KR100351458B1 - Organic Anti-reflective coating material and its preparation - Google Patents

Abstract

The present invention is to prevent the reflection of the lower layer layer in the ultra-fine pattern forming process using a photoresist for lithography using 248 nm KrF, 193 nm ArF and 157 nm F ₂ laser during the semiconductor device manufacturing process and to prevent ArF light and photoresist itself The present invention relates to an organic anti-reflective polymer capable of removing standing waves in a thickness change of the present invention, and to a method for synthesizing the same. The present invention also relates to an anti-reflective composition containing such an organic anti-reflective polymer, an anti-reflective film using the same, and a method of manufacturing the same. . When the polymer according to the present invention is used as an anti-reflection film in an ultra-fine pattern forming process in a semiconductor manufacturing process, it eliminates CD fluctuations resulting from standing waves, reflections and underlying films due to variations in optical properties and resist thickness of the underlying film layer on the wafer. As a result, stable ultrafine patterns of 64M, 256M, 1G, 4G, and 16G DRAMs can be formed, thereby increasing product yield.

Description

Organic Anti-Reflective Polymer and its Manufacturing Method

The present invention is to prevent the reflection of the lower layer layer in the ultrafine pattern formation process using the photoresist for lithography using 248 nm KrF, 193 nm ArF and 157 nm F ₂ laser during the semiconductor device manufacturing process, The present invention relates to an antireflection organic material capable of removing standing waves due to changes in thickness. More particularly, the present invention relates to an organic anti-reflective polymer that can be used in forming ultrafine patterns of 64M, 256M, 1G, and 4G DRAMs, and a method of manufacturing the same. The present invention also relates to an anti-reflective composition containing such an organic anti-reflective polymer, an anti-reflection film using the same, and a method of manufacturing the same.

In the ultra-fine pattern formation process in the semiconductor manufacturing process, CD (critical dimension) by standing wave, reflective notching due to the optical properties of the lower layer on the wafer and variation of the thickness of the photoresist layer, diffracted light from the lower layer and reflected light ) Inevitably occurs. Therefore, the introduction of a film layer capable of preventing reflection in the lower layer by introducing an organic material that absorbs light well in the wavelength range of light used as an exposure source has been proposed, and this film is an anti-reflective coating (ARC).

The antireflection film is classified into an inorganic antireflection film and an organic antireflection film according to the type of material used largely, or is classified into an absorption antireflection film and an interferometer antireflection film according to a mechanism. In the micropattern forming process using I-line of 365 nm wavelength, inorganic antireflection film is mainly used, TiN and amorphous carbon (Amorphous C) are used as an absorption system, and SiON is mainly used as an interferometer.

In the ultrafine pattern formation process using KrF light, SiON has been mainly used as an inorganic type, but efforts to use an organic compound in an antireflection film have been continued in recent years. In light of the trends to date, most of the existing organic anti-reflective coatings for KrF must satisfy the following basic conditions.

First, there should be no phenomenon that the photoresist is dissolved and peeled off by the solvent when the process is applied. To this end, the molded film must be designed to achieve a crosslinked structure, and chemicals should not be generated as a by-product.

Second, there should be no entry of chemicals such as acids or amines from the antireflection film. If the acid is migrated from the anti-reflection film, undercutting occurs at the bottom of the pattern, and bases such as amines tend to cause footing phenomenon.

Third, the anti-reflection film should have a relatively high etching rate compared to the upper photoresist so that a smooth etching process can be performed using the photoresist as a mask during etching.

Fourth, therefore, the antireflection film should be able to serve as a sufficient antireflection film with a thickness as thin as possible.

Meanwhile, a satisfactory anti-reflection film has not been developed in an ultrafine pattern forming process using ArF light. In the case of the inorganic antireflection film, a material for controlling the interference phenomenon at 193 nm, which is a light source, has not been announced yet, and efforts to use an organic antireflection film have been continued in recent years.

Therefore, in all photoresist films, it is necessary to use an organic anti-reflective material having a high absorption at a specific wavelength in order to prevent standing waves and reflections generated during exposure and to remove the influence of back diffraction and reflected light from the lower layer. It is an urgent task.

U.S. Patent No. 4,910,122 discloses such an organic antireflection film, which is introduced into the lower portion of the photosensitive layer such as photolithography to remove defects of the reflected light. The anti-reflection film includes a light absorbing dye component and has a uniform thin film form, and it has been described that the introduction of the anti-reflection film can produce a sharp photoresist pattern by absorbing light reflected from a conventional substrate. By the way, the conventional ARC for DUV has a problem that the configuration is complicated and there are many limitations in the selection of the material, which is difficult to apply to the process. Conventional anti-reflective coating compositions include, for example, polyamic acid, curcumin, bixin, sudan orange G, cyclohexanone (components described in the above-mentioned US patent). cyclohexanone), and N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) is composed of a mixture of six compounds. It consists of four compounds of dye system each component absorbs light of a specific wavelength and two solvents for dissolving them.The composition is complicated and it is not easy to prepare. There is also a problem of intermixing with a resist composition applied on top of an antireflection film, which may cause undesirable results.

Accordingly, an object of the present invention is to provide a novel organic compound that can be used as an anti-reflection film in the ultra-fine pattern forming process using 193 nm ArF, 248 nm KrF and 157 nm F ₂ light during the semiconductor device manufacturing process.

It is still another object of the present invention to provide a method for producing an organic compound capable of preventing diffuse reflection.

Still another object of the present invention is to provide an anti-reflective composition containing the compound for preventing anti-reflection and a manufacturing method thereof.

Still another object of the present invention is to provide an antireflection film formed using such an antireflection composition and a method of forming the same.

In the present invention, the polymer itself contains a chromophore having a high absorbance so that absorption occurs at wavelengths of 193 nm and 248 nm, and crosslinking reaction during hard bake after coating to give moldability, airtightness, and solubility of the organic antireflection film. The crosslinking mechanism of the functional group with the alcohol group in the resin was introduced so that this could occur. In particular, the present invention has maximized the efficiency and storage stability of the crosslinking reaction, the anti-reflective coating resin of the present invention has excellent solubility in all solvents of the hydrocarbon system and has a solvent resistance that does not dissolve in any solvent during hard baking . Therefore, no problem occurs when the photoresist film is applied, and undercutting and footing do not occur when the pattern is formed. In particular, since it is formed of an acrylate-based polymer, it has an excellent etching rate compared to the photoresist film during etching. The selection ratio was improved.

That is, this invention provides the polymer which has a structure of following General formula (4) in order to achieve the above objective, and whose molecular weight is in the range of 5000-1 million.

(Formula 4)

Where

R and R ₀ each represent hydrogen or a methyl group, R ₁ to R ₉ are hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, C ₁ to C ₆ substituted and unsubstituted straight or branched chain alkyl, or Alkoxyalkyl. x and y are each 0.01 to 0.99 mole fraction, and l and m each represent an integer of 1 to 2 and 2 to 4, respectively.

The polymer according to the present invention is designed to contain a chromophore (anthracene group) having high absorbance to absorb at 193 nm and 248 nm wavelengths, and to contain a hydroxyl group so that the antireflection film formed using the polymer can have a crosslinked structure. . However, the molecular weight of the polymer according to the present invention is a conventional molecular weight for the polymer for the anti-reflection film, and since it is well known to those skilled in the art before the present application (see US Pat. No. 5,886,102), these molecular weights are characterized by the present invention. It is not.

The polymer according to the present invention as described above may be prepared by polymerizing a 9-anthracenealkyl acrylate monomer (I) and a hydroxyalkyl acrylate monomer (II) with a initiator in a solvent as in Scheme 1 below. At this time, each monomer has a ratio of 0.01 to 0.99 mole fraction.

Wherein R and R ₀ each represent hydrogen or a methyl group, and R ₁ to R _{9 each} represent hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, C ₁ to C ₆ substituted and unsubstituted straight chain or Branched alkyl or alkoxyalkyl, l and m each represent an integer of 1 to 2 and 2 to 4;

The initiator that can be used to prepare the polymer according to the present invention may be a general radical initiator, preferably 2,2-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, t One selected from the group consisting of -butyl peroxide can be used.

In addition, in the method for producing a polymer according to the present invention as described above, a solvent may be used as a general organic solvent, preferably selected from the group consisting of tetrahydrofuran, toluene, benzene, methyl ethyl ketone or dioxane. Can be used.

And, in the method for producing a polymer according to the invention as described above, the reaction temperature is preferably carried out the polymerization reaction at 50 ~ 90 ℃.

In addition, the 9-anthracenealkyl acrylate monomer (I) used to prepare the polymer according to the present invention may be prepared by reacting 9-anthracenealkyl alcohol with an acryloyl chloride-based compound in a solvent as in Scheme 2 below. Can be.

Wherein R represents hydrogen or a methyl group, R ₁ to R ₉ represent hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, C ₁ to C ₆ substituted and unsubstituted straight or branched chain alkyl or alkoxyalkyl N represents an integer of 1 to 2.

In addition, the hydroxyalkyl acrylate monomer (II) and methyl methacrylate monomer (III) used to prepare the polymer according to the present invention can be obtained commercially or directly prepared.

The present invention also comprises a resin based on a combination of the polymer according to the present invention and the polymer of the following general formula 3, or together with one or two or more additives selected from the group consisting of anthracene derivatives shown in Table 1 below. It provides an anti-reflection film composition comprising a.

(Formula 3)

Where

R each represents hydrogen or a methyl group, and R ₀ represents a methyl group or an ethyl group.

In Table 1, R ₁ , R ₂ , or R ₃ are each independently hydrogen, hydroxy, hydroxymethyl or C ₁ -C ₅ substituted or unsubstituted straight or branched chain alkyl or alkoxyalkyl.

The polymer of Formula 3 is reacted with methacryloyl chloride (IV) and 4-hydroxybenzaldehyde (V) as shown in Scheme 3 to obtain a monomer 4-formylphenyl methacrylate (VI), and then The monomers can be prepared by polymerizing with an initiator in a solvent and then replacing the 4-formyl group with methanol or ethanol.

The antireflective coating composition according to the present invention is prepared by dissolving the polymer according to the present invention and the polymer of the general formula 3 in an organic solvent, and then adding 0.1 to 30% by weight of the compound selected from Table 1 alone or to it.

The organic solvent which can be used at this time can use a conventional organic solvent, Preferably it consists of ethyl 3-ethoxy propionate, methyl 3-methoxy propionate, cyclohexanone, and propylene glycol methyl ether acetate. One selected from the group may be used, and the amount thereof is preferably 200 to 5000% by weight of the antireflection film resin polymer.

The present invention provides an anti-reflection film comprising a composition according to the present invention, or together with a composition containing one or two or more compounds selected from the group consisting of anthracene derivatives of the above formulas (1) to (18). The anti-reflection film is manufactured by filtering the anti-reflection film composition, coating the wafer, and hard-baking the cross-linking anti-reflection film resin to produce a semiconductor device. This crosslinked structure makes it possible to form optically stable exposure conditions as the organic antireflection film when the photosensitive film is applied.

The antireflection film formed according to the present invention was found to exhibit excellent performance as an organic antireflection film in the ultrafine pattern formation process using 248 nm KrF, 193 nm ArF and 157 nm F ₂ laser, and 157 nm E- as an exposure light source in addition to ArF and KrF light. Even when using a beam, EUV (extremely ultraviolet), ion beam, etc., it was confirmed that excellent anti-reflective effect.

Hereinafter, the present invention will be described in more detail. However, this embodiment is not intended to limit the scope of the present invention, but is presented by way of example only.

Example 1 Synthesis of Poly [9-anthracenemethyl acrylate- (2-hydroxyethyl acrylate)] binary copolymer

Synthesis of 9-anthracenemethylacrylate

0.5 mol of 9-anthracenemethanol and 0.5 mol of pyridine are dissolved in tetrahydrofuran and 0.5 mol of acryloyl chloride is added to react. After filtering the reaction solution and again extracted with ethyl acetate, washed several times with distilled water and dried using a vacuum distillation to obtain 9- anthracene methyl acrylate represented by the following formula (19). At this time, the yield was 84%.

Synthesis of Poly [9-anthracenemethyl acrylate- (2-hydroxyethyl acrylate)] binary copolymer

Add 0.5 mole of 9-anthracenemethylacrylate monomer and 0.5 mole of 2-hydroxyethyl acrylate to a 500 ml round bottom flask, add 300 g of tetrahydrofuran (THF) prepared before stirring, and mix thoroughly. 0.1 g-3g of (AIBN) was added and reacted for 5-20 hours at a temperature of 60 ° C to 75 ° C under a nitrogen atmosphere. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, filtered and dried to obtain a poly [9-anthracenemethylacrylate- (2-hydroxyethylacrylate) having a structure represented by the following Chemical Formula 20, which is a polymer according to the present invention. )] A resin is obtained. At this time, the yield was 83%.

Example 2) Synthesis of Poly [9-anthracenemethylacrylate- (3-hydroxypropylacrylate)] binary copolymer

0.5 mole of 9-anthracene methyl acrylate monomer synthesized in Example 1 and 0.5 mole of 3-hydroxypropyl acrylate were added to a 500 ml round bottom flask, and 300 g of tetrahydrofuran (THF) prepared in advance was stirred. 0.1 g-3 g of azobisisobutylonitrile (AIBN) was added thereto, followed by reaction for 5-20 hours at a temperature of 60 ° C. to 75 ° C. under a nitrogen atmosphere. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, filtered and dried to obtain a poly [9-anthracenemethylacrylate- (3-hydroxypropylacrylate) having a structure represented by the following Chemical Formula 21, which is a polymer according to the present invention. )] A resin is obtained. At this time, the yield was 82%.

Example 3 Synthesis of Poly [9-anthracenemethylacrylate- (2-hydroxybutylacrylate)] Copolymer

0.5 mole of 9-anthracenemethylacrylate monomer synthesized in Example 1 and 0.5 mole of 4-hydroxyethyl acrylate were added to a 500 ml round bottom flask, and 300 g of tetrahydrofuran (THF) prepared in advance was stirred. 0.1 g-3 g of azobisisobutylonitrile (AIBN) was added thereto, followed by reaction for 5-20 hours at a temperature of 60 ° C. to 75 ° C. under a nitrogen atmosphere. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, and then filtered and dried to obtain a poly [9-anthracenemethylacrylate- (4-hydroxybutylacrylate) having a structure represented by Chemical Formula 22, which is a polymer according to the present invention. )] A resin is obtained. At this time, the yield was 81%.

Example 4 Synthesis of Poly [9-anthracenemethylmethacrylate- (2-hydroxyethylacrylate)] binary copolymer

Synthesis of 9-anthracenemethylmethacrylate

0.5 mole of 9-anthracenemethanol and 0.5 mole of pyridine are dissolved in tetrahydrofuran and 0.5 mole of methacryloylchloride is added. After filtering the reaction solution and again extracted with ethyl acetate, washed with distilled water several times and dried using a vacuum distillation to obtain 9- anthracene methyl methacrylate represented by the following formula (23). At this time, the yield was 83%.

Synthesis of Poly [9-anthracenemethylmethacrylate- (2-hydroxyethylacrylate)] binary copolymer

0.5 mole of 9-anthracene methyl methacrylate monomer and 0.5 mole of 2-hydroxyethyl acrylate were added to a 500 ml round bottom flask, and 300 g of tetrahydrofuran (THF) prepared before stirring was thoroughly mixed. Then, 2.2'-azobisisobutyloni was mixed. 0.1g-3g of krill (AIBN) was added and then reacted for 5-20 hours at a temperature of 60 ° C to 75 ° C under a nitrogen atmosphere. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, and then filtered and dried to obtain a methyl methacrylate- (2-hydroxyethyl acrylate)] resin having a structure represented by Chemical Formula 24, which is a polymer according to the present invention. Obtained. At this time, the yield was 79%.

Example 5 Synthesis of Poly [9-anthracenemethylmethacrylate- (3-hydroxypropylacrylate)] binary copolymer

0.5 mole of 9-anthracene methyl methacrylate monomer synthesized in Example 4 and 0.5 mole of 3-hydroxypropyl acrylate were added to a 500 ml round bottom flask, and 300 g of tetrahydrofuran (THF) prepared in advance was stirred. -0.1 g-3 g of azobisisobutylonitrile (AIBN) is added thereto, followed by reaction for 5-20 hours at a temperature of 60 to 75 ° C. under a nitrogen atmosphere. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, and then filtered and dried to obtain a poly [9-anthracene methacrylate- (3-hydroxypropylacrylate) having a structure represented by Chemical Formula 25, which is a polymer according to the present invention. )] A resin is obtained. At this time, the yield was 81%.

Example 6 Synthesis of Poly [9-anthracenemethylmethacrylate- (4-hydroxybutylacrylate)] binary copolymer

0.5 mole of 9-anthracene methyl methacrylate monomer synthesized in Example 4 and 0.5 mole of 4-hydroxybutyl acrylate were added to a 500 ml round bottom flask, and 300 g of tetrahydrofuran (THF) prepared in advance was stirred and mixed thoroughly. -0.1 g-3 g of azobisisobutylonitrile (AIBN) is added thereto, followed by reaction for 5-20 hours at a temperature of 60 to 75 ° C. under a nitrogen atmosphere. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, filtered and dried to obtain a poly [9-anthracenemethyl methacrylate- (4-hydroxybutylacryl) having a structure represented by Chemical Formula 26, which is a polymer according to the present invention. Rate)] resin is obtained. At this time, the yield was 81%.

Example 7 Synthesis of Poly [9-anthraceneethylacrylate- (2-hydroxyethylacrylate)] binary copolymer

Synthesis of 9-anthraceneethyl acrylate

0.5 mole of 9-anthraceneethanol and 0.5 mole of pyridine are dissolved in tetrahydrofuran and 0.5 mole of acryloyl chloride is added. The reaction solution was filtered and extracted again with ethyl acetate, washed several times with distilled water and dried using a vacuum distillation to obtain 9-anthracene ethyl acrylate represented by the following formula (27). At this time, the yield was 80%.

Synthesis of Poly [9-anthraceneethylacrylate- (2-hydroxyethylacrylate)] binary copolymer

0.5 mole of 9-anthraceneethyl acrylate monomer and 0.5 mole of 2-hydroxyethyl acrylate were added to a 500 ml round bottom flask, and 300 g of tetrahydrofuran (THF) prepared before stirring was thoroughly mixed. 0.1 g-3g of (AIBN) was added and reacted for 5-20 hours at a temperature of 60 ° C to 75 ° C under a nitrogen atmosphere. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, filtered and dried to obtain a poly [9-anthraceneethylacrylate- (2-hydroxyethylacrylate) having a structure represented by the following Chemical Formula 28, which is a polymer according to the present invention. )] A resin is obtained. At this time, the yield was 82%.

Example 8 Synthesis of Poly [9-anthraceneethylacrylate- (3-hydroxypropylacrylate)] Binary Copolymer

0.5 mole of 9-anthraceneethyl acrylate monomer synthesized in Example 7 and 0.5 mole of 3-hydroxypropyl acrylate were added to a 500 ml round bottom flask, and 300 g of tetrahydrofuran (THF) prepared in advance was stirred. 0.1 g-3 g of azobisisobutylonitrile (AIBN) was added thereto, followed by reaction for 5-20 hours at a temperature of 60 ° C. to 75 ° C. under a nitrogen atmosphere. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, filtered and dried to obtain a poly [9-anthraceneethylacrylate- (3-hydroxypropylacrylate) having a structure represented by the following Chemical Formula 29, which is a polymer according to the present invention. )] A resin is obtained. At this time, the yield was 81%.

Example 9 Synthesis of Poly [9-anthraceneethylacrylate- (4-hydroxybutylacrylate)] binary copolymer

0.5 mole of 9-anthraceneethyl acrylate monomer synthesized in Example 7 and 0.5 mole of 4-hydroxybutyl acrylate were added to a 500 ml round bottom flask, and 300 g of tetrahydrofuran (THF) prepared in advance was stirred. 0.1 g-3 g of azobisisobutylonitrile (AIBN) was added thereto, followed by reaction for 5-20 hours at a temperature of 60 ° C. to 75 ° C. under a nitrogen atmosphere. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, and then filtered and dried to obtain poly [9-anthraceneethylacrylate- (4-hydroxybutylacrylate) having a structure represented by Chemical Formula 30, which is a polymer according to the present invention. )] A resin is obtained. At this time, the yield was 80%.

Example 10 Synthesis of Poly [4- (1,1-dimethoxymethyl) phenylmethacrylate] Resin

Synthesis of Poly [4-formylphenylmethacrylate]

31.3 g (0.3 mol) of methacryloyl chloride was added to a 300 ml round-bottomed flask containing 200 g of tetrahydrofuran (THF), which was then completely dissolved. Then, 26 g of pyridine was added and 36.6 g (0.3 mol) of 4-hydroxybenzaldehyde. ) Is slowly added dropwise and reacted for 24 hours or more, washed with deionized water, and the monomer is separated and dehydrated to obtain 4-formylphenyl methacrylate.

0.5 mole of 4-formylphenyl methacrylate and 300 g of tetrahydrofuran (THF) were added to a 500 ml round bottom flask, and 0.1 g-3 g of 2.2'-azobisisobutylonitrile (AIBN) was added under a nitrogen atmosphere while stirring. The reaction is carried out at 60 ° C to 75 ° C for 5-20 hours. After completion of the reaction, the solution was precipitated in ethyl ether or normal nucleic acid solvent, filtered and dried to obtain a poly [4-formylphenyl methacrylate] resin. The yield was 80% at this time.

Synthesis of Poly [4- (1,1-dimethoxymethyl) phenylmethacrylate]

15 g of the obtained resin and 200 ml of tetrahydrofuran were added to a 400 ml Erlenmeyer flask, 0.5 g of HCl and 100 g of methanol were added, and then reacted at about 60 ° C. for about 12 hours. The solution was precipitated in an ethyl ether or normal hexane solvent, and then filtered. Drying affords a poly [4- (1,1-dimethoxymethyl) phenylmethacrylate] resin having the structure of formula (31) which is a polymer according to the invention. The yield was 82%.

Example 11) Synthesis of Poly [4- (1,1-diethoxymethyl) phenylmethacrylate] Resin

15 g of poly [4-formylphenyl methacrylate] resin and 200 ml of tetrahydrofuran (THF) synthesized in Example 10 were added to a 400 ml Erlenmeyer flask, 0.5 g of HCl and 150 g of ethanol were added, and the reaction was performed at about 60 ° C. for about 12 hours. The solution was precipitated in an ethyl ether or normal hexane solvent, filtered and dried to obtain a poly [4- (1,1-diethoxymethyl) phenyl methacrylate having a structure represented by the following Chemical Formula 32, which is a polymer according to the present invention. Resin is obtained. The yield was 80% at this time.

Example 12 Preparation of Anti-Reflection Film

After mixing the polymer according to the present invention prepared in Examples 1 to 9 and the same polymer as in Examples 10, 11 and dissolved in propylene glycol methyl ether acetate (PGMEA), this solution is used alone or in Table 1 0.1 to 30% by weight of the compound of Formulas 1 to 18 were added to dissolve completely, and then the filtered solution was applied to the wafer and hard baked at 80 to 300 ° C. for 10 to 1000 seconds. Then, a photosensitive film is apply | coated and a fine pattern formation process is performed.

As described above, the present invention comprises one or two or more additives selected from the group consisting of an anthracene derivative of Table 1 and a resin based on a combination of one of the polymers of Formula 4 and one of the polymers of Formula 3. An antireflection film is provided, which contains a chromophore in the resin itself and satisfies sufficient absorbance to have as the antireflection film.

In particular, in the present invention, the efficiency and storage stability of the crosslinking reaction are maximized, and the anti-reflective coating resin of the present invention has excellent solubility in all solvents of the hydrocarbon-based solvent and does not dissolve in any solvent during hard baking. . Therefore, no problem occurs when the photoresist film is applied, and undercutting and footing do not occur when the pattern is formed. In particular, since it is formed of an acrylate-based polymer, it has an excellent etching rate compared to the photoresist film during etching. The selection ratio was improved.

Therefore, by using the polymer according to the present invention as an anti-reflection film in the ultra-fine pattern forming process of the semiconductor manufacturing process, exposure is not only performed in lithography process using 248 nm KrF, 193 nm ArF and 157 nm F ₂ laser, but also in addition to ArF and KrF light. Even when 157nm E-beam, EUV (extremely ultraviolet), ion beam, etc. are used as the light source, it shows excellent anti-reflective effect, preventing reflection of lower layer layer and eliminating standing wave caused by thickness change of light and photoresist itself. It is possible to form stable ultra-fine patterns of 1G, 4G, and 16G DRAMs, thereby increasing the yield of products.

Claims (29)

delete The following 9-anthracenealkyl acrylate monomer (I) and hydroxyalkyl acrylate monomer (II) are polymerized in a solvent with an initiator as in Scheme 1 below to have a structure of the following general formula (4), and the molecular weight is 5000 to Method to manufacture a polymer in the range of 1000000. (Scheme 1) (Formula 4) Where R and R ₀ each represent hydrogen or a methyl group, R ₁ to R ₉ are hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, C ₁ to C ₆ substituted and unsubstituted straight or branched chain alkyl, or Alkoxyalkyl, x and y are each 0.01 to 0.99 mole fraction, and l and m are integers of 1 to 2 and 2 to 4, respectively. delete delete delete delete delete delete delete delete delete The method according to claim 2, wherein the molar ratio of each monomer has a molar ratio of 0.1-0.99: 0.1-0.99. The method of claim 2, wherein the initiator is selected from the group consisting of 2,2-azobisisobutyronitrile (AIBS), acetyl peroxide, lauryl peroxide, t-butyl peroxide Manufacturing method. The method of claim 2, wherein the solvent is selected from the group consisting of tetrahydrofuran, toluene, benzene, methylethylketone or dioxane. The method of claim 2, wherein the polymerization is carried out at a temperature in the range of 50 ° C-90 ° C. delete It has a structure of following General formula 4, and contains the polymer and anthracene derivative which have a molecular weight in the range of 5000-1 million, The composition for antireflection films characterized by the above-mentioned. (Formula 4) Where R and R ₀ each represent hydrogen or a methyl group, R ₁ to R ₉ are hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, C ₁ to C ₆ substituted and unsubstituted straight or branched chain alkyl, or Alkoxyalkyl, x and y are each 0.01 to 0.99 mole fraction, and l and m are integers of 1 to 2 and 2 to 4, respectively. 18. The method of claim 17, wherein the anthracene derivative includes anthracene, 9-anthracenemethanol, 9-anthracenecarbonitrile, 9-anthracenecarboxylic acid, ditranol, 1,2,10-anthracentriol, anthraflavic acid, 9- Anthaldehyde oxime, 9-anthralaldehyde, 2-amino-7-methyl-5-oxo-5H- [1] benzopyrano [2,3-b] pyridine-3-carbonitrile, 1-aminoanthraquinone , Anthraquinone-2-carboxylic acid, 1,5-dihydroxyanthraquinone, anthrone, 9-anthryltrifluoromethylketone, 9-alkylanthracene derivative of formula (16), 9-carboxy anthracene of formula (17) Derivatives, anti-reflective coating composition, characterized in that one or more compounds selected from the group consisting of 1-carboxyl anthracene derivative In the above formula R ₁ , R ₂ , R ₃ is —H, —OH, —CH ₃ , —CH ₂ OH, — (CH ₂ ) nCH ₃ or substituted or unsubstituted straight or branched chain alkyl of 1 to 5 carbon atoms, or alkoxy alkyl Where n is an integer from 1 to 3, After dissolving a polymer having a structure of the following general formula (4) and a molecular weight in the range of 5000 to 1000000 in an organic solvent, anthracene, 9-anthracenemethanol, 9-anthracenecarbonitrile, 9-anthracenecarboxylic acid, ditranol, 1,2,10-anthracentriol, anthraclavic acid, 9-anthralaldehyde oxime, 9-anthralaldehyde, 2-amino-7-methyl-5-oxo-5H- [1] benzopyrano [2, 3-b] pyridine-3-carbonitrile, 1-aminoanthraquinone, anthraquinone-2-carboxylic acid, 1,5-dihydroxyanthraquinone, anthrone, 9-anthryltrifluoromethylketone, formula 16 Preparation of an anti-reflective coating composition characterized in that the addition of one or two or more compounds selected from the group consisting of 9-alkyl anthracene derivative of the formula, 9-carboxyl anthracene derivative of the formula (17) Way. (Formula 4) Where R and R ₀ each represent hydrogen or a methyl group, R ₁ to R ₉ are hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, C ₁ to C ₆ substituted and unsubstituted straight or branched chain alkyl, or Alkoxyalkyl, x and y are each 0.01 to 0.99 mole fraction, and l and m are integers of 1 to 2 and 2 to 4, respectively. 20. The method of claim 19, wherein the amount of the anthracene derivative is 0.1-30 wt%. 20. The method of claim 19, wherein the organic solvent is selected from the group consisting of ethyl 3-ethoxypropionate, methyl 3-methoxy propionate, cyclohexanone, and propylene glycol methyl ether acetate. . It has a structure of following General formula 4, and mixed the polymer which has a molecular weight in the range of 5000-1 million, and the polymer which has a structure of following General formula 3, The composition for antireflection films characterized by the above-mentioned. (Formula 4) Where R and R ₀ each represent hydrogen or a methyl group, R ₁ to R ₉ are hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, C ₁ to C ₆ substituted and unsubstituted straight or branched chain alkyl, or Alkoxyalkyl, x and y are each 0.01 to 0.99 mole fraction, and l and m are integers of 1 to 2 and 2 to 4, respectively. (Formula 3) Where R each represents hydrogen or a methyl group, and R ₀ represents a methyl group or an ethyl group. 23. The antireflection film composition according to claim 22, further comprising an anthracene derivative. The anthracene derivative according to claim 23 is anthracene, 9-anthracenemethanol, 9-anthracenecarbonitrile, 9-anthracenecarboxylic acid, ditranol, 1,2,10-anthracentriol, anthraflavic acid, 9-anthane Tradaldehyde oxime, 9-anthralaldehyde, 2-amino-7-methyl-5-oxo-5H- [1] benzopyrano [2,3-b] pyridine-3-carbonitrile, 1-aminoanthraquinone, Anthraquinone-2-carboxylic acid, 1,5-dihydroxyanthraquinone, anthrone, 9-anthryltrifluoromethylketone, 9-alkylanthracene derivative of Formula 16, 9-carboxy anthracene derivative of Formula 17 , 1 or 2 or more compounds selected from the group consisting of 1-carboxyl anthracene derivative of the formula (18) After mixing a polymer having a structure of the following general formula (4) and a polymer having a molecular weight in the range of 5000 to 1000000 and a polymer having the structure of the following general formula (3) in an organic solvent, anthracene, 9-anthracenemethanol, 9-anthracenecarbonitrile , 9-anthracenecarboxylic acid, ditranol, 1,2,10-anthracentriol, anthraclavic acid, 9-anthralaldehyde oxime, 9-anthralaldehyde, 2-amino-7-methyl-5-oxo -5H- [1] benzopyrano [2,3-b] pyridine-3-carbonitrile, 1-aminoanthraquinone, anthraquinone-2-carboxylic acid, 1,5-dihydroxyanthraquinone, anthrone, 9 One or two or more compounds selected from the group consisting of anthryltrifluoromethyl ketone, the 9-alkylanthracene derivative of Formula 16, the 9-carboxy anthracene derivative of Formula 17, and the 1-carboxy anthracene derivative of Formula 18 Method for producing an antireflection film composition characterized in that it is added. The method of claim 25, wherein the amount of the anthracene derivative is 0.1 to 30% by weight. The method of claim 25, wherein the organic solvent is selected from the group consisting of ethyl 3-ethoxypropionate, methyl 3-methoxy propionate, cyclohexanone, and propylene glycol methyl ether acetate. . The method of claim 17, 22 or 23 after applying the anti-reflective coating composition to the lower layer comprising the step of hard-baking the wafer at a temperature of 80 ~ 300 ℃. A semiconductor device comprising an antireflection film containing the antireflection film composition according to claim 17, 22 or 23.