KR100956394B1 - Manufacturing method of 4-9-Anthracenylbenzyl methacrylate - Google Patents

Abstract

The present invention provides anthracenyl benzyl, which is easy to manufacture linear polymers and which can be used in optical materials such as organic bottom antireflective coating material (BARC) as a chromophore-containing monomer having high light absorption in a short wavelength light source. Provided is a method for preparing 4- (9-anthracenyl) benzyl methacrylate having the following Formula 1 substituted in the side chain.

Formula 1

In the formula, R represents hydrogen and n represents 1.

Organic bottom antireflection film, chromophore-containing monomer, absorbance

Description

Manufacturing method of 4- (9-Anthracenyl) benzyl methacrylate}

The present invention contains 4- (9-anthracenyl) benzyl group and has excellent light absorption ability at short wavelength light source of 248 nm excimer laser (hereinafter referred to as "KrF"), and it is a binder in the composition when preparing an optical material such as an organic antireflection film. The present invention relates to a chromophore-containing monomer which is copolymerizable with a comonomer in a binder resin.

Recently, in order to produce a gigabit (Gb) class ultra-high density semiconductor, a KrF class short wavelength exposure light source is used and a technique of obtaining 100 nm class high resolution by increasing the opening angle of the exposure apparatus has become common.

However, despite the remarkable growth of ultra-high density semiconductor manufacturing, the conventional optical microcircuit processing technology in which only the photoresist layer, which is a photosensitive material, is spin-coated on a silicon wafer and then exposed, is used as a 100 nm class. It is impossible to make stable ultrafine circuits. This is caused by base reflection, scattering, and the like of a shorter exposure light source. Therefore, the application of a special thin film to properly control the base reflection or scattering of incident light before or after applying the photoresist layer was required.

In the case of the bottom antireflective layer applied to the lower portion of the photoresist among such separate thin films, conventionally, an inorganic substance such as SiOxNy was applied by chemical vapor deposition to suppress base reflection or scattering. However, they have a disadvantage in that it is difficult to remove them completely when necessary to remove them after the process, impossible to rework when the process is defective, and expensive chemical vapor coating equipment is required. For this reason, in recent years, using a chromophore-containing polymer composition has been replaced by a spin coating method without additional equipment. Such an antireflection film suppresses standing wave effects caused by interference between incident light upon exposure and reflected light from the ground in the photoresist layer and prevents scattering in reflection or circuit bending due to a step resulting from an already formed lower circuit or It greatly reduces the tolerance of the manufacturing process by accurately reproducing the desired critical dimension (CD).

Prior arts of chromophore-containing monomers used in BARC (Bottom Anti-Reflective Coating) compositions include Brewer Science (USP 5,919,599 (1999)) and Rohm and Haas (USP 5,886,102 (1999)), both of which are KrF exposures. An anthracene chromophore derivative having excellent absorbance at wavelength was used. In particular, in the former case, anthracene chromophore was introduced into the side chain of the polymerized polymer or oligomer, and in the latter case, a polymerizable chromophore was prepared as 9-anthracenylmethyl methacrylate and used in binder resin for BARC. .

However, such anthracene-based chromophores act as defects of the final BARC composition by the method of introduction into the binder resin despite the high absorbance at the short wavelength. In particular, when anthracene carboxylic acid is introduced into a polymer or oligomer, it is very difficult to quantify the amount introduced, and the anthracene carboxylic acid remaining in the binder resin after the introduction reaction is sublimed during the drying process to be dried. It may cause contamination. Therefore, in the example of Rohm and Haas, copolymerization with monomer containing anthracene chromophore, such as 9-anthracenylmethyl methacrylate, is easy in terms of introduction amount and free from contamination due to sublimation, but benzyl moiety shown in Scheme 1 below. Acid-promoted pyrolysis or radical inhibition of anthracene at the 10 position as in Scheme 2 causes the production of nonlinear polymers, and these include the problem of being expressed as defects such as microgels.

  Examples of non-anthracene chromophores using naphthalene chromophores (SPIE proceedings, 3678, p. 518) and examples of using sulfone or urea as polymers as chromophores (USP 5,368,989 (1997)) have been reported at KrF exposure wavelengths. Compared with the anthracene derivatives, the absorbance was relatively low.

Accordingly, the present inventors synthesized a new chromophore-containing monomer which has an equivalent level of absorbance compared to anthracene-based chromophores and does not sublime by-products generated during acid-promoted pyrolysis and does not inhibit radicals during copolymerization to synthesize a binder resin for BARC. Invented a method for the preparation of a selectable material.

Accordingly, the present invention is to overcome the problems of the conventional anthracene-based chromophore exhibiting low absorbance at KrF exposure wavelength or causing decomposition of the chromophore by acid-promoted pyrolysis or generation of nonlinear polymer by radical inhibition reaction. In order to provide a method for preparing 4- (9-anthracenyl) benzyl methacrylate (hereinafter referred to as "ABMA") in which anthracenyl benzyl is substituted in a side chain.

The present invention provides 4- (9-anthracenyl) benzyl methacrylate represented by the following formula (1).

Formula 1

In addition, the present invention is a) a mixture of 9-bromoanthracene and 4-hydroxymethylphenylboronic acid in a solvent and cross-coupling reaction in the presence of a catalyst and a base (4- represented by the formula (4) Producing 9-anthracenyl) benzyl alcohol; And b) 4- (9-anthracenyl) represented by Chemical Formula 1 by mixing the produced 4- (9-anthracenyl) benzyl alcohol with halogenated methacrylic acid or methacrylic anhydride in a solvent and reacting in the presence of a base. It provides a method for preparing 4- (9-anthracenyl) benzyl methacrylate comprising producing benzyl methacrylate.

The solvent used in step a) is acetonitrile, a nitrile solvent including propionitrile, a halogenated hydrocarbon solvent including chloroform, carbon tetrachloride, methylene chloride, ether including tetrahydrofuran, dioxane and diethoxyethane. Solvents, amide solvents containing N, N-dimethylformamide, ethyl acetate, ester solvents containing methyl acetate, acetone, ketone solvents containing methyl ethyl ketone, aromatic hydrocarbons containing benzene, toluene It is preferably selected from the group consisting of alcohol solvents including solvents, methanol, ethanol and propanol.

In addition, the base used in step a) is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, pyridine, piperidine, morpholine, triethylamine, N-methylpyrrolidine It is preferred to be selected from the configured group.

4- (9-anthracenyl) benzyl methacrylate, a chromophore material prepared according to the present invention, exhibits an equivalent level of absorbance compared to conventional anthracene chromophores.

In addition, compared to the existing anthracene chromophore 9-anthracenylmethyl methacrylate (hereinafter referred to as "AMMA"), it is possible to prepare ABMA polymers more effectively by suppressing chemical structural stability and radical inhibition by the introduction of biphenyl groups. Since the ABMA polymer can be prepared more stable against acid-promoting pyrolysis, it is a polymerizable chromophore monomer capable of producing linear polymers with minimal induction of particles originating from nonlinear branching polymers in the preparation of the final BARC composition.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings and embodiments.

The present invention is a chromophore-containing monomer for BARC used in the optical microcircuit process of the semiconductor manufacturing process 4- (9-anthracenyl) benzyl methacrylate represented by the following formula (4- (9-Anthracenyl) benzyl methacrylate, ABMA).

In the formula, R represents hydrogen and n represents 1.

According to the present invention, a benzyl group is introduced by a cross-coupling reaction of 9-bromoanthracene represented by Chemical Formula 2 and 4-hydroxymethylphenylboronic acid represented by Chemical Formula 3 in the presence of a catalyst and a base. 4- (9-anthracenyl) benzyl alcohol, which is a novel intermediate represented by the formula (4), is prepared.

In which R represents hydrogen.

In the formula, n represents 1.

In the formula, R represents hydrogen and n represents 1.

In the synthesis of Formula 4, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, pyridine, piperidine, morpholine, triethylamine, N-methylpyrrolidine, and the like can be used. Can be.

Palladium (0) or palladium (II) complexes are used as catalysts. Among the palladium (0) complexes, Pd (PPhnRm) 4 (wherein R represents toluene in nPhnRm, n and m each independently represent an integer of 0 to 3). ) May be generally used. In addition, palladium (II) complexes and phosphine ligands can be used at the same time. In general, PdCl 2 (PPhnRm) 2 (wherein R in PPhnRm represents toluene and n and m each independently represents an integer of 0 to 3) or Pd (OAc ) And PPhnRm (wherein R in PPhnRm represents toluene and n and m each independently represents an integer of 0 to 3).

Reaction solvents include nitrile solvents such as acetonitrile and propionitrile, halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride and methylene chloride, ether solvents such as tetrahydrofuran, dioxane and diethoxyethane, and N, N-dimethyl. Amide solvents such as formamide, ester solvents such as ethyl acetate, methyl acetate, ketone solvents such as acetone and methyl ethyl ketone, aromatic hydrocarbon solvents such as benzene and toluene, alcohol solvents such as methanol, ethanol and propanol And the like, and may be used with water.

The reaction temperature may be carried out under heating, particularly preferably at 50 to 80 ° C., and the reaction time is 1 to 48 hours, preferably 12 to 24 hours, and the conventional method such as distillation or extraction. Purification was carried out to obtain 4- (9-anthracenyl) benzyl alcohol, an intermediate of Formula 4.

4- (9-anthracenyl) benzyl methacrylate (ABMA), a compound represented by Formula 1, which is an object of the present invention, is halogenated represented by 4- (9-anthracenyl) benzyl alcohol represented by Formula 4 and formula 5 It can be obtained by reacting methacrylic acid or methacrylic anhydride represented by the formula (6) in the presence of a base.

Wherein X represents a halogen element (eg chlorine, bromine or iodine).

In introducing the methacryl group capable of radical polymerization in Formula 4, sodium hydride, sodium methoxide, sodium ethoxide, pyridine, piperidine, morpholine, triethylamine, N-methylpyrrolidine, etc. may be used. Can be.

The reaction solvent is carried out in anhydrous aprotic organic solvent. Aprotic organic solvents used for this purpose include nitrile solvents such as acetonitrile and propionitrile, halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride and methylene chloride, ether solvents such as tetrahydrofuran and dioxane, N, Amide solvents such as N-dimethylformamide, ester solvents such as ethyl acetate, methyl acetate, ketone solvents such as acetone and methyl ethyl ketone, aromatic hydrocarbon solvents such as benzene, toluene, and the like.

The reaction temperature is not particularly limited, and the reaction can be carried out under cooling, at room temperature or warming, particularly preferably at room temperature or lower, and the reaction time is 1 to 24 hours, preferably 5 to 13 hours. Reaction and purification by conventional methods such as washing or distillation to obtain the target compound of formula (1).

Free radical polymerization of the object of the present invention formula (1) can be obtained in a high yield compared to the polymer obtained from the AMMA ABMA polymer such as the formula (7). These results show that the polymer for BAMA-containing BARC can be effectively synthesized.

The invention is illustrated in more detail by the following examples. The following examples illustrate the present invention and the present invention is not limited to the following examples.

Example

1.Synthesis of 4- (9- anthracenyl ) benzyl alcohol

In a nitrogen atmosphere, 9-bromoanthracene (0.05 mol, 12.9 g) was added to a 300 ml reaction flask, and tetrahydrofuran (150 ml) was added and dissolved. To the reaction was added 4-hydroxymethylphenylboronic acid (0.075mol, 11.4g) and tetrakis (triphenylphosphine) palladium (0) (0.001mol, 1.16g) and sodium carbonate (0.1mol, dissolved in 10ml) 10.6 g) is added slowly, and the reaction is stirred at reflux for 24 hours.

After the reaction, the reaction is cooled to room temperature and filtered. The filtrate is distilled under reduced pressure to remove the reaction solvent, and the concentrate is dissolved in dichloromethane and washed with water. The organic layer is dried, filtered and concentrated, and then n-hexane is added to give a pale yellow crystal. Yield 75%. 1 H-NMR (CDCl 3, δ) 4.87 (s, 2H), 7.31-8.02 (m, 9H), 8.04 (d, J = 8.4 Hz, 2H), 8.49 (s, 1H)

2. Synthesis of 4- (9-anthracenyl) benzyl methacrylate (ABMA)

4- (9-anthracenyl) benzyl alcohol (0.01 mol, 2.8 g) is added to a 200 ml reaction flask, followed by methylene chloride (75 ml) and triethylamine (0.01 mol, 1.0 g). Metaacryloyl chloride (0.012 mol, 1.9 g) was slowly added to the reaction at 0 ° C., and then stirred for 12 hours at room temperature.

After the reaction, the reaction is washed with water, the organic layer is dried, filtered and concentrated and methanol is added to give light yellow crystals. Yield 78%. 1 H-NMR (CDCl 3, δ) 2.05 (s, 3H), 5.38 (s, 2H), 5.65 (s, 1H), 6.26 (s, 1H), 7.31-7.67 (m, 9H), 8.04 (d, J = 8.7 Hz, 2H), 8.49 (s, 1H)

3. Synthesis of 4- (9- anthracenyl ) benzyl methacrylate ( ABMA ) polymer

     ABMA (0.0142 mol, 5 g) produced as described above was added to a 50 ml reaction flask and 20 ml of tetrahydrofuran was added to dissolve it. AIBN (0.00057 mol, 0.0935 g) was added as a polymerization initiator, and the mixture was heated and stirred at 65 ° C. for 5 hours. After cooling to room temperature, methanol was added to crystallize, filtered and dried to obtain poly (4- (9-anthracenyl) benzyl methacrylate) as pale yellow crystals. Yield 89%, MW: 70,000 (GPC)

Comparative example

(9- Anthracenyl ) methyl Methacrylate ( AMMA Polymer Synthesis

AMMA (0.0181 mol, 5 g) was added to a 50 ml reaction flask, and 20 ml of tetrahydrofuran was added to dissolve it. AIBN (0.0072mol, 0.119g) was added as a polymerization initiator, and it stirred for 5 hours by heating at 65 degreeC. After cooling to room temperature, methanol was added to crystallize, filtered and dried to give poly (9-anthracenylmethyl methacrylate) as dark yellow crystals. Yield 75%, MW: 75,000 (GPC)

1 is a UV spectral graph showing the absorbance of 4- (9-anthracenyl) benzyl methacrylate (ABMA) synthesized according to an embodiment of the present invention. As a comparison group for 4- (9-anthracenyl) benzyl methacrylate (ABMA) newly synthesized according to the present invention, a conventional anthracene chromophore, 9-anthracenylmethyl methacrylate (AMMA) monomer, was used. Each was diluted with 10-4 molarity in acetonitrile to measure absorbance.

Referring to Figure 1, the solid line represents the absorbance of the synthesized ABMA according to the present invention, the dotted line represents the absorbance of AMMA. It can be seen that the absorbance of the synthesized ABMA is almost the same as that of the existing AMMA at 248 nm or less. Therefore, the ABMA prepared according to the embodiment of the present invention has excellent light absorption ability that is inferior to the existing anthracene chromophore in the short wavelength light source.

2 is a poly (4- (9-anthracenyl) benzyl methacrylate polymer) prepared as described above according to an embodiment of the present invention and a poly (9-anthracenylmethyl methacrylate polymer prepared according to a comparative example ) And 10 mol% of 2-hydroxycyclohexyl tosylate (HCT) were respectively mixed to perform a thermogravimetric analysis (TGA) test. The graph shows the results.

Referring to FIG. 2, TGA (Thermo- gravimetric analysis) was tested by adding 2-hydroxycyclohexyl tosylate (HCT) to the obtained ABMA polymer as TAG (Thermal acid generate). The ABMA polymer showed a weight loss of less than 10 wt% up to 250 ° C, while the AMMA polymer had a weight loss of about 20 wt%. This indicates that the ABMA polymer can be more excellent in heat resistance than AMMA, and thus it is possible to synthesize a BAMA polymer containing ABMA as a more stable chromophore for acid-promoting pyrolysis.

Therefore, 4- (9-anthracenyl) benzyl methacrylate (hereinafter referred to as "ABMA"), which is a chromophore material prepared according to the present invention, has an equivalent level of absorbance as compared to conventional anthracene-based chromophores, but also existing anthracene-based chromophores. Compared with the chemical structural stability, inhibits radical inhibition, and is more stable against acid-promoted pyrolysis, ABMA polymers can be effectively prepared.

Although the above has been illustrated and described with respect to preferred embodiments of the present invention, the present invention is not limited to the above-described specific embodiments, and those skilled in the art without departing from the gist of the present invention. Anyone can make various modifications, as well as such modifications or variations are within the scope of the appended claims.

1 is a UV spectral graph measuring the absorbance of 4- (9-anthracenyl) benzyl methacrylate (ABMA) and 9-anthracenylmethyl methacrylate (AMMA) monomer prepared according to an embodiment of the present invention to be.

2 is a graph showing the results of thermogravimetric analysis of ABMA polymer and AMMA polymer according to an embodiment of the present invention.

Claims (8)

delete 4- (9-anthracenyl) benzyl alcohol represented by the following formula (4). Formula 4 In the formula, R represents hydrogen and n represents 1. a) 9-bromoanthracene represented by the following formula (2) and 4-hydroxymethylphenylboronic acid represented by the following formula (3) are mixed in a solvent, and cross-coupling reaction is carried out in the presence of a catalyst and a base. Producing 4- (9-anthracenyl) benzyl alcohol represented by Formula 4; And b) the 4- (9-anthracenyl) benzyl alcohol produced above and halogenated methacrylic acid represented by the formula (5) or methacrylic anhydride represented by the formula (6) are mixed with a solvent and reacted in the presence of a base, A process for preparing 4- (9-anthracenyl) benzyl methacrylate comprising producing 4- (9-anthracenyl) benzyl methacrylate. Formula 1

Formula 2

Formula 3

Formula 4

Formula 5

Formula 6

In the formula, R represents hydrogen, n represents 1, and X represents a halogen element. According to claim 3, wherein the solvent used in step a) is acetonitrile, a nitrile-based solvent comprising propionitrile, chloroform, carbon tetrachloride, a halogenated hydrocarbon solvent containing methylene chloride, tetrahydrofuran, dioxane, Ether solvents containing diethoxyethane, amide solvents containing N, N-dimethylformamide, ester solvents containing ethyl acetate, methyl acetate, ketone solvents containing acetone, methyl ethyl ketone, benzene, toluene Method for producing 4- (9-anthracenyl) benzyl methacrylate, characterized in that selected from the group consisting of an aromatic hydrocarbon solvent comprising, an alcohol solvent including methanol, ethanol, propanol. The method of claim 4, wherein the solvent is used together with water. The method of claim 3, wherein the base used in step a) is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, pyridine, piperidine, morpholine, triethylamine, N- A process for preparing 4- (9-anthracenyl) benzyl methacrylate, characterized in that it is selected from the group consisting of methylpyrrolidine. According to claim 3, wherein the catalyst used in step a) is a palladium (0) or palladium (II) complex is used, the palladium (0) complex is Pd (PPh3) 4 is used, the palladium (II) ) Complex is PdCl 2 (PPh 3) 2 or Pd (OAc) 2 and PPh 3 is used with the phosphine ligand method for producing 4- (9-anthracenyl) benzyl methacrylate. According to claim 3, wherein the solvent used in step b) is acetonitrile, a nitrile-based solvent comprising propionitrile, chloroform, carbon tetrachloride, a halogenated hydrocarbon solvent containing methylene chloride, tetrahydrofuran, dioxane Ether solvent containing, amide solvent containing N, N-dimethylformamide, ethyl acetate, ester solvent containing methyl acetate, acetone, ketone solvent containing methyl ethyl ketone, benzene, toluene containing A process for producing 4- (9-anthracenyl) benzyl methacrylate, which is selected from the group consisting of aromatic hydrocarbon solvents.

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