CN115873175A - Bottom anti-reflection coating for DUV lithography and preparation method and application thereof - Google Patents
Bottom anti-reflection coating for DUV lithography and preparation method and application thereof Download PDFInfo
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- CN115873175A CN115873175A CN202111146211.2A CN202111146211A CN115873175A CN 115873175 A CN115873175 A CN 115873175A CN 202111146211 A CN202111146211 A CN 202111146211A CN 115873175 A CN115873175 A CN 115873175A
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Abstract
The invention discloses a bottom anti-reflection coating for DUV lithography and a preparation method and application thereof. The polymer disclosed by the invention is prepared by the following method: preheating a solvent I; (2) Mixing a monomer shown as a formula (A), a monomer shown as a formula (B), a monomer shown as a formula (C), a cross-linking agent shown as a formula (L), an initiator and a solvent II to obtain a mixed solution; (3) Adding the mixed solution into a preheated solvent for polymerization reaction; wherein, the step (1) and the step (2) are not separated in sequence. The bottom anti-reflective coating can reduce the reflectivity, and scum formed by the bottom anti-reflective coating is not observed after the bottom anti-reflective coating is used for spin coating a photoresist.
Description
Technical Field
The invention relates to a bottom anti-reflection coating for DUV lithography and a preparation method and application thereof.
Background
In recent years, due to the continuous high integration of large scale integrated circuits (LSIs), the resolution of a photoresist used in a photolithography process has become a crucial factor for miniaturization of the photolithography process, particularly for performing a ultra-fine pattern process of 30nm node (node) or less. Therefore, since the wavelength of the exposure light is further shortened in the g-line or i-line region which is generally used, studies on photolithography using deep ultraviolet rays, krF excimer lasers, and ArF excimer lasers have been attracting attention.
However, when the wavelength of the exposure light source is shortened, a light interference effect due to reflected light reflected on a layer to be etched of a semiconductor substrate is increased, and problems of deterioration of a pattern profile or reduction of dimensional uniformity occur due to undercut (undercut), notching (notching), or the like. In order to prevent the above problem, bottom-anti-reflective coatings (BARCs) for absorbing exposure light (reflected light) are generally formed between the layer to be etched and the photoresist film.
The anti-reflective coating is classified into an inorganic bottom anti-reflective coating, which is used by optimizing reflectance, and an organic bottom anti-reflective coating, which absorbs light passing through a photoresist film, according to the kind of material used.
The inorganic bottom anti-reflective coating has excellent conformality (conformality) to the bottom step, but is not easily removed in a subsequent process, and a pattern floating phenomenon (footing) often occurs, so the organic bottom anti-reflective coating is widely used in recent years.
In general, an organic bottom anti-reflective coating has advantages in that a vacuum evaporation apparatus, a Chemical Vapor Deposition (CVD) apparatus, a sputtering (sputter) apparatus, or the like for forming a film is not required, and the absorptivity to radiation is excellent, as compared to an inorganic bottom anti-reflective coating. Therefore, in order to reduce the reflectance as much as possible, a technique of preventing the reflection of an underlying film by disposing an organic anti-reflective coating layer containing light-absorbable organic molecules under a photoresist to adjust the reflectance becomes important. Currently, there is a strong need in the industry to develop excellent bottom anti-reflective coatings (BARCs) materials.
Disclosure of Invention
The invention provides a bottom anti-reflection coating for DUV photoetching and a preparation method and application thereof, aiming at overcoming the defects that the existing bottom anti-reflection coating has higher reflectivity and is frequently subjected to pattern floating. The reflectivity can be adjusted with the bottom antireflective coating for DUV lithography, and scum from the bottom antireflective coating is not observed after the antireflective coating is spin coated with photoresist.
The present invention provides a method for preparing a polymer for preparing a bottom anti-reflective coating, the method comprising the steps of:
(1) Preheating a solvent I;
(2) Mixing a monomer shown in a formula (A), a monomer shown in a formula (B), a monomer shown in a formula (C), a cross-linking agent shown in a formula (L), an initiator and a solvent II to obtain a mixed solution;
the dosage of the monomer shown in the formula (A) is 500-1000 parts by weight; the dosage of the monomer shown in the formula (B) is 500-1000 parts by weight; the dosage of the monomer shown in the formula (C) is 500-1000 parts by weight; the dosage of the cross-linking agent shown in the formula (L) is 100-200 parts by weight.
(3) Adding the mixed solution into a preheated solvent for polymerization reaction;
wherein, the step (1) and the step (2) are not separated in sequence.
In the preparation method of the polymer, the solvent I can be an organic solvent, preferably one or more of aromatic hydrocarbon solvents, ether solvents, ketone solvents, amide solvents, sulfoxide solvents and ester solvents. The aromatic hydrocarbon solvent is preferably toluene and/or benzene. The ethereal solvent is preferably tetrahydrofuran. The ketone solvent is preferably methyl amyl ketone. The amide solvent is preferably N, N' -dimethylformamide. The sulfoxide solvent is preferably dimethyl sulfoxide. The ester solvent is preferably ethyl lactate and/or propylene glycol monomethyl ether acetate. The organic solvent is more preferably an amide-based solvent and a ketone-based solvent, such as N, N' -dimethylformamide and methyl amyl ketone.
In the method for preparing the polymer, the solvent I is preferably used in an amount of 600 to 1000 parts by weight, and more preferably 1000 parts by weight. If two or more solvents are contained at the same time, the parts of the different solvents are preferably the same. In the preparation method of the polymer, in the step (1), the solvent I is purged by using nitrogen. The purge time is preferably 20 to 50 minutes, and more preferably 30 minutes.
In the preparation method of the polymer, in the step (1), the preheating temperature of the solvent I is preferably 80-100 ℃, and more preferably 90 ℃.
In the preparation method of the polymer, the solvent II can be an organic solvent, preferably one or more of aromatic hydrocarbon solvents, ether solvents, ketone solvents, amide solvents, sulfoxide solvents and ester solvents. The aromatic hydrocarbon solvent is preferably toluene and/or benzene. The ethereal solvent is preferably tetrahydrofuran. The ketone solvent is preferably methyl amyl ketone. The amide solvent is preferably N, N' -dimethylformamide. The sulfoxide solvent is preferably dimethyl sulfoxide. The ester solvent is preferably ethyl lactate and/or propylene glycol monomethyl ether acetate. The organic solvent is more preferably an amide-based solvent and a ketone-based solvent, such as N, N' -dimethylformamide and methyl amyl ketone.
In the preparation method of the polymer, the amount of the solvent II is preferably 6000 to 10000 parts by weight, and more preferably 7000 parts by weight. When two or more solvents are contained at the same time, the parts of the different solvents are preferably the same.
In the preparation method of the polymer, in the step (2), the monomer represented by the formula (A) is preferably used in an amount of 650 to 800 parts by weight.
In the preparation method of the polymer, in the step (2), the monomer represented by the formula (B) is preferably used in an amount of 650 to 800 parts by weight.
In the preparation method of the polymer, in the step (2), the monomer shown in the formula (C) is preferably used in an amount of 650 to 800 parts by weight.
In the preparation method of the polymer, in the step (2), the crosslinking agent represented by the formula (L) is preferably used in an amount of 150 parts by weight.
<xnotran> , (2) , , 2,2' - () (AIBN), 2,2' - - - (2- ), 2,2' - - (4- -2,4- ), 2,2' - (2- ), 2,2' - (2,4- ), 2,2' - (2,4- ), 1,1' - ( ), , , , -2- , , , 2,2' - () / 2,2' - - - (2- ). </xnotran>
In the preparation method of the polymer, in the step (2), the amount of the initiator is preferably 1 to 10wt%, more preferably 3 to 5wt%, and the percentage is the ratio of the weight of the initiator to the total weight of all monomers.
In the method for producing a polymer, in the step (2), the mixed solution is purged with nitrogen. The purge time is preferably 30 minutes.
In the preparation method of the polymer, in the step (3), the adding mode is preferably introduced by a peristaltic pump. The introduction time is preferably 2.5 hours.
In the method for preparing the polymer, in the step (3), the polymerization reaction temperature may be 50 to 200 ℃, preferably 60 to 150 ℃, and more preferably 80 to 120 ℃.
In the method for producing a polymer, in the step (3), the polymerization reaction time is preferably 5 to 7 hours, and more preferably 6 hours.
In the method for preparing the polymer, the polymerization reaction may be carried out by isolating and purifying the polymer using a post-treatment which is conventional in the art, or the reaction solution may be directly used as a raw material without isolating and purifying the polymer.
In the preparation method of the polymer, the polymerization reaction can use the conventional post-treatment in the field and comprises the following steps: cooling, adding an organic solvent to the reaction solution, removing a supernatant portion, dissolving the remaining reaction mixture in tetrahydrofuran, pouring the resulting solution into water, filtering and drying.
In the method for producing a polymer, in the post-polymerization treatment, the cooling is preferably performed by cooling the reaction solution to room temperature.
In the method for producing a polymer, in the post-treatment of the polymerization reaction, the organic solvent is preferably a poor solvent for the polymer but a good solvent for the polymer solvent, more preferably n-hexane or n-heptane, and most preferably n-heptane. The organic solvent is preferably used in an amount of 6000 parts by weight.
In the method for producing a polymer, the amount of water used in the post-polymerization treatment is preferably 100000 parts by weight.
In the method for producing a polymer, the filtration is preferably a filtration under reduced pressure in the post-polymerization treatment.
In the preparation method of the polymer, in the polymerization reaction post-treatment, the preferable drying condition is drying in a vacuum oven overnight. The temperature setting of the vacuum oven is preferably 45 ℃.
It is another object of the present invention to provide a polymer for preparing a bottom anti-reflective coating, which is prepared by the above method.
The polymer may be of any structure, such as a random copolymer or a block copolymer.
Among the polymers, the molecular weight thereof is not particularly limited, and the molecular weight of the polymer obtained by the polymerization reaction can be controlled by various polymerization conditions such as polymerization time and temperature, concentration of the monomer and initiator used in the reaction, and reaction solvent, etc. When the polymerization reaction is ionic polymerization, the molecular weight of the polymer is preferably a narrow molecular weight distribution.
In the polymer, the weight average molecular weight is preferably 2000 to 5000000 when the molecular weight is measured as standard polystyrene by Gel Permeation Chromatography (GPC), and more preferably 3000 to 100000, most preferably 5087, 5183, 5309, 5369, 6037, 6093, 6198 or 6511 in view of film-forming property, solubility and thermal stability.
In the polymer, the number average molecular weight is preferably 3000 to 6000, more preferably 3400, 3688, 3739, 3957, 4491, 5128, 5724 or 5788.
In the polymer, the polydispersity index (PDI) is preferably 0.5 to 2, more preferably 0.89, 0.92, 1.27, 1.34, 1.39, 1.46, 1.54 or 1.82.
The present invention provides a composition for preparing a bottom anti-reflective coating comprising a polymer as described above, a solvent and a photoacid generator.
In the composition, the solvent may be any solvent, and is preferably one or more of an ether solvent, an ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, a ketone solvent and an amide solvent. The ether solvent is preferably one or more of propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and propylene glycol monomethyl ether. The ester solvent is preferably one or more of propylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methyl-propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, and butyl lactate. The alcoholic solvent is preferably propylene glycol. The aromatic hydrocarbon solvent is preferably toluene and/or xylene. The ketone solvent is preferably one or more of methyl ethyl ketone, cyclopentanone, and cyclohexanone. The amide solvent is preferably one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone. More preferably, the solvent is propylene glycol monobutyl ether and/or propylene glycol monobutyl ether acetate.
The amount of the solvent used in the composition is such that all the components can be dissolved, and is preferably 1000 to 2500 parts by weight, more preferably 1200 to 2000 parts by weight, and most preferably 1500 to 1800 parts by weight.
In the composition, the photoacid generator can assist the crosslinked polymer in decrosslinking upon exposure and thereby render the target bottom antireflective coating developable and photosensitive.
In the composition, the photoacid generator may be any compound capable of generating an acid when exposed to KrF excimer laser (wavelength: 248 nm), arF excimer laser (wavelength: 193 nm), or the like, and is preferably one or more of an onium salt compound, a sulfone imide derivative, and a disulfonyl diazomethane compound.
In the composition, the onium salt compound in the photoacid generator is preferably an iodonium salt compound, a sulfonium salt compound, or a crosslinkable onium salt compound. The iodonium salt compound is preferably one or more of diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro n-butane sulfonate, diphenyliodonium perfluoro n-octane sulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate. The sulfonium salt compound is preferably one or more of triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butane sulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate, and more preferably triphenylsulfonium hexafluoroantimonate and/or triphenylsulfonium trifluoromethanesulfonate. The crosslinkable onium salt compound is preferably bis (4-hydroxyphenyl) (phenyl) sulfonium trifluoromethanesulfonate, or bis (phenyl) sulfonium trifluoromethanesulfonate bis (4-hydroxyphenyl) (phenyl) sulfonium 1,2, 3, 4-nonafluorobutane-1-sulfonate phenyl bis (4- (2- (vinyloxy) ethoxy) -phenyl) sulfonium 1,2, 3, 4-octafluoro-butane-1, 4-disulfonate and tris (4- (2- (vinyloxy) ethoxy) -phenyl) sulfonium 1,2, 3, 4-octafluoro-butane-1, 4-disulfonate.
In the composition, in the photoacid generator, the sulfone imide derivative is preferably one or more of N- (trifluoromethanesulfonyloxy) succinimide, N- (fluoro-N-butanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, and N- (trifluoromethanesulfonyloxy) naphthalimide.
In the composition, in the photoacid generator, the disulfonyl diazomethane compound is preferably one or more of bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2, 4-dimethylbenzenesulfonyl) diazomethane, and methylsulfonyl-p-toluenesulfonyl diazomethane.
The photoacid generator is preferably used in an amount of 0.01 to 20 parts by weight, more preferably 1 to 15 parts by weight, for example 5 to 10 parts by weight, in the composition.
The amount of the polymer used in the composition is preferably 100 parts by weight.
The composition may also contain other additional components. The additional components include polymers other than the polymers described above, surfactants, and slip agents.
In the composition, the amount of the additional component is not particularly limited and may be appropriately determined depending on the target coating layer.
It is another object of the present invention to provide a method for preparing a composition for preparing a bottom anti-reflective coating, comprising the steps of: the components of the composition as described above are mixed.
In the method for preparing the composition, the mixing mode is preferably stirring, and the stirring is preferably performed under the following conditions: stirred at room temperature for 30 minutes.
In the preparation method of the composition, after the mixing, a filtering step can be further included, wherein the filtering mode can be filtering by using a filter, and the pore diameter of the filter is preferably 0.2-0.05 μm, and more preferably 0.05 μm.
In the method for preparing the composition, the composition prepared by the preparation method has excellent storage stability and can be stored at room temperature for a long time.
It is another object of the present invention to provide a bottom antireflective coating prepared from the composition as described above.
It is another object of the present invention to provide a method for preparing a bottom anti-reflective coating, which is prepared by the following method, comprising the steps of: the composition as described above is cast on a semiconductor substrate and fired to provide a bottom anti-reflective coating.
In the preparation method of the bottom anti-reflective coating, the casting tool is preferably a spin coater or a coater, preferably a spin coater.
In the preparation method of the bottom anti-reflection coating, the semiconductor substrate is preferably one of a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate or an ITO substrate, and more preferably a silicon wafer substrate.
In the preparation method of the bottom anti-reflection coating, the baking temperature is preferably 80-250 ℃, more preferably 100-250 ℃, and most preferably 190 ℃.
In the method for preparing the bottom anti-reflective coating, the baking time is preferably 0.3 to 5 minutes, more preferably 0.5 to 2 minutes, and most preferably 1 minute.
The present invention also provides a method of forming a photoresist pattern on a bottom anti-reflective coating layer, comprising the steps of:
s1: coating a photoresist on the bottom anti-reflective coating;
s2, soft roasting;
s3: exposing;
s4: roasting;
s5: and (6) developing.
In the method for forming a photoresist pattern on a BARC layer, the photoresist may be conventional in the art, and is preferably a positive photoresist, a negative photoresist or a Negative Tone Development (NTD) photoresist, and more preferably a positive photoresist, such as 248nm positive photoresist (SEPR-430 (TM) (manufactured by Shin-Etsu)) or 193nm positive photoresist (TOK corporation, tai-6990 PH).
In the method for forming a photoresist pattern on a bottom anti-reflective coating layer, the soft baking temperature is preferably 100 to 140 ℃, and more preferably 120 ℃. The soft baking time is preferably 0.5 to 2 minutes, and more preferably 60 seconds.
In the method for forming a photoresist pattern on a BARC layer, the exposure light may be light having a wavelength of 13.5-248 nm, preferably KrF excimer laser (wavelength: 248 nm), arF excimer laser (wavelength: 193 nm) or extreme UV light (wavelength: 13.5 nm), which is conventional in the art.
In the method of forming a photoresist pattern on a bottom anti-reflective coating layer, the baking temperature is preferably 80 to 150 ℃, more preferably 100 to 140 ℃, and most preferably 130 ℃.
In the method of forming a photoresist pattern on a bottom anti-reflective coating layer, the baking time is preferably 0.3 to 5 minutes, more preferably 0.5 to 2 minutes, and most preferably 60 seconds.
In the method of forming a photoresist pattern on a bottom anti-reflective coating layer, the developing is performed using a developing solution. The developer can easily dissolve and remove the bottom anti-reflective coating.
The developing solution may be an alkaline developing solution, preferably an aqueous solution of an alkali metal hydroxide, an aqueous solution of a tertiary ammonium hydroxide or an aqueous solution of an amine. The aqueous solution of the alkali metal hydroxide is preferably an aqueous solution of potassium hydroxide or an aqueous solution of sodium hydroxide. The aqueous solution of the tertiary ammonium hydroxide is preferably an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of tetraethylammonium hydroxide, or an aqueous solution of choline. The aqueous amine solution is preferably an aqueous ethanolamine solution, an aqueous propylamine solution or an aqueous ethylenediamine solution. More preferably, the developing solution is a 2.38wt% aqueous solution of tetramethylammonium hydroxide.
In the method of forming a photoresist pattern on a bottom anti-reflective coating layer, the developing solution may further include a surfactant.
In the method of forming a photoresist pattern on a bottom anti-reflective coating layer, the developing solution temperature is preferably 5 to 50 ℃, more preferably 25 to 40 ℃.
In the method of forming a photoresist pattern on a bottom anti-reflective coating layer, the developing time is preferably 10 to 300 seconds, and more preferably 30 to 60 seconds.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: (1) The present invention provides a bottom antireflective coating for DUV lithography that reduces reflectivity. (2) The bottom anti-reflective coating for DUV lithography is excellent in performance, and after spin-coating a photoresist, the cross-sectional shape of the pattern is observed in the area exposed to radiation, and its practical use does not present any problem, and scum formed by the bottom anti-reflective coating is not observed.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the description of the examples, "parts" and "%" mean "parts by weight" and "wt%" respectively, unless otherwise specified.
Preparation of polymers
The polymers P1-P8 and the comparative polymers CP1-CP7 are prepared according to the following steps, and the dosage of the monomer shown in the formula (A), the monomer shown in the formula (B), the monomer shown in the formula (C) and the cross-linking agent shown in the formula (L) required for preparing each polymer is shown in the table 1.
In a reaction vessel equipped with a stirrer, a condenser, a heater and a thermostat were placed by weight parts of N, N' -dimethylformamide (500 parts) and methyl amyl ketone (500 parts). The solvent was purged with nitrogen for 30 minutes and then heated to 90 ℃.
Separately, a monomer represented by the formula (a), a monomer represented by the formula (B), a monomer represented by the formula (C), a crosslinking agent represented by the formula (L), 2 '-azobis (isobutyronitrile) (a radical polymerization initiator AIBN (100 parts)), N' -dimethylformamide (3500 parts), and methyl amyl ketone (3500 parts) in parts by weight were placed in a sample container and stirred. The resulting mixture solution was purged with nitrogen for 30 minutes.
The mixture solution was then introduced into the reaction vessel by means of a peristaltic pump over a period of 2.5 hours. After the introduction was complete, the reaction mixture was kept at 80 ℃ for 6 hours.
After cooling to room temperature, the mixture was poured into n-heptane (60000 parts). The supernatant fraction was removed and the remaining reaction mixture was dissolved in tetrahydrofuran (6000 parts). The resulting solution was poured into water (100000 parts) to form a white precipitate. The precipitate was isolated by filtration under reduced pressure and dried in a vacuum oven at 45 ℃ overnight.
By drying, the copolymer was obtained in the form of white powder. The weight average molecular weight Mw and number average molecular weight of the product were measured by GPC (THF) to calculate the polydispersity index PDI.
TABLE 1
Examples 1-16, comparative examples 17-30: preparation of bottom anti-reflection coating
To the polymer prepared above, a solvent and a photoacid generator were added in amounts shown in Table 2. The obtained mixture was stirred at room temperature for 30 minutes, and then the mixture was filtered through a 0.05 μm pore size filter to prepare a composition for forming a bottom anti-reflective coating in the form of a solution.
The prepared composition for forming bottom anti-reflective coating was cast on a silicon microchip wafer by spin coating, and firing crosslinking was performed by heating at 190 ℃ for 60 seconds on a vacuum hot plate to prepare bottom anti-reflective coatings of examples 1 to 16 and comparative examples 1 to 14, wherein
The polymers used in Table 2 were polymers P1 to P8 and CP1 to CP7 prepared in the above Table 1.
TABLE 2
Application and effects embodiments
1. Optical performance detection
The refractive index (n value) and extinction coefficient (k value) at 248nm and 193nm were measured by ellipsometry of the obtained bottom anti-reflective coating.
2. Development Performance detection
(1) Method for forming photoresist pattern on bottom anti-reflection coating when exposure light wavelength is 248nm and developing performance detection
A commercial 248nm positive photoresist (SEPR-430 TM (manufactured by Shin-Etsu)) was spin-coated on the obtained antireflective coating. The resist layer formed was soft-baked at 120 ℃ on a vacuum hotplate and then imagewise exposed to 248nm radiation through a photomask. After the post-exposure baking at 130 ℃ for 60 seconds, the resist layer was developed using a 2.38wt% aqueous solution of TMAH. As a result of this development, the photoresist layer and underlying bottom antireflective coating are removed in the areas defined by the photomask. In the areas exposed to the radiation, the solvent resistance of the antireflective coating was observed. The cross-sectional shape of the pattern was observed. In addition, it was observed whether the bottom anti-reflective coating formed scum.
(2) Method for forming photoresist pattern on bottom anti-reflection coating when exposure light wavelength is 193nm and development performance detection
On the obtained bottom anti-reflective coating layer, a commercial 193nm positive photoresist (TOK Corp., tai-6990 PH) was spin coated. The resist layer formed was soft-baked at 120 ℃ for 60 seconds on a vacuum hotplate and then imagewise wet exposed to 193nm radiation through a photomask. After the post-exposure baking at 130 ℃ for 60 seconds, the resist layer was developed using a 2.38wt% aqueous solution of TMAH. As a result of this development, the photoresist layer and underlying bottom antireflective coating are removed in the areas defined by the photomask. In the areas exposed to the radiation, the solvent resistance of the antireflective coating was observed. The cross-sectional shape of the pattern was observed. In addition, it was observed whether the bottom anti-reflective coating formed scum.
The effects of the anti-reflective coatings B1 to B16 prepared in examples 1 to 16 and the CBs 1 to CB14 prepared in comparative examples 1 to 14 are shown in table 3.
TABLE 3
Remarking: regarding the cross-sectional shape of the pattern: a denotes that both the photoresist and the bottom antireflective coating show rectangular sides perpendicular to the substrate surface; b indicates that both the photoresist and the bottom anti-reflective coating show a side surface not perpendicular to but slightly inclined to the substrate surface, but there is no problem in practical use; c represents the side of both the photoresist and the bottom antireflective coating that exhibit a nesting shape with respect to the substrate surface.
Regarding scum: a represents that scum formed by the bottom anti-reflective coating was not observed; b indicates that slight scum is observed from the bottom anti-reflective coating, but practically negligible; c indicates that a large amount of scum formed by the bottom anti-reflective coating was observed.
As can be seen from table 3, the obtained bottom anti-reflective coating can reduce the reflectance; with the exception of B12, 193nm positive type photoresist and 248nm positive type photoresist were spin-coated on the obtained bottom anti-reflective coating layer, respectively, and the cross-sectional shape of the pattern was observed in the region exposed to the radiation such that both the photoresist and the bottom anti-reflective coating layer showed rectangular sides perpendicular to the substrate surface, and no scum formed by the bottom anti-reflective coating layer was observed. 193nm positive type photoresist and 248nm positive type photoresist were spin-coated on the obtained bottom anti-reflective coating layer B12, respectively, and the sectional shape of the pattern observed in the region exposed to the radiation was such that both the photoresist and the bottom anti-reflective coating layer showed a side face not perpendicular but slightly inclined to the substrate surface, but there was no problem in practical use and scum formed by the bottom anti-reflective coating layer was not observed. In the comparative examples, the cross-sectional shapes of the patterns were mostly such that both the photoresist and the BARC layer showed a side surface in a fitting shape with respect to the substrate surface, and a large amount of scum formed by the BARC layer was observed, which affected the use.
In view of the above, the present invention has developed a bottom anti-reflective coating for DUV lithography, which is capable of reducing reflectance, observing the cross-sectional shape of a pattern in an area exposed to radiation after spin-coating a photoresist, and which is practically usable without any problem, and in which scum formed by the bottom anti-reflective coating is not observed.
Claims (10)
1. A process for the preparation of a polymer for use in the preparation of a bottom antireflective coating, said process comprising the steps of:
(1) Preheating a solvent I;
(2) Mixing a monomer shown in a formula (A), a monomer shown in a formula (B), a monomer shown in a formula (C), a cross-linking agent shown in a formula (L), an initiator and a solvent II to obtain a mixed solution;
the dosage of the monomer shown in the formula (A) is 500-1000 parts by weight; the dosage of the monomer shown in the formula (B) is 500-1000 parts by weight; the dosage of the monomer shown in the formula (C) is 500-1000 parts by weight; the dosage of the cross-linking agent shown in the formula (L) is 100-200 parts by weight;
(3) Adding the mixed solution into a preheated solvent for polymerization reaction;
wherein, the step (1) and the step (2) are not separated in sequence.
2. The method for preparing the polymer according to claim 1, wherein in the step (1), the solvent I is an organic solvent, preferably one or more of an aromatic hydrocarbon solvent, an ether solvent, a ketone solvent, an amide solvent, a sulfoxide solvent and an ester solvent; the aromatic hydrocarbon solvent is preferably toluene and/or benzene; the ether solvent is preferably tetrahydrofuran; the ketone solvent is preferably methyl amyl ketone; the amide solvent is preferably N, N' -dimethylformamide; the sulfoxide solvent is preferably dimethyl sulfoxide; the ester solvent is preferably ethyl lactate and/or propylene glycol monomethyl ether acetate; the solvent I is more preferably an amide-based solvent and a ketone-based solvent, such as N, N' -dimethylformamide and methyl amyl ketone;
and/or, in the step (1), the amount of the solvent I is 600 to 1000 parts by weight, preferably 1000 parts by weight; if more than two solvents are contained at the same time, the parts of different solvents are preferably the same;
and/or, in the step (1), the solvent I is purged by using nitrogen; the purging time is preferably 20 to 50 minutes, and more preferably 30 minutes;
and/or in the step (1), the preheating temperature of the solvent I is 80-100 ℃, and preferably 90 ℃;
and/or in the step (2), the solvent II is an organic solvent, preferably one or more of an aromatic hydrocarbon solvent, an ether solvent, a ketone solvent, an amide solvent, a sulfoxide solvent and an ester solvent; the aromatic hydrocarbon solvent is preferably toluene and/or benzene; the ether solvent is preferably tetrahydrofuran; the ketone solvent is preferably methyl amyl ketone; the amide solvent is preferably N, N' -dimethylformamide; the sulfoxide solvent is preferably dimethyl sulfoxide; the ester solvent is preferably ethyl lactate and/or propylene glycol monomethyl ether acetate; the organic solvent is more preferably an amide-based solvent and a ketone-based solvent, such as N, N' -dimethylformamide and methyl amyl ketone;
and/or, in the step (2), the amount of the solvent II is 6000 to 10000 parts by weight, preferably 7000 parts by weight; if more than two solvents are contained at the same time, the parts of different solvents are preferably the same;
and/or in the step (2), the monomer shown in the formula (A) is used in an amount of 650-800 parts by weight;
and/or in the step (2), the monomer shown in the formula (B) is used in an amount of 650-800 parts by weight;
and/or in the step (2), the monomer shown in the formula (C) is used in an amount of 650-800 parts by weight;
and/or in the step (2), the dosage of the cross-linking agent shown in the formula (L) is 150 parts by weight;
and/or, in the step (2), the initiator is 2,2 '-azobis (isobutyronitrile), 2' -azobis-dimethyl- (2-methylpropionate), 2 '-azobis- (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis (2-cyclopropylpropionitrile), 2 '-azobis (2, 4-dimethylvaleronitrile) 1,1' -azobis (cyclohexanecarbonitrile), benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl diperoxyphthalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxypivalate, and butyl lithium; preferably 2,2' -azobis (isobutyronitrile) and/or 2,2' -azobis-dimethyl- (2-methylpropionate), more preferably 2,2' -azobis (isobutyronitrile);
and/or, in the step (2), the amount of the initiator is 1 to 10wt%, preferably 3 to 5wt%, and the percentage is the ratio of the weight of the initiator to the total weight of all monomers;
and/or, in the step (2), the mixed solution is purged by using nitrogen; the purge time is preferably 30 minutes;
and/or, in the step (3), the adding mode is that a peristaltic pump is used for introducing; the introduction time is preferably 2.5 hours;
and/or, in the step (3), the temperature of the polymerization reaction is 50-200 ℃, preferably 60-150 ℃, and more preferably 80-120 ℃;
and/or, in the step (3), the polymerization reaction time is 5 to 7 hours, preferably 6 hours.
3. A polymer for preparing a bottom anti-reflective coating, wherein the polymer is prepared by the polymer preparation method of claim 1 or 2.
4. The polymer of claim 3, wherein the polymer has a weight average molecular weight of 2000 to 5000000, preferably a weight average molecular weight of 3000 to 100000, more preferably 5087, 5183, 5309, 5369, 6037, 6093, 6198 or 6511;
and/or the polymer has a number average molecular weight of 3000 to 6000, preferably 3400, 3688, 3739, 3957, 4491, 5128, 5724 or 5788;
and/or the polymer polydispersity index is from 0.5 to 2, preferably 0.89, 0.92, 1.27, 1.34, 1.39, 1.46, 1.54 or 1.82.
5. A composition for preparing a bottom antireflective coating comprising the polymer of claim 3 or 4, a solvent, and a photoacid generator.
6. The composition according to claim 5, wherein the solvent is one or more of an ether solvent, an ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, a ketone solvent and an amide solvent; the ether solvent is preferably one or more of propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and propylene glycol monomethyl ether; the ester solvent is preferably one or more of propylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methyl-propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, and butyl lactate; the alcohol solvent is preferably propylene glycol; the aromatic hydrocarbon solvent is preferably toluene and/or xylene; the ketone solvent is preferably one or more of methyl ethyl ketone, cyclopentanone and cyclohexanone; the amide solvent is preferably one or more of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the solvent is more preferably propylene glycol monobutyl ether and/or propylene glycol monobutyl ether acetate;
and/or the solvent is used in an amount of 1000 to 2500 parts by weight, preferably 1200 to 2000 parts by weight, more preferably 1500 to 1800 parts by weight;
and/or the photoacid generator is one or more of an onium salt compound, a sulfone imide derivative, and a disulfonyl diazomethane compound;
and/or the photoacid generator is used in an amount of 0.01 to 20 parts by weight, preferably 1 to 15 parts by weight, for example 5 to 10 parts by weight;
and/or the polymer is used in an amount of 100 parts by weight.
7. The composition of claim 6, wherein the onium salt compound is an iodonium salt compound, a sulfonium salt compound, or a crosslinkable onium salt compound; the iodonium salt compound is preferably one or more of diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro n-butane sulfonate, diphenyliodonium perfluoro n-octane sulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate; the sulfonium salt compound is preferably one or more of triphenyl sulfonium hexafluoroantimonate, triphenyl sulfonium nonafluoro-n-butane sulfonate, triphenyl sulfonium camphor sulfonate and triphenyl sulfonium trifluoromethane sulfonate, and more preferably triphenyl sulfonium hexafluoroantimonate and/or triphenyl sulfonium trifluoromethane sulfonate; the crosslinkable onium salt compound is preferably bis (4-hydroxyphenyl) (phenyl) sulfonium trifluoromethanesulfonate, or bis (phenyl) sulfonium trifluoromethanesulfonate bis (4-hydroxyphenyl) (phenyl) sulfonium 1,2, 3, 4-nonafluorobutane-1-sulfonate phenyl bis (4- (2- (vinyloxy) ethoxy) -phenyl) sulfonium 1,2, 3, 4-octafluoro-butane-1, 4-disulfonate and tris (4-one or more of (2- (vinyloxy) ethoxy) -phenyl) sulfonium 1,2, 3, 4-octafluoro-butane-1, 4-disulfonate;
and/or the sulfone imide derivative is one or more of N- (trifluoromethanesulfonyloxy) succinimide, N- (fluoro-N-butane sulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide and N- (trifluoromethanesulfonyloxy) naphthalimide;
and/or the disulfonyl diazomethane compound is one or more of bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2, 4-dimethylbenzenesulfonyl) diazomethane and methylsulfonyl-p-toluenesulfonyl diazomethane.
8. The composition of claim 5, wherein the composition further comprises additional components, the additional components comprising a polymer other than the polymer of claim 3 or 4, a surfactant, and a smoothing agent.
9. A process for the preparation of a composition for the preparation of a bottom antireflective coating, characterized in that the process comprises the following steps: mixing the components of the composition according to any one of claims 5 to 8.
10. The method for preparing the composition according to claim 9, wherein the mixing means is stirring, and the stirring condition is preferably stirring at room temperature for 30 minutes; after the mixing, the method can further comprise a filtering step, wherein the filtering mode can be filtering by using a filter, and the pore diameter of the filter can be 0.2-0.05 μm, and is preferably 0.05 μm.
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