JPH10120628A - Carboxylic acid derivative having tricyclic aromatic skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound suitable as a component for a chemical amplification positive type resist material containing a tricyclic aromatic skeleton. SOLUTION: This carboxylic acid derivative is shown by formula I (R<1> to R<3> are each H, an alkyl, an alkoxy, etc.; R<4> is a bifunctional aliphatic hydrocarbon group, an alicyclic hydrocarbon group, etc., which may contain O, respectively; R<5> is an acid unstable group; (p) is 0 or 1; (k) (h) and (m) are each 0-9; (n) is 1-10; k+h+m+n<=10) such as 9-anthracenecarboxylic acid tert-amyl ester. The compound of formula I is obtained by reacting a 9-anthracenecarboxylic acid of formula II with trifluoroacetic acid anhydride, and then with tertamyl- alcohol of formula III (R<6> to R<8> are each H, an alkyl, an alkoxy, etc.). Since the compound of formula I has no sublimability, is high in light absorption in the far ultraviolet range and is decomposed in the presence of an acid to liberate a carboxylic acid, the compound has high resolution suitable for fine processing technology.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a high sensitivity to high energy rays such as far ultraviolet rays, electron beams and X-rays,
The present invention relates to a novel carboxylic acid derivative having a tricyclic aromatic skeleton suitable as a component of a chemically amplified positive resist material suitable for fine processing technology and capable of forming a pattern by developing with an aqueous alkali solution.

[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 (JP-B-2-27660, JP-A-63-27)
No. 829) is a resist material which has high sensitivity, resolution and 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, and 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. .

[0005] In general, as means for solving these,
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 of using a low transmittance resist material. 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 is volatilized from the resist film by pre-baking, and not only does the effect of preventing halation or 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 carbon at the β-position of a styrene 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,
A chemically amplified positive resist that has high resolution suitable for microfabrication technology and can provide a chemically amplified positive resist material that does not exhibit standing waves or halation even when used on highly reflective substrates. An object of the present invention is to provide a carboxylic acid derivative having a tricyclic aromatic skeleton suitable as a component of a material.

[0011]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, have found that tricyclic aromatic compounds represented by the following formulas (5) and (6). A carboxylic acid derivative having a tricyclic aromatic skeleton represented by the following general formula (1) or (2), which can be easily and inexpensively synthesized from a carboxylic acid derivative having a skeleton, has excellent properties as a light absorber. It has been found that this is suitable as a component of a chemically amplified positive resist material having a high resolution suitable for microfabrication technology, and can exert a great effect particularly in deep ultraviolet lithography.

[0012]

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 divalent aliphatic hydrocarbon group optionally containing an oxygen atom, substituted or unsubstituted optionally containing an oxygen atom, An unsubstituted divalent alicyclic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom or an oxygen atom, and R ⁵ is an acid labile group. 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 satisfies k + h + m + n ≦ 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. For this reason, there are no drawbacks such as an insufficient effect of preventing halation and standing waves, 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 cannot achieve the desired effect unless they are added in an amount equal to or greater than that of the acid generator and the dissolution inhibitor, while reducing the film thickness in unexposed areas and remaining undissolved areas in exposed areas. In addition, deterioration of the pattern profile such as rounding of the head and tailing of the hem, and further, deterioration of the storage stability, etc., occur, and as a result, there is often a contradiction that the performance is deteriorated by the addition for improving the performance. 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 light absorber 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. Therefore, there is no occurrence of scum or bridge, and the ratio of the alkali dissolution rates before and after exposure (called dissolution contrast) is large, so that the resolution can be improved.

Accordingly, a chemically amplified positive resist material containing one or more of the compounds represented by the above formulas (1) or (2) can be used with high energy rays such as far ultraviolet rays, electron beams and X rays. When used in conventional lithography (especially KrF excimer laser light), the pattern profile and the resolution do not deteriorate. Therefore, the novel compound of the present invention can exhibit excellent performance when used as a light absorber of a chemically amplified positive resist material, and obtain a resist image having high resolution and a wide depth of focus. Can be done.

Accordingly, the present invention provides a carboxylic acid derivative having a tricyclic aromatic skeleton represented by the above general formula (1) or (2).

Hereinafter, the present invention will be described in more detail. The carboxylic acid derivative having a novel tricyclic aromatic skeleton of the present invention is represented by the following general formula (1) or (2).

[0017]

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 divalent aliphatic hydrocarbon group optionally containing an oxygen atom, substituted or unsubstituted optionally containing an oxygen atom, An unsubstituted divalent alicyclic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom or an oxygen atom, and R ⁵ is an acid labile group. 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 satisfies k + h + m + n ≦ 10. )

In the above formulas (1) and (2), 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, a linear or branched It is an alkenyl group or an aryl group. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Those having 1 to 10 carbon atoms such as n-butyl group, sec-butyl group, tert-butyl group, hexyl group, cyclohexyl group and adamantyl group are preferable, and among them, methyl group, ethyl group, isopropyl group, tert-butyl group are preferable. Groups are more preferably used. Examples of the linear or branched alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-
Butoxy, tert-butoxy, hexyloxy,
Those having 1 to 8 carbon atoms such as cyclohexyloxy group are preferable, and among them, methoxy group, ethoxy group, isopropoxy group and tert-butoxy group are more preferably used.
Examples of the linear or branched alkoxyalkyl group include a methoxymethyl group, an ethoxypropyl group, a propoxyethyl group and a tert-butoxyethyl group.
10 to 10 are preferable, among which a 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, a phenyl group, a xylyl group, a toluyl group,
Those having 6 to 14 carbon atoms such as a cumenyl group are preferred.

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;

The substituted or unsubstituted divalent aliphatic hydrocarbon group which may contain an oxygen atom includes, for example, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec- Butylene group, -CH ₂
O- group, -CH ₂ CH ₂ O- group, -CH ₂ OCH ₂ - is preferred has 1 to 10 carbon atoms, such as radicals, among them methylene group, an ethylene group, -CH ₂ O- group, - CH ₂ CH ₂ O-
Groups are more preferably used.

The substituted or unsubstituted divalent alicyclic hydrocarbon group which may contain an oxygen atom includes, for example, 1,1,
4-cyclohexylene group, 2-oxacyclohexane-
1,4-ylene group, 2-thiacyclohexane-1,4-
Examples thereof include those having 5 to 10 carbon atoms such as an ylene group.

The substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom includes, for example, o-
Phenylene group, p-phenylene group, 1,2-xylene-
3,6-ylene group, toluene-2,5-ylene group, 1-
Those having 6 to 14 carbon atoms, such as cumene-2,5-ylene group, or arylalkylene group referred arylalkylene group (wherein the 6 to 14 carbon atoms -CH ₂ Ph- group, -C
H ₂ PhCH ₂ — group, —OCH ₂ Ph— group, —OCH ₂ Ph
It means a CH ₂ O— group or the like. Here, Ph is a phenylene group. ).

R ⁵ is an acid labile group. 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. It is not particularly limited as long as it decomposes below to release a functional group exhibiting alkali solubility, but particularly preferred are groups represented by the following general formulas (3a), (3b) and (3c).

[0024]

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 Alternatively, it is a branched alkenyl group or an aryl group, and these groups may contain a carbonyl group in the chain, but all of R ^{6 to} R ⁸ must not be hydrogen atoms. ⁶ and R ⁷ may combine with each other to form a ring, and R ⁹ is a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl A group or an aryl group, and these groups may contain a carbonyl group in the chain, and R ⁹ may be bonded to 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, a cyclohexylidene group, a cyclopentylidene group, a 3-oxocyclohexylidene group, a 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 is, 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 formula (3c), the ring formed by bonding R ⁹ and R ⁶ to each other includes, for example, 2-oxacyclohexylidene, 2-oxacyclopentylidene, 2-oxa-4- Those having 4 to 10 carbon atoms such as a methylcyclohexylidene group are exemplified.

Here, as the group represented by the above formula (3a), for example, tert-amyl group, 1,1-dimethylethyl group, 1,1-dimethylbutyl group, 1-ethyl-1
Tert-alkyl groups having 4 to 10 carbon atoms such as -methylpropyl group, 1,1-diethylpropyl group, etc., 1,1-dimethyl-3-oxobutyl group, 3-oxocyclohexyl group, 1-methyl-3 A 3-oxoalkyl group such as -oxo-4-oxacyclohexyl group is preferred.

The group represented by the above 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 above 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 n is an integer of 1 to 10, which satisfies k + h + m + n ≦ 10.

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

[0034]

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 synthesized from carboxylic acid derivatives having a tricyclic aromatic skeleton represented by the following formulas (5) and (6). be able to.

[0036]

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 J. Org. Chem. , 30,9
27 (1965).

[0038]

Embedded image (In the formula, R ⁶ , R ⁷ , and R ⁸ are the same as described above.)

In the above reaction, the amount of trifluoroacetic anhydride to be used is 1 to 10 mol, especially 1 to 1 mol of carboxyl group in the carboxylic acid represented by the formulas (5) and (6).
It is preferable to add at a ratio of up to 5 mol. The amount of the alcohol used is preferably 1 to 10 mol, particularly preferably 1 to 5 mol, per 1 mol of the carboxyl group in the carboxylic acid represented by the formulas (5) and (6).

The above reaction is preferably carried out in an organic solvent such as methylene chloride or THF at a temperature in the range of -70 to 50 ° C. The reaction time can be appropriately selected depending on the conditions, but the reaction is completed in about 30 minutes to 4 hours.

Further, as the acid labile group, the above-mentioned general formula (3)
There are various methods for synthesizing the compound having the group represented by b), and the method is not particularly limited. A preferable example is 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 this case, the amount of the silylalkyl halide of the above formula (8) is 1 to 1 mol of the carboxyl group in the carboxylic acid represented by the above formula (5) or (6).
It is desirable to add 10 mol, especially 1 to 5 mol.

The base used as the catalyst is not particularly limited, but specific examples include sodium hydrogencarbonate, sodium carbonate, potassium hydrogencarbonate, potassium carbonate, sodium hydride, potassium hydride, sodium methylate, and sodium ethylate. Lat, 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.

Further, an acid labile group represented by the above general formula (3)
There are various methods for synthesizing the compound having the group represented by c), and the method is not particularly limited. As a preferred example, the carboxylic acid represented by the formula (5) or (6) is added to There is a method of reacting a vinyl ether represented by the formula (9).

[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 1 to 10 mol, especially 1 to 1 mol of the carboxyl group in the carboxylic acid represented by the formula (5) or (6).
A proportion of 5 mol is preferred.

The acid catalyst used is not particularly limited, but specific examples include trifluoromethanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, p-
Examples include pyridinium toluenesulfonate and pyridinium m-nitrobenzenesulfonate. The acid catalyst is preferably used in an amount of 0.001 to 1 mol per 1 mol of the carboxyl group in the carboxylic acid represented by the above formulas (5) and (6).

The above reaction is preferably carried out using a solvent, and the reaction solvent used is not particularly limited. Specific examples include ethers such as tetrahydrofuran, tetrahydropyran and 1,4-dioxane. 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; and mixed solvents thereof. Among them, particularly preferred are tetrahydrofuran, tetrahydropyran, and mixtures thereof with halogenated hydrocarbons such as methylene chloride and chloroform.

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.

As a second preferred example of a method for synthesizing a compound having a group represented by the general formula (3c) as an acid labile group, 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 haloalkoxyalkyl represented by the following formula (10).

[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 used is not particularly limited, but specific examples include methoxymethyl chloride, methoxymethyl bromide, methoxymethyl iodide, ethoxyethyl chloride, ethoxymethyl chloride, ethoxybromide. Methyl, methoxyethoxymethyl chloride, tetrahydrofuranyl chloride, tetrahydropyranyl chloride and the like can be mentioned. The haloalkoxyalkyl represented by the formula (10) is preferably used in an amount of 1 to 10 molar equivalents relative to the carboxyl group of the carboxylic acid derivative of the formula (5) or (6) as the raw material.

The base used is not particularly limited, but specific examples include sodium hydrogencarbonate, sodium carbonate, potassium hydrogencarbonate, potassium carbonate, sodium hydride, potassium hydride, sodium methylate, and sodium ethylate. Or alkali metal salts such as potassium tert-butylate, or triethylamine, diisopropylmethylamine, dimethylaniline,
Pyridine, 4-N, N-dimethylaminopyridine, 4-
In addition to organic bases such as (1-piperidino) pyridine,
Various phase transfer catalysts are also included. The amount of the base to be used is preferably 1 to 10 molar equivalents relative to the carboxyl group in the carboxylic acid represented by the above formulas (5) and (6).

The above reaction is preferably carried out using a solvent. The reaction solvent used is not particularly limited, but specific examples include methanol, ethanol, propanol, 2-methylethanol, butanol and tert.
Alcohols such as -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; N, N-dimethyl Formamide, N, N-
Examples include aprotic polar solvents such as dimethylacetamide and dimethylsulfoxide, and mixed solvents thereof, among which acetone, N, N-dimethylformamide, and N, N-dimethylacetamide are particularly preferable. 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 compound of the above formula (1) or (2) is useful as a light absorber for a chemically amplified positive resist material.
In this case, as the light absorber, one kind of the compounds of the above formulas (1) and (2) may be used alone, or two or more kinds may be used in combination.

[0061]

The compounds of the formulas (1) and (2) of the present invention
When used as a light absorber for a chemically amplified positive resist material, it has no sublimability, has a very large light absorption in the deep ultraviolet region, and is decomposed in the presence of an acid to liberate a carboxylic acid. Therefore, the chemically amplified positive resist material containing the compound is sensitive to high energy rays such as far ultraviolet rays, electron beams, and X-rays, in particular, a KrF excimer laser,
While suppressing the appearance of standing waves and halation, it does not adversely affect the dissolution characteristics and storage stability, and has high resolution suitable for fine processing technology.

[0062]

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

Example 1 tert-Amyl 9-anthracenecarboxylate (in the formula (4a), R ⁵ = te
Synthesis of rt-amyl group compound) 11.1-g (0.05 mol) of 9-anthracenecarboxylic acid (compound of the above formula (4a) where R ⁵ = H) was
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-amyl alcohol while maintaining the temperature at 5 ° C. or lower 35.
3 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, 191 g of a 10% aqueous sodium hydroxide solution was added to the reaction solution to neutralize the acid, and extracted with 202 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. 8.5 g (yield 58)
%), 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-amyl are shown below.

[0065]

Embedded image < ¹ H-NMR: CDCl ₃ , δ (ppm)> (a) 0.89 triplet 3H (b) 1.60 quadruplet 2H (c) 1.80 singlet 6H (d) 7.26 -7.58 Multiplet 4H (e) 8.00 to 8.11 Multiplet 4H (f) 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: 82.2 H: 6.9 Found C: 82.5 H: 7.0

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 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), purity 98
%.

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

[0068]

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 ¹ H <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

Example 3 Synthesis of ethoxyethyl 9-anthracenecarboxylate (compound of the above formula (4a) wherein R ⁵ = ethoxyethyl group) Instead of chloromethyl methyl ether used in Example 2, 1-chloroethyl When the reaction was carried out in the same manner as in 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.

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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

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 a 5% aqueous sodium hydrogen carbonate solution 21 was added.
0 g was added to neutralize the acid and stop the reaction. The solvent was distilled off from the separated organic layer under reduced pressure to obtain an oil. The oily substance is purified by silica gel chromatography (elution solvent: ethyl acetate-hexane) to give tetrahydropyranyl 9-anthracenecarboxylate (see the following structural formula).
Was isolated. 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.

[0073]

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

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 Example 4 except that dihydrofuran was used instead of 3,4-dihydro-2Hpyran used in Example 4, and tetrahydrofuranyl 9-anthracenecarboxylate was obtained. Was obtained with a purity of 98% and a yield of 72%.

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 Example 4 except that n-propyl vinyl ether was used instead of 3,4-dihydro-2Hpyran used in Example 4, and 9-anthracene was obtained. N-Propoxyethyl carboxylate has a purity of 97% and a yield of 68%
Was obtained.

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 Example 4 except that tert-butyl vinyl ether was used in place of 3,4-dihydro-2Hpyran used in Example 4. Tert-Butoxyethyl anthracenecarboxylate was obtained with a purity of 98% and a yield of 70%.

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

Example 9 iso-butoxyethyl 9-anthracenecarboxylate (in the above formula (4a), R ⁵
= Iso-butoxyethyl group compound) In place of the ethyl vinyl ether used in Example 4, i-
When the reaction was carried out in the same manner as in Example 4 except that butyl vinyl ether was used, 9-anthracene carboxylic acid is
o-Butoxyethyl was obtained with a purity of 98% and a yield of 75%.

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

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

Example 12 The 9-anthracenecarboxylic acid used in Example 1 (in the above formula (4a), R ⁵ = H
In the same manner as in Example 1 except that 1-anthracenecarboxylic acid (compound of the above 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%;
46% yield

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

[Examples 23 to 33] Instead of 1-anthracenecarboxylic acid used in 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 Examples 12 to 22 except that the following compounds were used, respectively, to obtain the following compounds. Example 23 2-Anthracenecarboxylic acid tert-
Butyl (compound of R ⁵ = tert-butyl group in the formula (4c)) purity 99%, yield 46% <Example 24> Methoxymethyl 2-anthracenecarboxylate (R ⁵ = methoxymethyl in the formula (4c) the compounds of group) 98% pure, compounds of the R ⁵ = an ethoxyethyl group in a yield of 80% <example 25> 2-anthracene carboxylic acid ethoxyethyl (formula (4c)) 97% purity, 77% yield <embodiment Example 26> Tetrahydropyranyl 2-anthracenecarboxylate (compound of R ⁵ = tetrahydropyranyl group in the above formula (4c)) purity 97%, yield 66% <Example 27> Tetrahydrofuranyl 2-anthracenecarboxylate (the above-mentioned compound) R ⁵ = compound of tetrahydrofuranyl group) of 99% purity in the formula (4c), 69% yield <example 28> 2- Ant Sen carboxylic acid n- propoxyethyl (Formula (R ⁵ = n- compounds of propoxyethyl group in 4c)) 99% purity, 75% yield <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
% Pure 98% (R ⁵ = n- compounds of butoxyethyl In the formula (4c)) <Example 30> 2-anthracene carboxylic acid n- butoxyethyl, yield 64% <Example 31> 2- anthracene carboxylic Iso-butoxyethyl acid (in the formula (4c), R ⁵ = iso-
<Example 32> Ethoxypropyl 2-anthracenecarboxylate (compound of R ⁵ = ethoxypropyl group in the formula (4c)) 98% purity, 60% yield Example 33 Trimethylsilyl 2-anthracenecarboxylate (compound of R ⁵ = trimethylsilyl group in the above formula (4c)) purity 99%, yield 86%

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 resulting brown oil was purified by silica gel chromatography (eluent: ethyl acetate-hexane = 1: 10) to give ethyl 9-anthracene methoxyacetate (R in the above formula (4e)).
⁵ = ethyl group compound) was obtained as white crystals. Yield 14.2 g (34.5%), purity 95%.

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 liquid 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 then recrystallized from ethanol to give ethyl 9-anthracenemethoxyacetate (a compound of the formula (4e) where R ⁵ = H).
Was obtained as white crystals. Yield 6.9 g (53% yield),
97% purity.

The obtained 9-anthracene methoxyacetic acid was reacted in the same manner as in Example 12 except that the 1-anthracene carboxylic acid used in Example 12 was used, and tert-butyl 9-anthracene methoxyacetate was obtained. Obtained. Purity 99%, yield 51%.

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

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

[Examples 56 to 66] Instead of 1-anthracenecarboxylic acid used in Examples 12 to 22, 4-phenanthrenecarboxylic acid (in the above formula (4g), R ⁵ =
H) (the compound of H) was reacted in the same manner as in Examples 12 to 22, and the following compounds were obtained, respectively. <Example 56> 4-phenanthrenecarboxylic acid tert
- butyl (Formula (R ⁵ = tert compounds butyl group in 4g)) 99% purity, 46% yield <Example 57> 4-phenanthrene carboxylic acid methoxymethyl (R ⁵ = methoxy in the formula (4g) compounds of methyl group) 98% pure, compounds of the R ⁵ = an ethoxyethyl group in a yield of 80% <example 58> 4-phenanthrene carboxylic acid ethoxyethyl (formula (4g)) 97% purity, 77% yield < Example 59> Tetrahydropyranyl 4-phenanthrenecarboxylate (compound of R ⁵ = tetrahydropyranyl group in the above formula (4g)) 97% purity, 66% yield <Example 60> Tetrahydrofuranyl 4-phenanthrenecarboxylate ( formula R ⁵ = compound of tetrahydrofuranyl group) of 99% purity in (4g), 69% yield <example 61> - phenanthridine (compound of R ⁵ = n- propoxy ethyl group in the formula (4g)) Ren carboxylic acid n- propoxyethyl purity 99%, yield 75% <Example 62> 4-phenanthrene carboxylic acid tert
-Butoxyethyl (in the above formula (4g), R ⁵ = te
rt-butoxyethyl group compound) purity 97%, yield 6
0% <Example 63> 4-phenanthrenecarboxylic acid n-
Butoxyethyl (compound of the above formula (4g), wherein R ⁵ = n-butoxyethyl group): 98% purity, 64% yield <Example 64> 4-phenanthrene carboxylic acid iso-
Butoxyethyl (in the above formula (4g), R ⁵ = iso)
-Butoxyethyl group compound) 98% purity, 60% yield
<Example 65> Ethoxypropyl 4-phenanthrenecarboxylate (compound of R ⁵ = ethoxypropyl group in the above formula (4g)) 98% purity, 60% yield <Example 66> Trimethylsilyl 4-phenanthrenecarboxylate (the above formula (Compound of R ⁵ = trimethylsilyl group in (4 g)) 98% purity, 81% yield

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

The novel compounds of Examples 1 to 4 described above were prepared according to Dye. 1 to Dye. 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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[0093]

[Table 1]

As is clear from the results shown in Table 1, it was found that the compounds of the present invention can greatly increase the absorbance at 248 nm as compared with the conventional light absorbers.

[Formulation Examples 1 to 20, Comparative Formulation 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, The following formula wherein a hydrogen atom is partially protected by a tetrahydrofuranyl group (Polym.
2) polyhydroxystyrene represented by the following formula (Polym. 3) in which a hydrogen atom of a hydroxyl group is partially protected with a 1-ethoxyethyl group, or a hydrogen atom of a hydroxyl group is partially tert- A polyhydroxystyrene represented by (Polym. 4) protected with a butoxycarbonyl group and a 1-ethoxyethyl group, an onium salt, a sulfonic acid derivative of pyrogallol,
From the following formulas (PAG.1) to (PAG.7) selected from benzylsulfonic acid derivatives, bisalkylsulfonyldiazomethane derivatives, and N-sulfonyloxyimide derivatives
A compound in which the phenolic hydroxyl group of bisphenol A is substituted with a tert-butoxycarbonyl group, 2- (4-hydroxyphenyl) -2- {4-
From the following formula (DRI.1), which is selected from compounds in which the phenolic hydroxyl group of (4-methyl-4-hydroxyphenyl) cyclohexylpropane is partially substituted with a tert-butoxycarbonyl group or an ethoxyethyl group,
RI. 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, the silicon wafer was heated at 100 ° C.
Was baked on a hot plate for 120 seconds. Furthermore, an excimer laser stepper (Nikon Corporation, NSR2005
(EXNA = 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, an exposure amount that resolves the top and bottom of a 0.30 μm line and space at a ratio of 1: 1 is defined as an optimum exposure amount (sensitivity: Eop) and a minimum line width of a separated line and space at this exposure amount. Is the resolution of the evaluation resist. In addition, the shape of the resolved resist pattern,
The presence or absence of standing wave was observed using a scanning electron microscope. The occurrence of scum was also confirmed by observation using a scanning electron microscope.

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[0105]

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

[0106]

[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

[0107]

[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%)

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 501 G03F 7/004 501 7/039 601 7/039 601 (72) Inventor Shigehiro Nakura Nishijo-mura, Nakakubiki-gun, Niigata 28-1 Oishi Nishifukushima Synthetic Technology Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Toshinobu Ishihara 28-1 Nishifukushima, Niigata Pref.

Claims (2)

[Claims] 1. 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 divalent aliphatic hydrocarbon group optionally containing an oxygen atom, substituted or unsubstituted optionally containing an oxygen atom, An unsubstituted divalent alicyclic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom or an oxygen atom, and R ⁵ is an acid labile group. 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 satisfies k + h + m + n ≦ 10. ) 2. The acid labile group represented by R ⁵ in the general formula (1) or (2) is a group represented by the following general formula (3a), (3b) or (3c). Carboxylic acid derivatives of 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 Alternatively, it is a branched alkenyl group or an aryl group, and these groups may contain a carbonyl group in the chain, but all of R ^{6 to} R ⁸ must not be hydrogen atoms. ⁶ and R ⁷ may combine with each other to form a ring, and R ⁹ is a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl A group or an aryl group, and these groups may contain a carbonyl group in the chain, and R ⁹ may be bonded to R ⁶ to form a ring.)