TWI302537B - Organic anti-reflective coating compound, anti-reflective coating composition comprising the same and preparation methods thereof - Google Patents

Description

1302537 V. INSTRUCTIONS (1) Field of the invention: Organic anti-resistance in the process of lithographic printing of ultra-fine patterns using photoresist and 248 nm krypton fluoride (KrF) and 193 nm argon fluoride (ArF) The reflective polymer prevents "back reflection" of the low layer film and eliminates thickness variations caused by photoresist and light. More specifically, the organic anti-reflective polymer can be used to fabricate ultra-fine patterns of 64M (106 bit), 256M, 1G (109 bit) and 4G DRAM (Dynamic Random Access Memory) semiconductor devices. The present invention also provides an antireflective coating comprising the composition of the organic antireflective polymer, and a process for preparing the same. Technical background: In the process of manufacturing ultra-fine patterns of semiconductor devices, due to the optical properties of the low-film layer of the wafer and the thickness variation of the photoresist film, it is inevitable that "standing wave" and reflection scoring will occur. In addition, another problem caused by diffraction and reflection of the low film layer is the change in CD (critical dimension). Therefore, scientists have proposed to introduce anti-reflective coatings using organic substances that are highly absorptive in the wavelength range of the light source used. Incorporating to prevent back reflection of the low film layer. The material used for the anti-reflective coating can be divided into inorganic and organic anti-reflective coatings, or the mechanism depending on the operation can be divided into an absorptive and interfering anti-reflective coating. For lithographic printing of I-line (3 65 nm wavelength) radiation, inorganic anti-reflective coatings are mainly used; TiN and amorphous carbon are used for absorption systems, and KrF (fluorine) is used for SiCN* r in interference systems.氪)) Laser manufacturing ultra-fine patterns, mainly using SiON as inorganic anti-reflective film. However, in the case of inorganic anti-reflective film, 1302537 V. Description of invention (2) No material is known. Controls the interference of 93 nm (the wavelength of the light source). Therefore, there is much room for improvement in the organic compound as an anti-reflective coating. For a good organic anti-reflective coating, the following conditions must be met. (1) For lithographic printing, the photoresist layer must not be stripped by dissolving in a solvent. To achieve this goal, the molded coating must be designed to form a crosslinked structure without any chemical by-products. (2) For example, acid or amine chemistry The drug must not be incorporated into the anti-reflective coating or ooze out from the reflective coating. This is because if the acid oozes out from the anti-reflective coating, the bottom of the pattern will have a lower cut, and if a base such as an amine oozes, it will have a flaking phenomenon. (3) The anti-reflective coating must be etched faster than the upper photosensitive film to etch the photomask as a mask. (4) The anti-reflective coating must be as thin as possible to act as a competent anti-reflective coating. The role of existing organic antireflective substances are two types: (1) a polymer containing a chromophore, a crosslinking agent (single molecule) capable of crosslinking a polymer, and an additive (thermally variable oxidizing agent), and (2) Polymers containing chromophores and additives (thermally variable oxidizing agents) and which are themselves crosslinked. However, the problem of these two types of antireflective substances is that k値 control is almost impossible because of chromophores. The content is fixed at the time of polymerization. Thus, the polymer is re-synthesized by changing k. The present invention is a novel organic polymer for antireflective coating and a process for the preparation thereof. The antireflection coating of the foregoing polymer and a method for preparing the same; and the method for forming the antireflection coating by submicron lithography to form a pattern -4-1302537 5, the invention (3) semiconductor device. Inventive, the following compounds (1) and (2) can be used for anti-reflective coatings: (1)

In the above formulas (1) and (2): 1^ to Rd are each independently hydrogen or methyl;

Ra to Rd and R, to R, 8 are each independently 'system_H,_〇H,_〇c〇CH3 '--C00H '-ch2〇h ', fine or unsubstituted, straight or branched

Ci-5 alkyl or alkoxyalkyl; each of m' and n is an integer selected from 丨'2'3, 4 or 5; W, X, y and ζ are each a decimal number from 0. 01 to 0 99.

Rl9 and R2. Each is independent of a straight or branched Ci-I. Alkoxy group and 1302537 V. Description of invention (4) R21 is hydrogen or methyl. The compound (2) is produced by polymerizing (meth)acrolein to obtain (meth)acrylaldehyde, and then reacting the obtained polymerization product with a C, hydrazine linear or branched substituted alkanol. Specifically, the methacrylic acid is first dissolved in an organic solvent, a polymerization initiator is added, and polymerization is carried out in a vacuum at 60 to 270 ° C for 4 to 6 hours. The resulting polymer and the branched or linear substituted alkanol are then reacted at room temperature for 20 to 30 hours in the presence of trifluoromethanesulfonic acid as a catalyst. In the foregoing process, a suitable organic solvent is selected from the group consisting of tetrahydrofuran (THF), cyclohexanone, dimethylformamide, dimethyl hydrazine, dioxane, methyl ethyl ketone, benzene, toluene, xylene, and mixtures thereof. The polymerization initiator may be 2,2-azobisisobutyronitrile (AIBN), benzoquinone peroxygen, acetylated peroxygen, lauryl peroxide, tributyl acrylate, tert-butyl peroxygen Hydrogen or double tert-butylation peroxygen. Preferably, the alkanol is ethanol or methanol. Preferred compound (2) is selected from the group consisting of compounds (3) to (6): (3) Η

1302537 V. Description of invention (5) (5)

The above compounds (3) to (6) are easily hardened in the presence of an acid and other polymers having a hydroxyl group. The compound (1) is reacted with a 9-fluorenylmethylimide ester monomer, a hydroxyalkyl acrylate monomer, a glycidyl acrylate monomer and 9-decyl methacrylate in an organic solvent, and then The resulting compound is polymerized by adding a polymerization initiator. Any organic solvent can be used in the process, but preferred solvents are tetrahydrofuran, toluene, benzene, methyl ethyl ketone, dioxane or a mixture thereof. The polymerization initiator may be any conventional free radical initiator, preferably selected from 2,2f-azobisisobutyronitrile, acetylated peroxygen, lauryl peroxide and tertiary butylated peroxygen. The foregoing polymerization is preferably carried out at a temperature of from 50 to 9 (TC), and the monomer has a molar fraction of from 0.01 to 0.99. The present invention also provides an anti-polymer (1) and polymer (2) resistant The present invention also provides an antireflective coating composition comprising the compound (1), the compound (2) and an anthracene derivative as an additive. The non-limiting range of an anthracene derivative additive is selected from the group consisting of ruthenium. , 9-indole methanol, 9-indene nitrile, 9-fluorene carboxylic acid, -7- 1302537 V. Description of invention (6) Bi-l-ol, 1,2,10-nonanetriol, phthalic acid, 9_ Furfural oxime, 9-furfural '9-amine-7-methyl-5-oxo-5H[1]benzopyrano[2,3_b]pyridine-3-carbonitrile, amidoxime, hydrazine- 3-carboxylic acid, anthracene, 5-dihydroxyindole, anthrone, 9-fluorene trifluoromethanone, 9-alkyl anthracene derivative (7), 9-carboxyindole derivative (8), 1-carboxyindole derivative (9) and mixtures thereof. (7) (8) (9)

〇 I C = 〇

c=o

Wherein Ri to R5 are -?, -OH, -CH2OH or Cm substituted or unsubstituted, straight or branched alkyl or alkoxyalkyl. 1 Shi g compound (1)

The invention also provides a method for preparing an organic anti-reflective coating, the package & 1302537, the invention description (7) and the compound (2) are dissolved in an organic solvent, and the obtained solution is filtered alone or in combination with at least one of the aforementioned anthracene derivatives, and the filtrate is coated. At the bottom layer, the coating is hard baked. More specifically, the organic solvent used in the process is ethyl 3-ethoxypropionate methyl 3-methoxypropionate, cyclohexanone and propylene glycol methyl ether acetate. Preferably, the solvent is present in an amount of from 200 to about 5,000% by weight based on the total weight of the antireflective coating polymer. The preferred temperature range for hard roasting is from about 100 to about 3 Torr. An improved semiconductor device can be fabricated from any of the foregoing antireflective coating compositions. According to the invention, two monomers with high absorbency chromophore (yttrium methyl methacrylate and methyl methacrylate) are synthesized first, so that the polymer prepared by them has a wavelength of 248 nm. High absorbency. Thus, the polymer produced by the two monomers is the main polymer (Compound 1). Since the two monomers having a chromophore are weakly alkaline, any undercut due to acidity imbalance can be avoided after the coating is prepared. In addition, in order to improve the properties of the resulting organic anti-reflective coating, such as good moldability, air tightness and solvent resistance, a secondary polymer (compound 2) is also synthesized, which reacts with a hydroxyl group in the resin to form a crosslink. Therefore, cross-linking is caused in the baking step after the coating step. That is, the secondary polymer and the main polymer are crosslinked by thermal reaction. Specifically, the crosslinking agent used in the present invention in the form of a polymer can be designed to maximize the crosslinking efficiency, so that the ratio of the main polymer can be controlled, and the k値 of the antireflection coating can be freely adjusted. Further, although the antireflective coating resin is insoluble in any solvent in the hard baking step, it has good solubility in all hydrocarbon solvents. In addition, there will be no undercut or edging during the pattern making process. In particular, because the anti-reflective coating resin used in the invention is made of an acrylate polymer, the etching rate is higher than that of the photosensitive film during the etching process, and thus the anti-reflective coating is used. The resin improves the etch selectivity. By way of example, the expert can better understand the true meaning and skill of the present invention. However, the examples are only preferred examples and are not intended to limit the scope of the invention. Example 1: Poly-f-acrylic acid 9-fluorenylmethylimine ethyl ester acrylic acid 2_Zan 7, ester)_ glycidyl methacrylate-(methacrylic acid 9-yellomethyl ester method in a 500 ml round bottom flask Stirring 0.1 mole of acrylic acid 9_蒽methylimine ethyl ester monomer/0.3 mole Acrylic acid 2-hydroxyethyl ester/0.3 mol methyl methacrylate/0.3 mol -9-methyl methacrylate And 300 g of separately prepared tetrahydrofuran was added to the obtained mixture, followed by the addition of 〇.ι-3 gram of 2,2'-azobisisobutyronitrile, and the polymerization was initiated at 60 to 75 ° C under nitrogen. After the completion of the reaction, the obtained solution was precipitated by adding diethyl ether or n-hexane solvent, filtered and dried to give the titled resin (10) (yield: 83%).

-10- 1302537 V. INSTRUCTIONS (9) Example 2: Polyf-methyl methacrylate 9-fluorenylmethylimine ethyl ester-(A propyl glycerin 2 hydroxyethyl ester)-glycidyl methacrylate-(methyl Method for preparing acrylic acid 9-1:methyl ester) 1 was stirred in a 500 ml round bottom flask with 〇. 1 mol methacrylic acid 9-fluorenylmethylimine ethyl ester monomer/0.3 mol methacrylic acid 2- Hydroxyethyl ester / 0.3 mol of methyl acrylate / 0.3 mol of 9-fluorenylmethyl methacrylate, and 300 g of separately prepared tetrahydrofuran was added to the resulting mixture. Thereafter, 0.1 to 3.0 g of 2,2'-azobisisobutyronitrile was added, and the polymerization reaction was initiated at 60 to 75 ° C under nitrogen for 5 to 20 hours. After completion of the reaction, the obtained solution was precipitated by adding diethyl ether or n-hexane solvent, filtered and dried to give the title compound (yield: 84%). (Π)

Example 3: Polyf-acrylic acid 9-nonylmethylimine propionic acid 3-hydroxypropanol V Methyl methacrylate-methyl methacrylate 1 was stirred in a 500 ml round bottom flask Add 0.1 mol of 9-mercaptomethyl propyl acrylate monomer / 0.3 mol of 3-hydroxypropyl acrylate / 0.3 mol of methyl methacrylate / 0.3 mol of 9-fluorenyl methacrylate - and The resulting mixture is -11-1302537. V. Inventive Note (1 2 3 4 5 6 7 ) 300 g of separately prepared tetrahydrofuran is added. Thereafter, 0.1 to 3.0 g of 2,2'-azobisisobutyronitrile was added, and polymerization was initiated at 6 to 75 t under nitrogen for 5 to 20 hours. After completion of the reaction, the obtained solution was precipitated by diethyl ether or n-hexane solvent, filtered and dried to give the title compound (1 2), yield 84%. (12)

C00 -12- 1 : Poly"9-imethylimine propyl methacrylate-(2-hydroxy-ethyl methacrylate-glycidyl methacrylate-(methacrylic acid 9-1: methyl ester) Process 2 In a 500 ml round bottom flask, 0.1 mol of methacrylic acid 9- 3 蒽methylimine propyl ester monomer / 0.3 mol of 2-hydroxyethyl methacrylate / 0.3 mol of 4 methacrylic acid was stirred. Methyl ester / 0.3 mol of 9-fluorenylmethyl methacrylate, and 300 g of separately prepared tetrahydrofuran was added to the resulting mixture, followed by the addition of 5 0.1-3.0 g of 2,2'-azobisisobutyronitrile. 6 to 20t and 6 times of polymerization under nitrogen to initiate polymerization for 5 to 20 hours. After the reaction is completed, diethyl ether or n-hexane 7 solvent is added to precipitate the solution, which is filtered and dried to obtain the title resin (13), yield 83% 〇 1302537. Description of the invention (11) (13)

C00 Example 5: Preparation method of poly [methyl 9-fluorenyl imino propyl acrylate - (3-hydroxypropyl acrylate) - methyl glycidyl acrylate - (9-fluorenyl methacrylate) 1] Add 0.1 mol of 9-mercaptomethylimidopropyl methacrylate monomer / 0.3 mol of 3-hydroxypropyl acrylate / 0.3 mol of methyl methacrylate / 0.3 mol in a 500 ml round bottom flask. 9-methyl methacrylate was added, and 300 g of separately prepared tetrahydrofuran was added to the resulting mixture. Thereafter, 〇·1 - 3.0 g of 2,2'-azobisisobutyronitrile was added, and the polymerization reaction was initiated at 60 to 75 t under nitrogen for 5 to 20 hours. After completion of the reaction, the obtained solution was precipitated by adding diethyl ether or n-hexane solvent, filtered and dried to give titled (1 4). -13- ---------- 1302537 V. Description of invention (12) (14)

Example 6: fl[g-based propylene acid 9-i-methylimine propyl ester _ (acrylic acid 4 _ butyl illv methacrylic acid glycidol house 1 (methacrylic acid 9- fluorene methyl ester eve method in 500 cc Stirring in a round bottom flask with 〇. i mole methacrylic acid 9_ 蒽methylimine propyl ester monomer / 〇 _3 molar 4-hydroxybutyl acrylate / 0.3 mol Methyl methacrylate / 0.3 mol 9-fluorenyl methacrylate, and 300 g of separately prepared tetrahydrofuran is added to the resulting mixture, followed by the addition of 1-3.1-3 2 2,2 azobisisobutyronitrile at 60 to 75 ° C and The polymerization was initiated under nitrogen for 5 to 20 hours. After completion of the reaction, the obtained solution was precipitated by adding diethyl ether or n-hexane solvent, filtered and dried to give the titled resin (15), yield 80%. -14-1302537. (13) (15)

Sinus Example 7: Preparation of j-reflex-coated sputum roll The polymer (1) and the polymer (2) obtained in any of Examples 1 to 6 were dissolved in propylene glycol methyl ether acetate. The resulting solution is separately or re-dosed in an amount of from about 1% to about 30% by weight of at least one anthraquinone derivative until complete dissolution, filtration, application to the wafer, and hard baking at about 100 to about 300 ° C for about 10 to about 1,000 second. Then, a photosensitive film is applied thereon, and a general ultra-fine pattern is processed. The crosslinking agent used is preferably in the form of a polymer to maximize crosslinking efficiency. In addition, by controlling the ratio of the main polymer, the anti-reflective organic coating can be freely modified. Therefore, it can overcome the trouble of not being able to control k値 in the past. Further, the antireflective coating resin of the present invention contains two monomers each having a highly absorptive chromophore, and the polymer produced therefrom has a high absorbance at 248 nm. Since one of the two chromophores is weakly alkaline, the undercut can be prevented from occurring due to acidity imbalance after the coating is prepared. In addition, the anti-reflective coating resin is quite soluble in all hydrocarbon solvents, but is not soluble in any solvent during hard baking, and has no undercuts and inlays during pattern processing. -15-1302537 5. Invention (14) The phenomenon. In particular, since the antireflective coating resin contains an acrylate polymer, the etching rate is higher than that of the photosensitive film, so that the etching selectivity can be improved. The present invention has been described with reference to the embodiments of the present invention. It is understood that the terminology is used for the description of the features and not for the limitation of the scope of the invention. -16- Apply for the case number 〇[ 〇X φφ Category c〇^Γ6ιο Invention new patent specification (Revised May 2008 i) Chinese organic anti-reflective coating compound, anti-reflective coating composition containing the same and preparation method thereof Invention new honey name in English

Organic ant i- reflect ive coating compound, ant i-reflective coating composition including the same and preparation methods thereof_ Name Nationality 1·HONG (Sung-eun) 2·Zheng Zheng (JUNG, Min-ho) 3 ·Zheng Zaichang (JUNG , Jae-chang) 4. Lie Shou (LEE, Geun-su) 1-5 are all Republic of Korea 5. Baiji, Ki-ho Inventor's residence, residence 1. The Republic of Korea, Gyeonggi-do, South M-dong district Meidong 141, Fenglin Apartment, No. 404, No. 404 2. No. 1102, Building 205, Xianpu Apartment, Zengpudong, Lichuan City, Gyeonggi-do, Korea. 3, No. 1304, Building 107, Daegu-dong, Dong-dong, Gyeonggi-do, Icheon, Republic of Korea. 4. Gyeonggi-do, Republic of Korea No. 302, Building 103, Sanyi Apartment, Xinheli, Fuchuan City 5. No. 402, No. 203, Daewoo Apartment, Zengpudong, Lichuan City, Gyeonggi Province, Korea Name (Name) Nationality Hynix Semiconductor Inc. Korea 1 , Applicant's residence, residence (office), Gyeonggi-do, Gyeonggi-do, Gyeonggi-do, Ishikawa, Japan 136-1 Representative name CHENG, Dong-soo

Claims (1)

1302537 Sixth, the patent application scope table 90120244 "Organic anti-reflective coating compound, including its anti-reflective coating composition and its preparation method" patent case (amended in May 2008) VI. Patent application scope 1 · One with the following formula ( 1) Structure of the compound: Wherein V to Rd each represent hydrogen or methyl; 1 to Rd& 1 to Rl8 are each independently 咄, _〇H, -〇c〇CH3 '-COOH'-CHAH' or substituted or unsubstituted, straight chain Or a branched Ch5 alkyl or alkoxyalkyl group; 1 'm' and η are each an integer selected from 1' 2' 3' 4 or 5; w, X, y and oxime are each 0.01 to 0.99 molar fraction rate. 2 · As claimed in the patent specification, the compound of the first item 'is a poly[acrylic acid E-methylimine ethyl acetate _ (2-propane acid is glycidyl methyl methacrylate - (methacrylic acid-9) -Cang methyl ester)], in the formula "and Rb 1302537 VI. The patent application scope is independent hydrogen, ^ and ! ^ are each independent methyl, 1 ^ to 1 and 1 ^ to R18 are independent hydrogen , 1, m and η are both 2, and w, X, y and ζ are 0.1' 0.3' 0.3 and 0.3, respectively. 3. The compound of claim 1 is poly [methacryl oxime methyl amide] Amine ethyl ester-(2-hydroxyethyl methacrylate)-glycidylmethyl methacrylate (-9-fluorenylmethyl methacrylate)], wherein Ra, Rb and Rd are each independently methyl, Re methyl , Ra to Rd and Ri to R18 are each independently gas, l, m and η are both 2, and w, x, y and ζ are 0. 1,0. 3,0 . 3 and 0.3. 4 . A compound according to claim 1 which is a poly [acrylic acid yttrium methyl imidate-(3-hydroxypropyl acrylate)-glycidyl methacrylate (-9-fluorenyl methacrylate) ], where Ra and Rb are each independently hydrogen, and Re and Rd are independent For the methyl group, 1 to 1 and 1^ to R18 are each independently hydrogen, and l, m and η are respectively 3, 3, 2, and w, X, y and Ζ are 0.1, 0.3, 0.3 and 0.3, respectively. For example, the compound of claim 1 is poly[methylpropionate methyl iminopropyl propyl ester-(2-hydroxyethyl methacrylate)-glycidyl methacrylate (methacrylic acid-9-fluorene) Methyl ester)], wherein Ra, Rb, Rc and Rd are each independently methyl, Ra to Rd and 1^ to R18 are each independently hydrogen, and l, m and η are 3, 2 and 2, respectively, and *, $ , ^ and 2 are 0.1, 0.3, 0.3 and 0.3, respectively. 6. The compound of claim 1 is poly [methyl methacrylate methacrylate - (3-hydroxypropyl acrylate)] - shrinkage of methacrylic acid 1302537 VI. Patent application range glycerol (-9-methyl methacrylate)], where Ra, Re and Rd are each independently methyl, Rb is hydrogen, Ra to Rd and 1^ to R18 Each of them is independently hydrogen, and l, m and η are 3, 3 and 2, respectively, and ~, \, 丫 and ζ are 0.1, 0.3, 0.3 and 0.3 respectively. 7. The compound of claim 1 is Poly [methacrylic acid methyl iminopropyl propyl ester - (c 4-Hydroxybutyl 4-(hydroxybutyrate)-glycidylmethyl methacrylate (9-fluorenylmethyl methacrylate)], wherein Ra, Re and Rd are each independently methyl, Rb is hydrogen, 1^ to Rd and ^ Each of R18 is independently hydrogen, l, m and η are g [J is 3, 4 and 2, and \^,} (:, 7 and ζ are 0.1, 0.3, 0.3 and 0.3, respectively. 8. A method for producing a compound as claimed in claim 1, wherein the 9-mercaptomethylimide ester monomer, hydroxyalkyl acrylate, glycidyl acrylate monomer and methacrylic acid 9 - The decyl ester is reacted in a solvent, and the resulting product is subjected to polymerization using a polymerization initiator. 9. The method of claim 8, wherein the solvent is selected from the group consisting of tetrahydrofuran, toluene, benzene, methyl ethyl ketone, dioxane, and mixtures thereof. The method of claim 8, wherein the polymerization initiator is selected from the group consisting of 2,2'-azobisisobutyronitrile, acetaminophen peroxyl, and lauryl peroxide peroxidation a group of oxygen and its mixtures. 1 1 The method of claim 8, wherein the polymerization is carried out at 50 to 90 °C. 1302537 VI. Scope of Application for Patention 1 2 - An anti-reflective coating composition containing the compound (1) as in the first paragraph of the patent application and the following compound (2); (2) Wherein R19 and R2Q are each independently a linear or branched substituted 10 oxa group oxy group, and R21 is a hydrogen group or a methyl group. i 3 . The anti-reflective coating composition of claim 12, wherein the cerium comprises an cerium derivative additive selected from the group consisting of hydrazine, 9-fluorenyl methanol, 9-phthalonitrile, 9-fluorene carboxylic acid, and diterpene. Alcohol, 1,2,10-nonanetriol, phthalic acid, 9-formaldehyde oxime, 9-furaldehyde, 2-amine-7-methyl-5-oxo-5H[1]benzopyran [2,3 - b ]pyridine-3-carbonitrile, 1-amine hydrazine, hydrazine-2 -carboxylic acid, 1,5-dihydroxyindole, anthrone, 9-fluorene trifluoromethanone, 9-alkane Anthracene derivatives, 9-carboxyindole derivatives, 1-carboxyindole derivatives and mixtures thereof. 1 4. A method of producing an anti-reflective coating comprising the steps of: - dissolving an anti-reflective coating composition as claimed in claim 12 in an organic solvent; - filtering the resulting solution alone or in combination with an anthracene derivative Additives selected from the group consisting of hydrazine, 9-hydrazine carbonitrile, 9-phthalonitrile, 9-fluorene carboxylic acid, bis-tertanol, 1,2,10-nontriol, phthalic acid, 9-formaldehyde oxime, 9 -furfural, 2-amine-7-methyl-5-oxo-5H[1]benzopyrano[2,3-b]pyrim-4-1302537 VI. Patent application range pyridine-3 -carbonitrile, 1 -amine oxime, oxime-2 -carboxylic acid, 1,5-dihydroxyindole, fluorenone, 9-fluorene trifluoromethanone, 9-alkyl hydrazine derivative, 9-carboxy hydrazine derivative, 1-carboxylate Anthraquinone derivatives and mixtures thereof; - coating the filtrate on the bottom layer; and - hard baking coating. The method of claim 14, wherein the organic solvent is selected from the group consisting of ethyl 3-ethoxypropionate, methyl 3-methoxyoxypropionate, cyclohexanone and propylene glycol methyl ether acetate. The group is used in an amount of 200 to 5,000% by weight based on the total weight of the antireflective coating resin. 16. The method of claim 14, wherein the hard baking step is carried out at 100 to 300 °C. A semiconductor device produced by an anti-reflective coating composition as disclosed in claim 12 or 13.