranyl group) of 99% purity in (4g), 69% yield <synthesis example 61> - phenanthridine (compound of R ⁵ = n- propoxy ethyl group in the formula (4g)) Ren carboxylic acid n- propoxyethyl purity 99%, yield 75% <Synthesis Example 62> 4-phenanthrene carboxylic acid tert
-Butoxyethyl (in the above formula (4g), R ⁵ = te
rt-butoxyethyl group compound) purity 97%, yield 6
<Synthesis Example 63> n-butoxyethyl 4-phenanthrenecarboxylate (compound of R ⁵ = n-butoxyethyl group in the above formula (4g)) 98% purity, 64% yield <Synthesis Example 64> 4-phenanthrene Carboxylic acid iso-
Butoxyethyl (in the above formula (4g), R ⁵ = iso)
- compounds of butoxyethyl) 98% pure, compounds of the R ⁵ = ethoxypropyl in 60% yield <Synthesis Example 65> 4-phenanthrene carboxylic acid ethoxy propyl (Formula (4g)) 98% pure, yield 60 <Synthesis Example 66> Trimethylsilyl 4-phenanthrenecarboxylate (compound of R ⁵ = trimethylsilyl group in the above formula (4g)) 98% purity, 81% yield

[Synthesis Examples 67 to 77] In place of 1-anthracenecarboxylic acid used in Synthesis Examples 12 to 22, 9- (1
-Ethoxy-5-methoxyethylphenanthrene) carboxylic acid (the compound of the formula (4h) wherein R ⁵ = H) was used in the same manner as in Synthesis Examples 12 to 22 to obtain the following compounds. Was done. <Synthesis Example 67> 9- (1-ethoxy-5-methoxy-ethyl phenanthrene) carboxylic acid tert- butyl (compound of R ⁵ = tert- butyl group in the formula (4g)) 99% purity, 55% yield <Synthesis Example 68> Methoxymethyl 9- (1-ethoxy-5-methoxyethylphenanthrene) carboxylate (compound of R ⁵ = methoxymethyl group in the above formula (4 g)) purity 99%, yield 91% <Synthesis Example 69> 9 Ethoxyethyl- (1-ethoxy-5-methoxyethylphenanthrene) carboxylate (compound of R ⁵ = ethoxyethyl group in the above formula (4g)) purity 99%, yield 89% <Synthesis Example 70> 9- (1- ethoxy-5-methoxy-ethyl phenanthrene) carboxylic acid tetrahydropyranyl in (formula (4g) R ⁵ = tetrahydropyranyl group Compound) 99% purity, 66% yield <Synthesis Example 71> 9- R ⁵ = compound of tetrahydrofuranyl group in (1-ethoxy-5-methoxy-ethyl phenanthrene) carboxylic acid tetrahydrofuranyl (Formula (4g)) 99 <Synthesis Example 72> n-Propoxyethyl 9- (1-ethoxy-5-methoxyethylphenanthrene) carboxylate (compound of R ⁵ = n-propoxyethyl group in the above formula (4g)) Purity 99 <Synthesis Example 73> tert-butoxyethyl 9- (1-ethoxy-5-methoxyethylphenanthrene) carboxylate (compound of R ⁵ = tert-butoxyethyl group in the above formula (4 g)) purity 99 <Synthesis Example 74> 9- (1-ethoxy-5-methoxyethylphenanthrene) carboxylic acid - butoxyethyl (Formula (R ⁵ = n-compound of butoxyethyl in 4g)) 99% purity, 62% yield <Synthesis Example 75> 9- (1-ethoxy-5-methoxy-ethyl phenanthrene) carboxylic acid iso -Butoxyethyl (compound of the above formula (4g), R ⁵ = tert-butyl group) purity 99%, yield 75% <Synthesis Example 76> ethoxypropyl 9- (1-ethoxy-5-methoxyethylphenanthrene) carboxylate (Compound of formula (4g) wherein R ⁵ = tert-butyl group) Purity 99%, Yield 73% <Synthesis Example 77> Trimethylsilyl 9- (1-ethoxy-5-methoxyethylphenanthrene) carboxylate (Formula (4) In 4g), R ⁵ = compound of trimethylsilyl group) purity 99%, yield 86%

The light absorbers comprising the novel compounds obtained in the above Synthesis Examples 1 to 4 were prepared according to the following Dye. 1 to Dy
e. 4 and a conventional light absorber Dye. 10
And Dye. Table 1 shows the molar absorption coefficient of the ultraviolet absorption spectrum (solvent: methanol) of No. 11 at 248 nm.

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[0136]

[Table 1]

As is clear from the results shown in Table 1, the light absorber comprising the compound of the above formula (1) or (2)
It has been found that the absorbance in nm can be significantly increased as compared with a conventional light absorber.

Examples 1 to 20, Comparative Examples 1 to 7 Polyhydroxystyrene represented by the following formula (Polym. 1) in which a hydrogen atom of a hydroxyl group is partially protected by a tert-butoxycarbonyl group, hydrogen of a hydroxyl group The following formula (Polym. 2) in which atoms are partially protected by a tetrahydrofuranyl group
A polyhydroxystyrene represented by the following formula (P) in which a hydrogen atom of a hydroxyl group is partially protected by a 1-ethoxyethyl group.
olym. The polyhydroxystyrene represented by 3) or the hydrogen atom of the hydroxyl group was partially protected with a tert-butoxycarbonyl group and a 1-ethoxyethyl group (P
olym. 4) a polyhydroxystyrene represented by the formula:
An acid generator represented by the following formulas (PAG.1) to (PAG.7) selected from onium salts, sulfonic acid derivatives of pyrogallol, benzylsulfonic acid derivatives, bisalkylsulfonyldiazomethane derivatives, and N-sulfonyloxyimide derivatives; Compound in which the phenolic hydroxyl group of bisphenol A is substituted with a tert-butoxycarbonyl group, 2- (4-hydroxyphenyl) -2- {4- (4
-Methyl-4-hydroxyphenyl) cyclohexyl}
From the following formula (DRI.1), which is selected from compounds in which a phenolic hydroxyl group of propane is partially substituted with a tert-butoxycarbonyl group or an ethoxyethyl group,
I. 3) and a dissolution controlling agent represented by the following formula (Dye.
11) to (Dye.11) were dissolved in a solvent to prepare resist materials having various compositions shown in Tables 2 to 4.

After the obtained resist material was filtered through a 0.2 μm Teflon filter to prepare a resist solution, the resist solution was spin-coated on a silicon wafer and applied to 0.7 μm.

Next, this silicon wafer was heated at 100 ° C.
Was baked on a hot plate for 120 seconds. Furthermore, an excimer laser stepper (Nikon Corporation, NSR2005E
(XNA = 0.5), baked at 90 ° C. for 90 seconds, and developed with a 2.38% aqueous solution of tetramethylammonium hydroxide to obtain a positive pattern.

The obtained resist pattern was evaluated as follows. The results are shown in Tables 2 to 4. Resist pattern evaluation method: First, the sensitivity (Eth) was determined. Next, 0.30
μm line and space top and bottom 1: 1
And the minimum line width of the separated line and space at this exposure amount was taken as the resolution of the evaluation resist. The shape of the resolved resist pattern and the presence or absence of standing waves were observed using a scanning electron microscope. The occurrence of scum was also confirmed by observation using a scanning electron microscope.

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[Table 2] PGMEA: Propylene glycol monomethyl ether acetate EL / BA: Mixed solution of ethyl lactate (85 wt%) and butyl acetate (15 wt%)

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[Table 3] PGMEA: Propylene glycol monomethyl ether acetate EL / BA: Mixed solution of ethyl lactate (85 wt%) and butyl acetate (15 wt%) EIPA: 1-ethoxy-2-propanol NMP: N-methylpyrrolidone PE: Piperidine ethanol TEA: Triethanol Amine

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[Table 4] PGMEA: propylene glycol monomethyl ether acetate EIPA: 1-ethoxy-2-propanol EL / BA: Mixed solution of ethyl lactate (85 wt%) and butyl acetate (15 wt%)

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H01L 21/30 502R (72) Inventor Shigehiro Nakura 28-1 Nishifukushima, Nishifukushima, Oku-ku, Niigata Niigata Shin-Etsu Chemical Synthetic Technology Laboratory Co., Ltd. (72) Inventor Toshinobu Ishihara 28-1 Nishifukushima, larger section of Kushiro-mura, Nakakubijo-gun, Niigata Prefecture Synthetic Technology Laboratory Co., Ltd.

Claims (8)

[Claims] 1. A light absorber comprising a carboxylic acid derivative having a tricyclic aromatic skeleton represented by the following general formula (1) or (2). Embedded image (Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, R ⁴ is a linear or branched alkenyl group or an aryl group, R ⁴ is a substituted or unsubstituted aliphatic hydrocarbon group which may contain an oxygen atom, a substituted or unsubstituted group which may contain an oxygen atom. An alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group which may contain an oxygen atom or an oxygen atom, R ⁵ is an acid labile group, and p is 0 or 1. k , H, and m are each an integer of 0 to 9, n is an integer of 1 to 10, and k + h + m + n
Satisfies ≦ 10. ) 2. An acid labile group R of the formulas (1) and (2)
^2. The light absorber according to claim 1, wherein ⁵ has a structure represented by the following formula (3a), (3b) or (3c). Embedded image (Wherein, R ^{6 to} R ⁸ are each independently a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl or aryl group, which may contain a carbonyl group in the chain, all of R ⁶ to R ⁸ must not be hydrogen atoms. in addition, the R ⁶ R ⁷ may combine with each other to form a ring, R ⁹ may be a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl group, or Aryl groups, and these groups may contain a carbonyl group in the chain, and R ⁹ may combine with R ⁶ to form a ring.) (A) an organic solvent; (B) an alkali-insoluble or hardly soluble resin having an acidic functional group protected by an acid labile group, which is alkali-soluble when the acid labile group is dissociated. A chemically amplified positive resist material comprising: (C) an acid generator; and (D) the light absorber according to claim 1. 4. The resin of component (B) has a weight average molecular weight of 3,0 in which hydrogen atoms of some hydroxyl groups are substituted with acid labile groups.
4. The chemically amplified positive resist composition according to claim 3, wherein the composition is a polyhydroxystyrene of from 00 to 300,000. 5. The chemically amplified positive resist composition according to claim 3, wherein a dissolution controlling agent is blended as the component (E). 6. The chemically amplified positive resist material according to claim 3, wherein a basic compound is blended as the component (F). 7. As a component (G), ΔC-CO is present in the molecule.
7. The chemically amplified positive resist material according to claim 3, further comprising an aromatic compound having a group represented by OH. 8. The chemically amplified positive resist composition according to claim 3, wherein a light absorber different from the component (D) is blended as the component (H).