KR100479686B1 - A thermally stable polymer containing n-hydroxyphenylmaleimide, and an anti-reflective coating compositon for photolithography comprising the same - Google Patents

Abstract

The present invention can be used to suppress the diffuse reflection of the light exposed during the fine pattern processing in the semiconductor manufacturing, organic polymer containing N -hydroxyphenylmaleimide repeat unit having a high light absorption in the far ultraviolet region of 193nm wavelength, including the same It relates to an antireflection film composition and a method for producing the same. The bottom anti-reflection film containing the organic polymer according to the present invention is used in the manufacture of highly integrated semiconductor devices of Giga-bit DRAMs, which can greatly suppress inter-layer diffuse reflection and standing wave phenomena of circuits, and thus, ultra-70 nm to 120 nm It is possible to stably form high resolution microcircuits to increase the yield of semiconductor products.

Description

N-hydroxyphenylmaleimide-containing heat resistant polymer, and an anti-reflective coating composition and anti-reflective coating comprising the same {A THERMALLY STABLE POLYMER CONTAINING

The present invention, in photolithography, which is an exposure process for forming a microcircuit of a highly integrated semiconductor using short-ultraviolet rays of 200 nm or less, suppresses reflective notching occurring in the filling of a substrate under a photoresist. Regarding the organic polymer photosensitive material for bottom antireflective coating layer, the bottom antireflective coating composition containing the same, and a method of manufacturing the same, which can eliminate standing wave effects due to changes in thickness of the light source and photoresist used. will be.

An antireflective coating (ARC) is a very thin layer of light-absorbing photoresist that is essential for the production of gigabit (Gb) class ultra-high density semiconductors, typically 100nm to 200nm circuits and future sub-100nm ultrafine It is used in optical microcircuit processing process to stably form a circuit. Therefore, the anti-reflection film should be well matched with the high-resolution photoresist (PR) material used in the existing semiconductor production process and mutual adhesion interface and optical properties. This antireflection film is referred to as " bottom ARC = BARC " because it is first applied before the photoresist layer is applied during the short wavelength ultraviolet exposure process. In the currently developed highly integrated semiconductor optical microfabrication process, an organic bottom antireflection film having high absorbance is generally used. Since the organic antireflection film must have high light absorption at a specific exposure wavelength, the development of a highly integrated semiconductor microfabrication process It should be able to cope with shortening of the light source (e.g., 430 nm G-ray, 365 nm I-ray, 248 nm KrF laser, 193 nm ArF laser, 157 nm F2 laser, etc.) (M. Padmanaban et al ., Proc. SPIE , 3678). , 550 (1999); GE Bailey et al. Proc. SPIE , 3999 , 521 (2000); M. Padmanaban et al ., Proc. SPIE , 3333 , 206 (1998)).

In recent years, the technology of the ultra-high-density semiconductor manufacturing process has developed remarkably. However, the conventional micro-fine processing technology that rotates and exposes a photoresist, a photoresist material, on a silicon wafer to expose a stable 70-150nm ultrafine circuit It became impossible to produce. Accordingly, it is necessary to apply a special thin film to prevent reflection in the exposure process before applying the photoresist layer. The antireflective film prevents standing wave effects caused by interference of incident light and reflected light from the substrate inside the photoresist layer during exposure, and also at reflections or edges due to topography resulting from circuit layers made in conventional processes. It is to prevent or significantly reduce the diffuse reflection of the. Therefore, it is possible to accurately control the desired critical dimension (CD), thereby increasing the process latitude of the manufacturing process conditions. The anti-reflection film used for the above-mentioned purpose is an organic material system using spin coating according to its composition and an inorganic material system using chemical vapor deposition. However, in recent years, an anti-reflection film of an organic material system which is convenient for the process is used.

In particular, due to the need for an exposure process using a large energy short wavelength such as far ultraviolet rays having a wavelength of 193 nm, a chromophore having high light absorption in such a short wavelength region has been required. Accordingly, an aromatic system containing a benzene ring has recently been developed. The invention of organic anti-reflective coating materials using derivatives has become mainstream (Shao et al ., J. Photopolym. Sci. Technol ., 14 , 481 (2001); J. Meador et al ., Proc. SPIE , 3678 , 800 (1999); G. Taylor et al ., Proc. SPIE , 3678 , 174 (1999); S.-H, Hwang et al ., Polymer , 41 , 6691 (2000); K. Mizutani et al ., Proc SPIE , 3678 , 518 (1999); US Patent, 6,090,531, Fuji Photo Film (Japan), July 18, 2000; US Patent 6,033,830, Shipley Co. (Mass., USA), March 7, 2000; US Patent, 6,080,530. , Brewer Science , Inc. (Mo., USA), June 27, 2000; Korean Patent Publication No. 2001-003934 (published Jan. 15, 2001), Hyundai Electronics Industry.

Among the short wavelength far ultraviolet rays, the role of the anti-reflection film has become more important after the optical microcircuit processing process using a krypton fluoride (KrF) excimer laser having a wavelength of 248 nm has been in full swing. In addition, the composition for organic bottom antireflection film used in the 193 nm wavelength argon fluoride (ArF) excimer laser micromachining process to achieve ultra high resolution is required to meet the requirements as described below (H. Yoshino et al. , Proc SPIE , 3333 , 655 (1998); P. Trefonas et al., Proc. SPIE , 3678 , 701 (1999); W.-B. Kang et al., J. Photopolym. Sci. Technol ., 10 , 471 (1997)).

-Should have suitable optical constants, i.e. suitable refractive index (n) and light absorption constant (k), for the light source used for semiconductor manufacturing.

The organic bottom anti-reflection film should have a high selectivity at the plasma dry etch rate compared to the top photoresist, and there should be no image defects due to dry etch.

There should be no intermixing between the photoresist and the bottom anti-reflective coating. For this purpose, a reactor must be included in the organic polymer chain to form an appropriate crosslinking structure.

The organic bottom anti-reflection film should not have undercutting or footing at the bottom of the photoresist micropattern due to the interfacial action of the photoresist when developing the solution after the exposure process.

In the film forming process by rotating coating, suitable thin film thickness control ability, excellent film forming ability and film uniformity are required.

Accordingly, an object of the present invention is to provide a novel organic polymer that can be used as an antireflection film material in an ultrafine circuit processing process using an ArF excimer laser having a wavelength of 193 nm as an exposure source during an ultra-high density semiconductor device manufacturing process.

Another object of the present invention is to provide an organic anti-reflective coating composition having excellent heat resistance and excellent crosslinking performance, and a method for producing the same, which can prevent diffuse reflection from an underlayer during a short wavelength exposure process.

It is still another object of the present invention to provide a method for producing an antireflection film that can be used in a 193 nm short wavelength exposure process using the bottom antireflection film composition.

Monomers used in the preparation of the organic polymer for a bottom anti-reflective coating according to the present invention essentially include hydroxyphenylmaleimide chromophores and derivatives thereof having high light absorption at short exposure wavelengths of 193 nm and below. It is preferable to have a hydroxyl group and a cyanate group for the crosslinking in the process of forming a. In addition, since the organic polymer of the present invention requires physical properties such as heat resistance and adhesiveness, it includes a terpolymer or quaternary copolymer prepared from three or four different monomers using a comonomer in order to control them. In particular, the hydroxyphenylmaleimide monomer used in the preparation of the organic polymer of the present invention is preferably a monomer having a properly protected chemical structure or crosslinking function for ease of manufacturing the polymer. The organic polymer for a bottom anti-reflection film according to the present invention, which satisfies all the above characteristics, has a structure as shown in the following formula (1).

In Formula 1, R represents H, tetrahydropyranyl, -COOR ³ , (SiR ⁴ ) ₃ or a t-butyl group, where R ³ and R ⁴ are each methyl, t-butyl or C ₂ -C ₃ alkyl R ¹ and R ² each independently represent hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy alkyl, C ₁ -C ₆ hydroxy alkyl or C ₁ -C ₆ halogenated alkyl.

The ratio of each monomer is based on the total mole fraction x + y + z + p of the monomer, and the molar fraction of x is 0.1 to 0.7, the molar fraction of y is 0 to 0.8, the molar fraction of z is 0 to 0.55, and the molar fraction of p is 0 to 0. It is preferable that it is 0.5.

The organic polymer of the present invention having the structure shown in Chemical Formula 1 may be generally represented as-(Ma) x- (Mb) y- (Mc) z- (Md) p-. Wherein Ma is N- (4-hydroxyphenyl) maleimide structure protected with hydroxyphenylmaleimide, precisely N- (4-hydroxyphenyl) maleimide or a suitable protecting group such as represented by R in Formula 1 to have, Mb is a methacrylic acid ester structure having a suitable functional group, such as those indicated by R ¹ in the formula 1, Mc is a vinyl ether structure having a suitable functional group, such as those represented by R ² in formula 1, Md is the thermal resistance N- (4-cyanatophenyl) maleimide having a crosslinking function simultaneously.

The poly (hydroxyphenylmaleimide) derivative according to the present invention having the structure shown in Chemical Formula 1 may be produced by polymerizing a maleimide monomer having a structure as shown in the following Chemical Formula 2.

In Formula 2, R is the same as described in Formula 1 above.

The polymer of Chemical Formula 1 according to the present invention has a very high light absorption in the 193 nm wavelength region of the argon fluoride excimer laser, is easy to polymerize due to a hydroxyl group-protected functional group property, and has excellent heat resistance of the antireflection film material. Excellent adhesion to the wafer. The polymer material of the present invention prepared by using a hydroxyphenylmaleimide derivative as a monomer has a high glass transition temperature of 200 ° C. or higher and a high pyrolysis temperature of 300 ° C. or higher, compared to a polymer material using a methacrylate monomer used in a conventional antireflection film. Indicates. That is, the glass transition temperature of the N -hydroxyphenylmaleimide containing polymer which concerns on this invention was 215 degreeC, and the thermal decomposition temperature was observed at 350 degreeC.

Next, the manufacturing method of the polymer of the present invention as shown in the general formula (1) will be described. The polymer of Chemical Formula 1 may be obtained by reacting a monomer as described above according to a conventional radical polymerization method for 2 hours to 24 hours using a radical polymerization initiator under an inert gas atmosphere such as nitrogen and argon. The radical polymerization initiator may be selected from various known thermal polymerization initiators such as benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), di-t-butylperoxide (DTBP), and the reaction temperature. It is preferably in the range of 50 ° C to 90 ° C. As a solvent of a polymerization reaction, aromatic solvents, such as dioxane, tetrahydrofuran, or benzene, can be used. In the present invention, by adjusting the weight ratio between the monomer and the polymerization solvent or by controlling the amount of the radical initiator, it is possible to produce a polymer of the appropriate molecular weight required in the semiconductor exposure step. The molecular weight of the polymer of Chemical Formula 1 is controlled to adjust the polymerization conditions so that the molecular weight measured using gel permeation chromatography (GPC) is in the range of 5,000 to 100,000. Among the polymers obtained by the same method as described above, a polymer having a molecular weight having an appropriate coating ability is used as the antireflection film material.

Next, the composition for organic bottom antireflection films concerning this invention is demonstrated. The organic bottom anti-reflective coating composition of the present invention comprises a polymer of Formula 1 as a solvent for propylene glycol monomethyl ether acetate (PGMEA), ethyl 3-ethoxypropionate, ethyl lactate, methyl 3-meth It is prepared by dissolving 0.2 to 20% by weight in an organic solvent having excellent film forming ability such as oxypropionate or cyclohexanone, and then adding various functional additives to the solution as appropriate. At this time, the content of each additive is 0.1 to 15% by weight of the crosslinking agent, 0.1 to 20% by weight of the photoacid generator, 0.1 to 10% by weight of the stabilizer and the like to the polymer used.

The mixed solution at the above ratio is filtered in a fine particle filtration apparatus, spun applied on a silicon wafer, and crosslinked at an appropriate temperature to obtain a desired antireflection film. The anti-reflection film prepared in this manner serves to remove the problems caused by the reflection of light in the exposure process of the short-wavelength ultra-ultraviolet microcircuit processing, so that the semiconductor device production process can be performed smoothly. In addition, the anti-reflection film exhibited excellent light absorption as an organic bottom anti-reflection film for forming a semiconductor microcircuit in a 193 nm exposure wavelength region of an ArF excimer laser having a short wavelength far ultraviolet of 200 nm or less, and a reflection based on a general methacrylate-based polymer. As it has superior heat resistance compared to the prevention film, it was found to be useful for processing ultrafine circuits with a line width of 70 nm to 150 nm in semiconductor device processing.

Example

Hereinafter, the present invention will be described in detail through examples. However, the embodiments are only illustrative of the present invention, and the scope of the present invention is not limited thereto.

Example 1. N Hydroxyphenylmaleimide (HOPMI) monomers One Synthesis of

In a 250 ml round bottom flask equipped with a reflux condenser, maleic anhydride (39.20 g, 0.40 mol) and 4-aminophenol (41.40 g, 0.38 mol) are added and 50 ml of dimethylformamide (hereinafter referred to as "DMF"). ), And reacted at room temperature for 90 minutes. Filtered and the yellow solid product produced after the reaction, and three with distilled water-washed by four times, and then dried, N-hydroxyphenyl maleamic acid N - (4-hydroxyphenyl) maleamic acid, hereinafter referred to as "HOPMA")) 75.40g ( Yield 96.0%), and melting point was 180 ℃.

Subsequently, the resulting HOPMA (75.40 g, 0.36 mole) was placed in a 250 ml round bottom flask equipped with a reflux condenser, and reacted at 80 ° C. while slowly adding phosphorus pentoxide (P ₂ O ₅ , 10.00 g, 0.07 mole) as a side reaction. After the resulting water was removed, a solution of 4 ml of sulfuric acid diluted in 20 ml of DMF was slowly added dropwise to the reaction mixture. The reaction product formed by reacting for 2 hours was precipitated in excess distilled water to obtain a monomer product, and then recrystallized from propanol to give 56.37 g of pure N -hydroxyphenylmaleimide (hereinafter referred to as "HOPMI") monomer 1 of orange crystals ( Yield 81.9%), and the melting point was 182 ℃.

Example 2. N -(4-tetrahydropyranyloxyphenyl) maleimide (THP-OMPI) monomer 2 Synthesis of

In a 500 ml round bottom flask, monomer 1 (47.30 g, 0.25 mol) and dihydropyran (105.20 g, 1.25 mol) were added and dissolved in 150 ml of tetrahydrofuran (hereinafter referred to as "THF"). 0.5 ml of concentrated sulfuric acid was diluted in 100 ml of THF and slowly added dropwise to the reaction, followed by stirring at room temperature for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the remaining product was precipitated in excess distilled water, and the resulting precipitate was filtered and washed with distilled water several times. The product was recrystallized in propanol to give 53.20 g (yield 77.9%) of N -tetrahydropyranyloxymaleimide (THP-OPMI) monomer 2 , a protected monomer of orange crystals, with a melting point of 120 ° C.

Example 3. N -(4-cyanatophenyl) maleimide (CyPMI) monomer 3 Synthesis of

In a 250 ml round bottom flask, monomer 1 (15.00 g, 0.79 mol) and cyanozen bromide (10.10 g, 0.95 mol) were dissolved in 120 ml of acetone, cooled in an ice bath at 0 ° C. and triethylamine (9.60 g, 0.95 Mole) was slowly dropped for 20 minutes and then reacted for 4 hours. The resulting reaction was filtered to remove the ammonium salt and the filtrate was precipitated in excess distilled water to recover the product. The product was recrystallized in a mixed solution of hexane and acetone (6: 1) to obtain 13.74 g (yield 80.9%) of N -cyanotophenylmaleimide (hereinafter referred to as "CyPMI") monomer 3 of orange crystals and a melting point of 132 ° C.

Example 4. N -(4-t-butoxycarbonyloxyphenyl) maleimide (t-BOCOPMI) monomer 4 Synthesis of

Monomer 1 (19.76 g, 0.104 mol) was dissolved in 40 ml pyridine and 160 ml THF in a 500 mL round bottom flask. Di-t-butyldicarbonate (DTBDC) (105.20 g, 1.25 mol) was added to the reaction mixture, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the product was filtered to remove the pyridinium salt, and the filtrate was precipitated in excess distilled water to recover the product. The product was recrystallized from a mixture of hexane and acetone (6: 1) to obtain 27.10 g (yield 90.0%) of N- t-butoxycarbonyloxyphenylmaleimide (t-BOCOPMI) monomer 4 as a protected monomer of yellow crystals. The melting point was 142 ° C.

Example 5. Monomers One Synthesis of Methyl Methacrylate (MMA) (1: 1) Copolymers

In a 20 ml pyrex glass polymerization tube, monomer 1 (2.50 g, 0.013 mol), methyl methacrylate (1.30 g, 0.013 mol), initiator 2,2'-azobisisobutylonitrile (hereinafter referred to as "AIBN") (0.077 g, 3 mol% relative to the total monomers) was added, dissolved in 8.0 ml of dioxane, and then replaced with nitrogen gas and sealed after three freeze / thaw cycles. The sealed polymerization tube was polymerized at 60 ° C. for 8 hours, and then added dropwise to 300 ml of methanol to filter the precipitated polymer, followed by reprecipitation twice in methanol, followed by filtration and drying. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (HOPMI / MMA) showed a ratio of monomer 1: 1 and methyl methacrylate at 36:64. The obtained polymer showed a molecular weight of 37,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of copolymer P (HOPMI / MMA) was 3.01 g (79.2%).

Example 6. Monomer One Synthesis of Methyl Methacrylate (MMA) (1: 2) Copolymers

In the same manner as in Example 5, the copolymerization reaction was carried out using a monomer 1 (2.50 g, 0.013 mol) and methyl methacrylate (2.64 g, 0.02 mol) with a molar ratio of 1: 2. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (HOPMI / MMA) showed 25:75 ratio of monomer 1 and methyl methacrylate. The obtained polymer had a molecular weight of 41,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of copolymer P (HOPMI / MMA) was 4.12 g (80.2%).

Example 7. Monomer One And Synthesis of Butyl Vinyl Ether (BuVE) (1: 1) Copolymer

In the same manner as in Example 5, the copolymerization reaction was performed using a monomer 1 (2.50 g, 0.013 mol) and a BuVE monomer (1.30 g, 0.013 mol) with a molar ratio of 1: 1. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (HOPMI / BuVE) showed a ratio of 49:51 of monomer 1 and butyl vinyl ether. The obtained polymer showed a molecular weight of 43,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of copolymer P (HOPMI / BuVE) was 3.10 g (81.2%).

Example 8: Monomer 2 And synthesis of methyl methacrylate (1: 1) copolymer

In the same manner as in Example 5, the copolymerization reaction was carried out using a monomer 2 (2.50 g, 0.0091 mol) and methyl methacrylate (0.91 g, 0.0091 mol) with a molar ratio of 1: 1. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (HOPMI / MMA) showed a ratio of 48:52 of monomer 2 and methyl methacrylate. The obtained polymer had a molecular weight of 48,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed.

The yield of copolymer P (HOPMI / MMA) was 2.85 g (83.6%).

Example 9: Monomer 3 And synthesis of methyl methacrylate (1: 1) copolymer

In the same manner as in Example 5 using the monomer 3 (2.50g, 0.011 mole) and methyl methacrylate 1.16g (0.011 mol) and the molar ratio 1: 1 was carried out the copolymerization reaction. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (CyPMI / MMA) was 43:57 in the ratio of monomer 3 and methyl methacrylate. The obtained polymer had a molecular weight of 56,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of copolymer P (CyPMI / MMA) was 3.12 g (85.2%).

Example 10 Monomer 4 And synthesis of methyl methacrylate (1: 1) copolymer

In the same manner as in Example 5, copolymerization was carried out using a monomer 4 (2.50 g, 0.0086 mol) and methyl methacrylate (0.86 g, 0.0086 mol) with a molar ratio of 1: 1. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (t-BOCOPMI / MMA) was 41:59 in the ratio of monomer 4 and methyl methacrylate. The obtained polymer had a molecular weight of 35,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of copolymer P (t-BOCOPMI / MMA) was 2.56 g (76.2%).

Example 11: Monomer 2 And monomers 3 And synthesis of methyl methacrylate (1: 1: 2) terpolymer

In a 100 ml pyrex glass polymerization tube, monomer 2 (10.0 g, 0.037 mol), monomer 3 (7.84 g, 0.037 mol), methyl methacrylate (7.32 g, 0.073 mol) and initiator AIBN (0.48 g, 2 for total monomers) Mole%), dissolved in 30 ml of dioxane, then replaced with nitrogen gas and sealed after three freeze / thaw cycles. After polymerization of the sealed polymer tube at 60 ° C. for 5 hours, the mixture was added dropwise to 500 ml of methanol, and the precipitated polymer was collected by filtration. The mixture was reprecipitated twice with methanol, and the polymer was purified and dried. As a result of analyzing the NMR spectrum, the polymer P (THP-OPMI / CyPMI / MMA) composition obtained had a ratio of monomer 2 : monomer 3 : methyl methacrylate at 23:25:52. The obtained polymer had a molecular weight of 72,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of ternary copolymer P (THP-OPMI / CyPMI / MMA) was 20.90 g (83.1%).

Example 12 Monomer 2 And monomers 3 And Synthesis of Butyl Vinyl Ether (1: 1: 2) Terpolymer

Monomer 2 (10.0 g, 0.037 mole), monomer 3 (7.84 g, 0.037 mole), butyl vinyl ether (7.33 g, 0.073 mole) and initiator AIBN (0.72 g, 3 mole relative to total monomers) in 100 ml pyrex glass polymer tubes %), Dissolved in 30 ml of dioxane and then sealed after 3 freeze / thaw cycles with nitrogen gas substitution. After polymerization of the sealed polymer tube at 60 ° C. for 5 hours, the mixture was added dropwise to 500 ml of methanol, and the precipitated polymer was collected by filtration. The mixture was reprecipitated twice with methanol, and the polymer was purified and dried. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (THP-OPMI / CyPMI / BuVE) showed 26:23:51 ratio of monomer 2 : monomer 3 : butyl vinyl ether. The obtained polymer had a molecular weight of 78,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of ternary copolymer P (THP-OPMI / CyPMI / BuVE) was 20.46 g (81.3%).

Example 13: Monomer 2 Of butyl vinyl ether, metel methacrylate (1: 1: 2) terpolymer

100 ml pyrex glass polymerization tubes with monomer 2 (10.0 g, 0.037 mol), butyl vinyl ether (3.66 g, 0.037 mol), methyl methacrylate (7.40 g, 0.074 mol) and initiator AIBN (0.24 g, total monomers) 1 mole%), dissolved in 30 ml of dioxane, and then sealed after 3 freeze / thaw cycles with nitrogen gas substitution. After polymerization of the sealed polymer tube at 60 ° C. for 6 hours, the reaction mixture was added dropwise to 500 ml of methanol, and the precipitated polymer was collected by filtration, reprecipitated twice in methanol, and the polymer was purified and dried. As a result of analyzing the NMR spectrum, the polymer P (THP-OPMI / BuVE / MMA) composition obtained had a ratio of monomer 2 : butylene ether: methyl methacrylate at 23:21:56. The obtained polymer showed a molecular weight of 54,000 measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of ternary copolymer P (THP-OPMI / BuVE / MMA) was 16.52 g (78.4%).

Example 14 Monomer 2,  Monomer 3 And Synthesis of Hydroxybutyl Vinyl Ether (HOBVE) (1: 1: 2) Terpolymer

100 ml pyrex glass polymerization tubes with monomer 2 (10.0 g, 0.037 mole), monomer 3 (7.84 g, 0.037 mole), hydroxybutyl vinyl ether (12.02 g, 0.073 mole) and initiator AIBN (0.72 g, total monomers) 3 mol%), dissolved in 30 ml of dioxane, and then sealed after 3 freeze / thaw cycles with nitrogen gas substitution. After polymerization of the sealed polymer tube at 60 ° C. for 6 hours, the reaction mixture was added dropwise to 500 ml of methanol, and the precipitated polymer was collected by filtration, reprecipitated twice in methanol, and the polymer was purified and dried. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (THP-OPMI / CyPMI / HOBVE) showed a ratio of monomer 2 : monomer 3 : hydroxybutyl vinyl ether to 24:25:51. The obtained polymer showed a molecular weight of 54,000 measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of ternary copolymer P (THP-OPMI / CyPMI / HOBVE) was 23.82 g (79.8%).

Example 15 Monomer 2 , Monomer 3 And Synthesis of Chloroethyl Vinyl Ether (CEVE) (1: 1: 2) Terpolymer

In a 100 ml pyrex glass polymer tube, monomer 2 (10.0 g, 0.037 mol), monomer 3 (7.84 g, 0.037 mol), chloroethyl vinyl ether (7.80 g, 0.073 mol) and initiator AIBN (0.72 g, 3 for total monomers) Mole%), dissolved in 30 ml of dioxane, then replaced with nitrogen gas and sealed after three freeze / thaw cycles. After polymerization of the sealed polymer tube at 60 ° C. for 6 hours, the reaction mixture was added dropwise to 500 ml of methanol, and the precipitated polymer was collected by filtration, reprecipitated twice in methanol, and the polymer was purified and dried. As a result of analyzing the NMR spectrum, the obtained polymer P (THP-OPMI / CyPMI / CEVE) composition showed a ratio of monomer 2 : monomer 3 : chloroethyl vinyl ether in 25:23:52. The obtained polymer showed a molecular weight of 53,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of ternary copolymer P (THP-OPMI / CyPMI / CEVE) was 20.20 g (78.4%).

Example 16: Monomer 4 , Monomer 3 And synthesis of methyl methacrylate (2: 1: 3) terpolymers

In a 100 ml pyrex glass polymerization tube, monomer 4 (10.0 g, 0.035 mol), monomer 3 (3.70 g, 0.017 mol), methyl methacrylate (5.19 g, 0.052 mol) and initiator AIBN (0.51 g, 3 for total monomers) Mole%), dissolved in 30 ml of dioxane, then replaced with nitrogen gas and sealed after three freeze / thaw cycles. After polymerization of the sealed polymer tube at 60 ° C. for 6 hours, the reaction mixture was added dropwise to 500 ml of methanol, and the precipitated polymer was collected by filtration, reprecipitated twice in methanol, and the polymer was purified and dried. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (t-BOCOPMI / CyPMI / MMA) was 32:17:51 in the ratio of monomer 4 : monomer 3 : methyl methacrylate. The obtained polymer had a molecular weight of 36,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of the terpolymer (P-BOCOPMI / CyPMI / MMA) was 14.91 g (78.9%).

Example 17 Monomer One , Monomer 2 And synthesis of methyl methacrylate (1: 2: 3) terpolymer

In a 100 ml pyrex glass polymerization tube, monomer 1 (10.0 g, 0.053 mol), monomer 2 (28.89 g, 0.106 mol), methyl methacrylate (15.90 g, 0.159 mol) and initiator AIBN (1.57 g, 3 for total monomers) Mole%), dissolved in 30 ml of dioxane, then replaced with nitrogen gas and sealed after three freeze / thaw cycles. After polymerization of the sealed polymer tube at 60 ° C. for 6 hours, the reaction mixture was added dropwise to 500 ml of methanol, and the precipitated polymer was collected by filtration, reprecipitated twice in methanol, and the polymer was purified and dried. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (HOPMI / THP-OPMI / MMA) was found to be 14:32:54 in the ratio of monomer 1 : monomer 2 : methyl methacrylate. The obtained polymer had a molecular weight of 38,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of ternary copolymer P (HOPMI / THP-OPMI / MMA) was 41.79 g (76.3%).

Example 18 Monomer 2 , Monomer 3 Of butyl vinyl ether and methyl methacrylate (1: 1: 2: 1) quaternary copolymers

Monomer 2 (10.0 g, 0.037 mol), monomer 3 (7.84 g, 0.037 mol), butyl vinyl ether (7.33 g, 0.073 mol), methyl methacrylate (3.66 g, 0.037 mol) Initiator AIBN (0.90 g, 3 mol% relative to total monomers) was added, dissolved in 30 ml of dioxane and then sealed after 3 freeze / thaw cycles with nitrogen gas substitution. After polymerization of the sealed polymer tube at 60 ° C. for 6 hours, the reaction mixture was added dropwise to 500 ml of methanol, and the precipitated polymer was collected by filtration, reprecipitated twice in methanol, and the polymer was purified and dried. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (THP-OPMI / CyPMI / BuVE / MMA) was found to be 18: 16: 36: 30 in the ratio of monomer 2 : monomer 3 : butyl vinyl ether: methyl methacrylate. The obtained polymer showed a molecular weight of 62,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of the employee copolymer P (THP-OPMI / CyPMI / BuVE / MMA) was 23.22 g (80.5%).

Example 19 Monomer 2 , Monomer 3 Of ethyl, ethyl vinyl ether (EVE) and methyl methacrylate (1: 1: 2: 1) quaternary copolymers

Monomer 2 (10.0 g, 0.037 mol), monomer 3 (7.84 g, 0.037 mol), ethyl vinyl ether (5.28 g, 0.073 mol), methyl methacrylate (3.66 g, 0.037 mol) Initiator AIBN (0.90 g, 3 mol% relative to total monomers) was added, dissolved in 30 ml of dioxane and then sealed after 3 freeze / thaw cycles with nitrogen gas substitution. After polymerization of the sealed polymer tube at 60 ° C. for 6 hours, the reaction mixture was added dropwise to 500 ml of methanol, and the precipitated polymer was collected by filtration, reprecipitated twice in methanol, and the polymer was purified and dried. As a result of analyzing the NMR spectrum, the composition of the obtained polymer P (THP-OPMI / CyPMI / EVE / MMA) was found to be 17: 18: 36: 29 in the ratio of monomer 2 : monomer 3 : ethyl vinyl ether: methyl methacrylate. The obtained polymer had a molecular weight of 47,000 as measured by GPC using THF as a solvent, and a colorless transparent film was easily formed. The yield of employee copolymer P (THP-OPMI / CyPMI / EVE / MMA) was 21.61 g (80.7%).

Example 20 Preparation and Application of Organic Bottom Antireflection Film Composition

Various copolymers obtained in Examples 5-19 are dissolved in 0.2 to 20% by weight in a propylene glycol monomethyl ether acetate solvent having excellent film forming ability, and then various functional additives are appropriately added to the solution. At this time, the content of each additive is 0.1 to 15% by weight of the crosslinking agent, 0.1 to 20% by weight of the photoacid generator, 0.1 to 10% by weight of the stabilizer and the like to the polymer used. This solution was filtered with a microporous membrane filter to prepare a composition for an organic antireflection film for short wavelength far ultraviolet exposure. The solution was spun onto a silicon wafer, heated at 100 ° C. to 250 ° C. for 10 to 120 seconds to crosslink to form an antireflection film with a thickness of 30-80 nm. Thereafter, commercial photoresist was applied on the anti-reflective coating layer in a general semiconductor microcircuit processing step, followed by exposure to short wavelength far ultraviolet rays to perform optical microcircuit processing.

As described above, the organic anti-reflection film using a polymer based on the copolymer, ternary copolymer, or quaternary copolymer of hydroxyphenylmaleide according to the present invention has a high temperature by introducing a new high absorbance chromophore covalently into the polymer chain. It has excellent heat resistance and stability even when thermal cross-linking is performed, and it has sufficient absorbance that an organic bottom anti-reflection film should have. Therefore, it suppresses reflection occurring in the lower layer layer during the microcircuit exposure process, and the standing wave due to the change in thickness of the light source and photoresist used. Can be removed and the circuit can be transferred to the substrate stably due to the high etching ability for plasma etching. Accordingly, the bottom anti-reflection film based on the hydroxyphenylmaleimide polymer according to the present invention is a memory device of 1 gigabit DRAM or more when used as a bottom anti-reflection film in an exposure process using an excimer laser having a wavelength of 193 nm and a short wavelength when manufacturing a semiconductor. Since microcircuit fabrication of system integrated circuits in units of 70-150 nm can be stably performed, production yield of ultra-high integration semiconductor devices can be increased.

Claims (6)

A polymer of protected N -hydroxyphenylmaleimide, represented by the following general formula (I): (I) Wherein R represents H, tetrahydropyranyl, -COOR ³ , (SiR ⁴ ) ₃ or a t-butyl group, R ³ and R ⁴ each represent methyl, t-butyl or C ₂ -C ₃ alkyl, R ¹ and R ² each independently represent hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy alkyl, C ₁ -C ₆ hydroxy alkyl or C ₁ -C ₆ halogenated alkyl, The ratio of each monomer is based on the total mole fraction x + y + z + p of the monomer, the molar fraction of x is 0.1 to 0.7, the molar fraction of y is 0 to 0.8, the molar fraction of z is 0 to 0.55, and the molar fraction of p is 0. To 0.5. The compound of claim 1, wherein R represents tetrahydropyranyl, -COOR ³ , (SiR ⁴ ) ₃ or a t-butyl group, and R ³ and R ⁴ are each methyl, t-butyl or C ₂ -C ₃ alkyl , Polymers having an average molecular weight of 5,000 to 100,000. Organic solvents selected from the group consisting of propylene glycol monomethylether acetate (PGMEA), ethyl 3-ethoxypropionate, ethyl lactate, methyl 3-methoxypropionate and cyclohexanone, 0.2 to 20% by weight of the polymer according to the organic solvent, and 0.1 to 15% by weight of crosslinking agent, 0.1 to 20% by weight of photoacid generator and 0.1 to 10% by weight of stabilizer based on the weight of the polymer, A composition for producing an organic antireflection film used in a semiconductor ultrafine circuit exposure process using an excimer laser having a wavelength of 193 nm and 157 nm. An organic antireflection film for use in an exposure process for fabricating a semiconductor ultrafine circuit using an excimer laser having a wavelength of 193 nm and 157 nm, comprising the N -hydroxyphenylmaleimide copolymer according to claim 1. delete delete