Coated combination of photoresist and Si-based hard mask

Abstract

The present invention relates to a photoresist coating composition for a bilayer photoresist coating, a method of coating a microelectronic device by coating such a composition as a combined photoresist (PR) and Si-based hard mask (SiHM), and a method of forming a patterned device by coating such a composition.

Description

Technical Field

[0001] The present invention relates to a photoresist coating composition for a bilayer photoresist coating, a method of coating a microelectronic device by coating such a composition, and a method of forming a patterned device by coating such a composition, as a combined photoresist (PR) and Si-based hard mask (SiHM). Background Art

[0002] To improve the performance and productivity of electronic devices, the semiconductor industry often needs to produce smaller but more dense features for IC manufacturing. To be able to fabricate smaller devices, new and better microlithography materials and methods are required.

[0003] Generally, it is necessary to reduce the thickness of the imaging layer to produce high-resolution finer feature pattern sizes. Multilayer imaging stacks are required to pattern semiconductor devices, which may consist of a single-layer photoresist, an etch-resistant Si-based hard mask layer, and a C layer, to obtain better etch selectivity and image transfer.

[0004] To reduce complexity and cost, the photoresist and the hard mask layer can be combined into a bilayer photoresist. Prior art such as U.S. Patent Nos. 5,338,818, 5,385,804, 5,985,524, 6,087,064, 6,939,664, 7,041,748 of IBM, Japanese Patent No. 4,192,068, U.S. Patent No. 7,875,417 of Shin-Etsu Chemical Co., U.S. Patent No. 4,745,169 of Hitachi, U.S. Patent No. 6,074,962 of TOK, U.S. Patent Nos. 6,531,260, 6,846,895, 7,041,748 of JSR, U.S. Patent Nos. 6,296,985, 6,589,705, 7,217,493 of FujiFilm, U.S. Patent No. 6,589,707 of Hyundai Electronics, and U.S. Patent No. 9,842,852 of Samsung Electronic Company teach the use of bilayer photoresists in microlithography patterning. Additionally, bilayer photoresists are shown in the teachings of the following prior art: U.S. Patent Nos. 7,625,687, 8,088,547, 8,148,043 of Dow Corning Corp. and U.S. Patent Nos. 6,146,793, 6,916,543, 6,615,682 of Arch Specialty Chemicals.

[0005] Improvements in bilayer photoresist (PR / hard mask) materials are always welcome for solving many integration problems that arise during semiconductor device fabrication. SUMMARY OF THE INVENTION

[0006] One object of the present invention is to provide a photoresist coating composition for a bilayer photoresist coating, wherein a photoresist layer and an Si-based etch-resistant layer are combined as a bilayer system to enhance microlithography in the semiconductor device manufacturing process.

[0007] Another object of the present invention is to provide a photoresist coating composition for a bilayer photoresist coating, wherein the bilayer photoresist coating is positive tone, patterned with ArF exposure, and developed with an alkaline developer.

[0008] Another object of the present invention is to provide a photoresist coating composition for a bilayer photoresist coating, wherein the bilayer photoresist coating is converted into a hard mask (HM) with good etch selectivity during lithography and etching processes.

[0009] Furthermore, the combination of the available physical properties of the photoresist (PR) and the Si-based hard mask (SiHM) is referred to as PR / SiHM or bilayer photoresist in the present invention.

[0010] Another object of the present invention is to provide a composition of the PR / SiHM layer material. The composition is based on a silicone copolymer that contains Si-H units in its main chain structure, thereby obtaining alkali solubility, a higher Si-content, and thus better etch selectivity during reactive ion etching (RIE).

[0011] Another object of the present invention is to provide a composition of the PR / SiHM layer material. The composition is based on a silicone copolymer that contains polarity-converting side groups as acid-labile groups on the silicone backbone of the silicone copolymer to obtain dissolution contrast.

[0012] Another object of the present invention is to provide a composition of the bilayer photoresist layer material. The composition is based on a silicone copolymer that contains Si-OH side groups as polar groups for better adhesion and easier development on the silicone backbone of the silicone copolymer.

[0013] Another object of the present invention is to provide a composition of the bilayer photoresist layer material. The composition is based on a silicone copolymer that has a specific molar percentage of Si (%Si) on the silicone backbone of the silicone copolymer to adjust the etch selectivity performance of the coating. The amount of Si in the starting monomer mixture is in the range of 8 mol% to 45 mol%, preferably in the range of 30 to 40 mol%.

[0014] The Si-containing copolymer of the present invention improves the etch resistance and the etch selectivity to the organic underlayer.

[0015] In a specific embodiment, the present invention provides a photoresist coating composition for a bilayer photoresist coating, which has the following siloxane copolymer structure:

[0016] [R 1 SiO 1.5 a [R 2 SiO 1.5 b [Si(OH)O 1.5 c [SiO2] d [R 3 SiO 1.5 e [R 4 SiO 1.5 f

[0017] where 0 < a, b, c, d, e, f < 0.9 and a + b + c + d + e + f = 1,

[0018] Preferably, 0.1 < a < 0.5, 0.1 < b < 0.50, 0.05 < c < 0.30, 0.01 < d < 0.20, 0.05 < e < 0.40, 0.05 < f < 0.40.

[0019] R 1 is a (meth)acrylate-derived structural unit containing a polycyclic group, such as adamantyl, methyladamantyl, ethyladamantyl, propyladamantyl, butyladamantyl or norbornyl; R 1 is readily dissociable into an acid-labile group by a strong acid generated by a photoacid generator such as t-butyl ester lithography to obtain an adjustable dissolution contrast;

[0020] R 2 is H to obtain alkali solubility and better etch selectivity;

[0021] R 3 is a (meth)acrylate-derived structural unit containing a polycyclic group, such as adamantyl, methyladamantyl, ethyladamantyl, propyladamantyl, butyladamantyl or norbornyl containing a hydroxyl group, and the hydroxyl group serves as a polar group for alkali solubility in an alkali developer, thus improving the pattern resolution;

[0022] SiO2 serves as a Q structure in the main chain (e.g., a (Si-O)4 linker with four Si-O bonds) to obtain stability and etch resistance;

[0023] R​​​​​4 is a (meth)acrylate-derived structural unit containing a lactone group or a group containing a lactone group, such as γ-butyrolactone, for better adhesion.

[0024] The silicone copolymer solution of the bilayer photoresist layer material can be spin-coated, pre-baked, ArF-exposed, post-baked, developed, and RIE-etched to produce a target photopatterned structure.

[0025] Another object of the present invention is to provide a method for coating a microelectronic device, comprising:

[0026] (i) preparing a photoresist coating composition for the bilayer photoresist coating of the present invention,

[0027] (ii) providing an organic solvent,

[0028] (iii) providing a photoacid catalyst,

[0029] (iv) providing a base quencher,

[0030] (v) providing an additive,

[0031] (vi) coating a solution mixture comprising (i), (ii), (iii), (iv), and (v) on a substrate,

[0032] (vii) evaporating the solvent from the coating using pre-baking,

[0033] (viii) exposing the film to ArF to produce a photopattern,

[0034] (ix) post-baking the film,

[0035] (x) developing the film to produce a photolithographic pattern.

[0036] According to the above method, wherein the solution mixture in step (iv) is spin-coated on the substrate.

[0037] According to the above method, wherein the solvent in step (vii) is evaporated during the spin-coating process.

[0038] According to the above method, wherein the coating in step (vi) is dried by heating at about 100 °C to about 250 °C for about 30 to about 120 seconds.

[0039] According to the above method, wherein the thickness of the film in step (x) is about 100 nm to about 500 nm.

[0040] Another object of the present invention is to provide a method for forming a patterned device, comprising:

[0041] a. coating a photoresist coating composition of the bilayer photoresist coating of the present invention on a device substrate to form a silicon-rich photoresist,

[0042] b. The ArF light-patterned bilayer photoresist is post-baked and developed to form a resist pattern.

[0043] c. The resist pattern is transferred to the underlying layer using RIE.

[0044] d. The exposed areas are removed by etching to produce the patterned device. Description of the Drawings

[0045] In Figure 1 Examples of applying the bilayer photoresist coating of the present invention in semiconductor device manufacturing are illustrated. The photolithography, patterning, and etching steps are illustrated in the following figures:

[0046] Figure 1 A illustrates a cross-section of a coated stack of a mask (filled black area), (1) bilayer photoresist, and (2) organic layer on a substrate, where the downward arrow shows ArF exposure.

[0047] Figure 1 B illustrates the patterned photoresist (1) layer exposed and developed on top of other layers.

[0048] Figure 1 C illustrates etching to transfer the photoresist (1) pattern to the organic layer (2).

[0049] Figure 1 D illustrates pattern transfer to the IC layer.

[0050] Figure 1 E illustrates removal of the organic layer (2) to leave the final pattern on the target IC layer.

[0051] Detailed Description of the Invention

[0052] In context, the terms "photoresist coating composition" and "photoresist composition" are interchangeable, "bilayer photoresist coating" and "bilayer photoresist" are interchangeable, and "bilayer" and "PR / SiHM layer" are interchangeable.

[0053] One object of the present invention is to provide a photoresist coating composition for a bilayer photoresist coating, wherein a photoresist layer and an Si-based etch-resistant layer are combined into a bilayer system to enhance microlithography in the semiconductor device manufacturing process.

[0054] Another object of the present invention is to provide a photoresist coating composition for a bilayer photoresist coating, wherein the bilayer photoresist coating is positive, patterned with ArF exposure, and developed with an alkaline developer.

[0055] Another object of the present invention is to provide a photoresist coating composition for a bilayer photoresist coating, wherein the bilayer photoresist coating is converted into a hard mask (HM) with good etch selectivity during lithography and etching processes.

[0056] Furthermore, the combination of the available photoresist (PR) and Si-based hard mask (SiHM) properties is referred to as PR / SiHM or bilayer photoresist in the present invention.

[0057] Another object of the present invention is to provide a composition of the PR / SiHM layer material. The composition is based on a siloxane copolymer that contains Si-H units in its backbone structure, thereby obtaining alkali solubility, a higher Si-content, and thus better etch selectivity during reactive ion etching (RIE).

[0058] Another object of the present invention is to provide a composition of the PR / SiHM layer material. The composition is based on a siloxane copolymer that contains polar conversion side groups as acid-labile groups on the siloxane backbone of the siloxane copolymer to obtain dissolution contrast.

[0059] Yet another object of the present invention is to provide a composition of a bilayer photoresist layer material. The composition is based on a siloxane copolymer that contains Si-OH side groups as polar groups for better adhesion and easier development on the siloxane backbone of the siloxane copolymer.

[0060] Yet another object of the present invention is to provide a composition of a bilayer photoresist layer material. The composition is based on a siloxane copolymer that has a specific Si molar percentage (%Si) on the siloxane backbone of the siloxane copolymer to regulate the etch selectivity performance of the coating.

[0061] The Si-containing copolymer of the present invention improves the etch resistance and the etch selectivity for the organic underlying layer.

[0062] Furthermore, the combination of both a photoresist and a Si-containing hard mask layer is combined in a bilayer photoresist system, comprising:

[0063] (I) A siloxane copolymer formed by hydrosilylation of a hydrogenated silsesquioxane polymer with one or more functional cycloolefins having reactive groups, preferably carried out in a one pot process, and the siloxane copolymer A has the following formula:

[0064] [R 1 SiO 1.5 a [R 2 SiO 1.5 b [Si(OH)O 1.5 c [SiO2]​​​d [R 3 SiO 1.5 e [R 4 SiO 1.5 f

[0065] where 0 < a, b, c, d, e, f < 0.9 and a + b + c + d + e + f = 1,

[0066] Preferably, 0.1 < a < 0.5, 0.1 < b < 0.50, 0.05 < c < 0.30, 0.01 < d < 0.20, 0.05 < e < 0.40, 0.05 < f < 0.40,

[0067] R 1 is a methacrylate-derived structural unit containing a polycyclic group, such as an adamantyl group, methyladamantyl group, ethyladamantyl group, propyladamantyl group, butyladamantyl group, or norbornyl group; R 1 is easily dissociated from a strong acid generated by a photoacid generator, such as tert-butyl ester lithography, into an acid-labile group to obtain an adjustable dissolution contrast,

[0068] R 2 is H to obtain alkali solubility and better etching selectivity,

[0069] R 3 is a methacrylate-derived structural unit containing a polycyclic group, such as an adamantyl group, methyladamantyl group, ethyladamantyl group, propyladamantyl group, butyladamantyl group, or norbornyl group containing a hydroxyl group; the hydroxyl group serves as a polar group for alkali solubility in an alkali developer, thus improving pattern resolution,

[0070] SiO2 serves as a Q structure in the main chain (e.g., a (Si-O)4 linker with four Si-O bonds) to obtain stability and etching resistance,

[0071] R 4 is a methacrylate-derived structural unit containing a lactone group or having a lactone-containing group, such as a γ-butyrolactone group, for better adhesion,

[0072] (II) an organic solvent,

[0073] (III) a photo-generated catalyst, and

[0074] (IV) a basic compound as an acid quencher.

[0075] ​​The organic solvent may be selected from ketones, ethers, esters, and diols, such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, cyclohexanone, N-methylpyrrolidone, N,N-dimethylacetamide, propylene glycol methyl ether, dibutyl ether, methoxy-2-propanol, dipentyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, 2-butanone, tetrahydrofuran, 1,2-diethoxyethane, 1,2-dimethoxymethane, diethyl oxalate, butyl lactate, dimethoxyethane, γ-butyrolactone, and methyl tert-butyl ether, wherein the amount of the solvent is about 80 wt% - about 99 wt%, based on the total coating composition.

[0076] The photo-generated catalyst may be selected from ionic photoacid generators, such as triphenylsulfonium perfluoro-1-butanesulfonate (TPSNF), or non-ionic photoacid generators, such as 2-[2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutanesulfonyloxyimino)-pentyl]-fluorene (ONPF) (BASF CIBA / GICI 1907-oximesulfonate), etc.

[0077] The ionic photoacid generator and / or non-ionic photoacid generator may be used in a total amount of 0.1 to 5 wt% of the total weight of the formulation.

[0078] The basic compound may be selected from amines, amides, imides, and nitrogen-containing compounds, such as; methylamine, dimethylamine, dimethanolamine, trimethylamine, trimethanolamine, methanolamine, ethylamine, ethanolamine, diethylamine, triethylamine, triethanolamine, isopropylamine, isopropanolamine, diisopropanolamine, diisopropylamine, triisopropylamine, triisopropanolamine, n-butylamine, n-butanolamine, di-n-butylamine, di-n-butanolamine, tri-n-butanolamine, tri-n-butylamine, tert-butylamine, tert-butanolamine, di-tert-butylamine, di-tert-butanolamine, tri-tert-butanolamine, tri-tert-butylamine, 1-tert-butoxycarbonyl (Boc)-4-piperidone, 3-tert-butoxycarbonyl-amino-1-propanol, 1-tert-butoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonyl-L-proline, N-tert-butoxycarbonyl-diethanolamine, N-tert-butoxycarbonyl-2-(2-hydroxyethyl)piperidine, and combinations thereof. The basic compound may be used in a total amount of 0.1 to 10 wt% of the total weight of the photoacid generator.

[0079] The siloxane copolymer of the present invention is formed in a one-pot synthesis method by hydrosilylation of a hydridosilsesquioxane polymer with one or more functional cycloolefins having reactive groups such as: (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-methylcyclopentylbicyclo[2.2.1]hept-5-ene-2-carboxylate, 1-methylcyclohexylbicyclo[2.2.1]hept-5-ene-2-carboxylate, tert-butylbicyclo[2.2.1]hept-5-ene-2-carboxylate, 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and 8,8,8-trifluoro-7-hydroxy-7(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, norbornene sulfonamide, and combinations thereof.

[0080] Hydridosilsesquioxane polymers have been known for many years and are white solids in dry form but are soluble in organic solvents such as benzene, toluene, xylene, hexane, heptane, octane, cyclohexane, phenyl ether, dibutyl ether, methyl isobutyl ketone, methyl ethyl ketone, etc. Hydridosilsesquioxane polymers are commercially produced as specialty chemicals around the world.

[0081] Hydrosilylation catalysts are well known and can be found in the literature as transition metal complexes such as platinum, rhodium or nickel complexes. A well-known hydrosilylation catalyst is the catalyst of Karlstad, Pt2[(Me2SiCH=CH2)2O]3, which is formed by treating hexachloroplatinic acid [H3O]2[PtCl6] with 1,3-divinyltetramethyldisiloxane or other platinum complexes such as platinum-carbonyl, platinum vinylmethylcyclosiloxane or other transition metal complexes such as rhodium- or nickel-containing complexes, etc. The amount of the hydrosilylation catalyst can be 50 - 2,000 ppm, based on the amount of the Si-H containing reactant. Toluene can be used as the hydrosilylation solvent.

[0082] Another useful feature of the siloxane copolymer for the bilayer photoresist of the present invention is to control the amount of %Si in the composition based on the siloxane copolymer by controlling the amount of the siloxane copolymer, thereby controlling the etching selectivity of the PR / HM coating material.

[0083] Another useful component of the siloxane copolymer of the bilayer photoresist of the present invention is that the silanol (Si-OH) functional groups present in the final bilayer photoresist siloxane copolymer contribute to the adhesion and alkali solubility of standard developers such as aqueous TMAH (tetramethylammonium hydroxide).

[0084] Another useful component of the silicone copolymer of the double-layer photoresist of the present invention is the presence of Q units (e.g., (Si-O)4 linkages with four Si-O bonds) in the structure, which enhance stability.

[0085] The silicone copolymer for the double-layer photoresist of the present invention can have a weight-average molecular weight (Mw) of about 800 to about 30,000, which is determined by gel permeation chromatography (GPC). The preferred Mw range is 1,000 to 20,000.

[0086] In some embodiments, the double-layer photoresist silicone-copolymer component can account for 1 wt% to 10 wt% of the total double-layer photoresist / hard mask PR / SiHM formulation of the coating solution.

[0087] Spin coating can be used as a method for applying the double-layer photoresist silicone copolymer PR / SiHM formulation in semiconductor device manufacturing. The spin coating method generally requires pouring a small amount of the PR / SiHM solution as a paste onto the surface of the semiconductor device, followed by an acceleration of 4000 - 5000 rpm to a selected final speed of 2000 to 3000 rpm, which spreads the material on the surface and maintains it at the final speed for 10 - 20 seconds before completing the rotation. In this way, a uniform coating of the double-layer photoresist silicone copolymer PR / SiHM formulation as a PR / SiHM layer is formed on the surface of the semiconductor device.

[0088] The double-layer photoresist / hard mask (PR / SiHM) is spin-coated on the surface of the underlying coating, followed by pre-baking and exposure to ArF light patterning, post-exposure baking, and development to produce a patterned photoresist structure. The next step is to transfer the patterned photoresist pattern to the underlying layer using reactive ion etching (RIE). The step after the pattern transfer through the underlying layer is oxygen plasma etching to convert the photoresist / hard mask of the present invention into a patterned hard mask layer. This patterned hard mask will also be able to transfer the pattern to the sub-layer using a suitable RIE etching chemistry, and then the hard mask and the protected target patterned structure are removed on the semiconductor device.

[0089] Figure 1 Examples of applying the photoresist / hard mask (PR / SiHM) coating of the present invention in semiconductor device manufacturing are illustrated, however, this is not the only use and should not be used as a limiting factor for the uses of the present invention, and the coatings of the present invention can be used in many other ways. The geometries and dimensions used in this example are only for illustration to better clarify the example and do not represent the actual geometries and dimensions.

[0090] The substrate can be a conductive material or a semiconductor material such as SiGe, gallium arsenide, etc., or an insulator such as SiO2, Si3N4, etc., or their doped variants or mixtures. An example of the target layer to be patterned in this instance is a dielectric layer. Figure 1 Layer (2) in a stack is a carbon-based layer. The photoresist / hard mask (PR / SiHM) silicone copolymer composition of the present invention is spin-coated on layer (2) at a speed of about 2000 to about 3000 rpm for a period of about 10 seconds to about 20 seconds. Then the photoresist / hard mask (PR / SiHM) coating is thermally baked at a temperature of about 100 °C to about 250 °C for a period of about 30 seconds to about 90 seconds. ArF is patternwise exposed through an exposure mask ( Figure 1 , filled black areas) and post-exposure baked, and finally developed to remove the exposed areas. The photolithography, patterning, and etching steps are illustrated in more detail in the following figures Figure 1 A - E:

[0091] Figure 1 A illustrates a cross-section of a coated layer of a stack of a mask (filled black areas), (1) bilayer photoresist, (2) organic layer, (3) dielectric layer on a substrate, where the downward arrow shows ArF exposure.

[0092] Figure 1 B illustrates the patterned bilayer photoresist (1) exposed and developed on top of other layers.

[0093] Figure 1 C illustrates the conversion of the photoresist / hard mask of the present invention into a patterned hard mask layer by pattern transfer through oxygen plasma etching through the underlying pattern.

[0094] Figure 1 D illustrates the removal of the bilayer photoresist (1) layer from the stack, leaving a patterned structure.

[0095] Figure 1 E illustrates the removal of the organic layer (2) from the stack, leaving a patterned target layer.

[0096] The following synthetic examples showing the production of various compositions illustrate their synthesis and the results of the coatings. These examples should not be considered restrictive. The general procedure for preparing the bilayer photoresist silicone-copolymer is based on the cohydrosilylation of a hydrogen silsesquioxane polymer with one or more functional cycloolefins having reactive groups such as: (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-methylcyclopentylbicyclo[2.2.1]hept-5-ene-2-carboxylate, 1-methylcyclohexylbicyclo[2.2.1]hept-5-ene-2-carboxylate, tert-butylbicyclo[2.2.1]hept-5-ene-2-carboxylate, 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and 8,8,8-trifluoro-7-hydroxy-7(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, norbornene sulfonamide, and combinations thereof, where the molar % concentration of each monomer in the starting monomer mixture is 0.00 < monomer < 95%, preferably 20% < monomer < 50% and more preferably 40% < monomer 50%, and the total molar amount of monomers = 100%.

[0097] Compared with the prior art, the present invention has the following advantages:

[0098] The present composition uses a novel copolymer of silicone having a unique structure in order to obtain enhanced photopatterning and better etch resistance.

[0099] The Si-O bonds of the backbone of the silicone copolymer having a network structure render the present composition stable at high temperatures and under UV exposure conditions. Additionally, a higher %Si in such a composition improves the RIE etch resistance of the coating. The side groups are carefully selected to produce an enhanced photopatterning structure. Detailed Description

[0100] Examples

[0101] Example 1

[0102] Synthesis of hydrogen silsesquioxane (HSQ):

[0103] A 5000 mL jacketed glass container is equipped with a condenser, a mechanical overhead stirrer, and an N2 purge and wash (KOH / H2O) system. A mixture of sodium 4-octylbenzenesulfonate (1.5 g, 0.006 mol) and (95%) sulfuric acid solution (150.0 g, 1.53 mol) is added to the container at 20 °C, and then toluene (480 g) is slowly added to the stirred mixture. A mixture of toluene (1200 g) and trichlorosilane (HSiCl3) (90.0 g, 0.66 mol) is added to the stirred reaction vessel over 5 hours using a peristaltic pump to maintain the internal mixture temperature at about 20 °C. After the addition is complete, the reactor mixture is mixed for 0.5 hour. Finally, 500 g of water and 300 g of ethyl acetate are added to the product mixture and the phases are separated, and the aqueous phase is removed. The organic phase is washed with 1000 g of distilled water, and then the aqueous phase is removed and the washing process is repeated four times before finally adding 200 g of ethyl acetate. The solvent is removed from the neutral reaction mixture and then dried under vacuum to produce a white solid HSQ powder product with a yield of 98%. GPC: Mw 12,500 daltons, Pd 2.12.

[0104] Example 2

[0105] Synthesis of a copolymer of HSQ and (2-methyl-2-adamantyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate:

[0106] A 500 mL jacketed glass container is equipped with a condenser and a mechanical overhead stirrer and an N2 purge. A mixture of (2-methyl-2-adamantyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate (14.3 g, 0.05 mol) and toluene (50 g) is added to the container, and then a 200 ppm "Pt" complex catalyst is added. A mixture of toluene (90 g) and hydrogenated sesquisiloxane (HSQ, from Example 1) (42.40 g, 0.10 mol) is slowly added to the stirred reaction vessel over 1 hour using a peristaltic pump to maintain the internal mixture temperature at about 20 °C. After the addition is complete, the reactor mixture is heated and refluxed for 10 hours. The solvent is removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 18,400 daltons, Pd 2.65.

[0107] Example 3

[0108] Synthesis of a copolymer of HSQ and 1-methylcyclopentyl bicyclo[2.2.1]hept-5-ene-2-carboxylate:

[0109] A 500 mL jacketed glass container is equipped with a condenser, a mechanical overhead stirrer, and an N2 purge. A mixture of 1-methylcyclopentyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (11.6 g, 0.05 mol) and toluene (50 g) is added to the container, and then a 200 ppm "Pt" complex catalyst is added. A mixture of toluene (90 g) and hydrogen silsesquioxane (HSQ, from Example 1) (42.40 g, 0.10 mol) is slowly added to the stirred reaction vessel over 1 hour to maintain the internal mixture temperature at about 20 °C. After the addition is complete, the reactor mixture is heated and refluxed for 10 hours. The solvent is removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 19,300 daltons, Pd 2.33.

[0110] Example 4

[0111] Synthesis of copolymer of HSQ and 1-methylcyclohexyl bicyclo[2.2.1]hept-5-ene-2-carboxylate:

[0112] A 500 mL jacketed glass container is equipped with a condenser, a mechanical overhead stirrer, and an N2 purge. A mixture of 1-methylcyclohexyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (12.3 g, 0.05 mol) and toluene (50 g) is added to the container, and then a 200 ppm "Pt" complex catalyst is added. A mixture of toluene (90 g) and hydrogen silsesquioxane (HSQ, from Example 1) (42.40 g, 0.10 mol) is slowly added to the stirred reaction vessel over 1 hour to maintain the internal mixture temperature at about 20 °C. After the addition is complete, the reactor mixture is heated and refluxed for 10 hours. The solvent is removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 20,500 daltons, Pd 2.57.

[0113] Example 5

[0114] Synthesis of copolymer of HSQ and tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate:

[0115] A 500 mL jacketed glass container is equipped with a condenser, a mechanical overhead stirrer, and an N2 purge. A mixture of tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (9.71 g, 0.05 mol) and toluene (50 g) is added to the container, and then a 200 ppm "Pt" complex catalyst is added. A mixture of toluene (90 g) and hydrogen silsesquioxane (HSQ, from Example 1) (42.40 g, 0.10 mol) is slowly added to the stirred reaction vessel over 1 hour using a peristaltic pump to maintain the internal mixture temperature at about 20 °C. After the addition is complete, the reactor mixture is heated and refluxed for 10 hours. The solvent is removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 18,900 Dalton, Pd 2.68.

[0116] Example 6

[0117] Synthesis of a copolymer of HSQ, 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, and (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate:

[0118] A 500 mL jacketed glass container is equipped with a condenser, a mechanical overhead stirrer, and an N2 purge. A mixture of (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate (14.3 g, 0.05 mol), 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate (5.77 g, 0.02 mol), and toluene (80 g) is added to the container, and then a 400 ppm "Pt" complex catalyst is added. A mixture of toluene (180 g) and hydrogen silsesquioxane (HSQ, from Example 1) (63.60 g, 0.15 mol) is slowly added to the stirred reaction vessel over 1 hour using a peristaltic pump to maintain the internal mixture temperature at about 20 °C. After the addition is complete, the reactor mixture is heated and refluxed for 10 hours. The solvent is removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 19,200 Dalton, Pd 2.45.

[0119] Example 7

[0120] Synthesis of a copolymer of HSQ, 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate, and bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride:

[0121] A 500 mL jacketed glass container is equipped with a condenser, a mechanical overhead stirrer, and an N2 purge. A mixture of (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate (14.3 g, 0.05 mol), 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate (5.77 g, 0.02 mol), bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (4.92 g, 0.03 mol), and toluene (90 g) is added to the container, and then a 400 ppm "Pt" complex catalyst is added. A mixture of toluene (200 g) and hydrogen silsesquioxane (HSQ, from Example 1) (76.32 g, 0.18 mol) is slowly added to the stirred reaction vessel over 1 hour using a peristaltic pump to maintain the internal mixture temperature at about 20 °C. After the addition is complete, the reactor mixture is heated and refluxed for 10 hours. The solvent is removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 19,800 daltons, Pd 2.87.

[0122] Example 8

[0123] Synthesis of a copolymer of HSQ, 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, and tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate:

[0124] A 500 mL jacketed glass container is equipped with a condenser, a mechanical overhead stirrer, and an N2 purge. A mixture of tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (9.71 g, 0.05 mol), 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate (5.77 g, 0.02 mol), and toluene (80 g) is added to the container, and then a 400 ppm "Pt" complex catalyst is added. A mixture of toluene (180 g) and hydrogen silsesquioxane (HSQ, from Example 1) (63.60 g, 0.15 mol) is slowly added to the stirred reaction vessel over 1 hour using a peristaltic pump to maintain the internal mixture temperature at about 20 °C. After the addition is complete, the reactor mixture is heated and refluxed for 10 hours. The solvent is removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 21,600 daltons, Pd 2.75.

[0125] Example 9

[0126] Synthesis of Copolymer of HSQ, 3-Hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, tert-Butyl Bicyclo[2.2.1]hept-5-ene-2-carboxylate and Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic Anhydride:

[0127] A 500 mL jacketed glass vessel was equipped with a condenser, a mechanical overhead stirrer and an N2 purge. A mixture of tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (9.71 g, 0.05 mol), 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate (5.77 g, 0.02 mol), bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (4.92 g, 0.03 mol) and toluene (90 g) was added to the vessel, and then a 400 ppm “Pt” complex catalyst was added. A mixture of toluene (200 g) and hydrogen silsesquioxane (HSQ, from Example 1) (76.32 g, 0.18 mol) was slowly added to the stirred reaction vessel over 1 hour to maintain the internal mixture temperature at about 20 °C. After the addition was complete, the reactor mixture was heated and refluxed for 10 hours. The solvent was removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone or EL. GPC: Mw 22,100 daltons, Pd 2.69.

[0128] Example 10

[0129] Synthesis of Copolymer of HSQ, 8,8,8-Trifluoro-7-hydroxy-7(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate and tert-Butyl Bicyclo[2.2.1]hept-5-ene-2-carboxylate:

[0130] A 500 mL jacketed glass vessel was equipped with a condenser, a mechanical overhead stirrer and an N2 purge. A mixture of tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (9.71 g, 0.05 mol), 8,8,8-trifluoro-7-hydroxy-7(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate (7.77 g, 0.02 mol) and toluene (80 g) was added to the vessel, and then a 400 ppm “Pt” complex catalyst was added. A mixture of toluene (180 g) and hydrogen silsesquioxane (HSQ from Example 1) (63.60 g, 0.15 mol) was slowly added to the stirred reaction vessel over 1 hour to maintain the internal mixture temperature at about 20 °C. After the addition was complete, the reactor mixture was heated and refluxed for 10 hours. The solvent was removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone or EL. GPC: Mw 20,700 daltons, Pd 2.60.

[0131] Example 11

[0132] Synthesis of a copolymer of HSQ, 8,8,8-trifluoro-7-hydroxy-7-(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate, and bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride:

[0133] A 500 mL jacketed glass vessel was equipped with a condenser, a mechanical overhead stirrer, and an N2 purge. A mixture of tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (9.71 g, 0.05 mol), 8,8,8-trifluoro-7-hydroxy-7-(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate (7.77 g, 0.02 mol), bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (4.92 g, 0.03 mol), and toluene (90 g) was added to the vessel, followed by the addition of a 400 ppm “Pt” complex catalyst. A mixture of toluene (200 g) and hydrogen silsesquioxane (HSQ, from Example 1) (76.32 g, 0.18 mol) was slowly added to the stirred reaction vessel over 1 hour to maintain the internal mixture temperature at about 20 °C. After completion of the addition, the reactor mixture was heated and refluxed for 10 hours. The solvent was removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 21,400 daltons, Pd 2.76.

[0134] Example 12

[0135] Synthesis of a copolymer of HSQ, 8,8,8-trifluoro-7-hydroxy-7-(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, and (2-methyl-2-adamantyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate:

[0136] A 500 mL jacketed glass container is equipped with a condenser, a mechanical overhead stirrer, and N2 purge. A mixture of (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate (14.3 g, 0.05 mol), 8,8,8-trifluoro-7-hydroxy-7-(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate (7.77 g, 0.02 mol), and toluene (80 g) was added to the container, followed by the addition of a 400 ppm "Pt" complex catalyst. A mixture of toluene (180 g) and hydrogen silsesquioxane (HSQ, from Example 1) (63.60 g, 0.15 mol) was slowly added to the stirred reaction vessel over 1 hour to maintain the internal mixture temperature at about 20 °C. After the addition was complete, the reactor mixture was heated and refluxed for 10 hours. The solvent was removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 20,100 daltons, Pd 2.74.

[0137] Example 13

[0138] Synthesis of a copolymer of HSQ, 8,8,8-trifluoro-7-hydroxy-7-(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate, and bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride:

[0139] A 500 mL jacketed glass container is equipped with a condenser, a mechanical overhead stirrer, and N2 purge. A mixture of (2-methyl-2-adamantyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate (14.3 g, 0.05 mol), 8,8,8-trifluoro-7-hydroxy-7-(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate (7.77 g, 0.02 mol), bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (4.92 g, 0.03 mol), and toluene (90 g) was added to the container, followed by the addition of a 400 ppm "Pt" complex catalyst. A mixture of toluene (200 g) and hydrogen silsesquioxane (HSQ, from Example 1) (76.32 g, 0.18 mol) was slowly added to the stirred reaction vessel over 1 hour to maintain the internal mixture temperature at about 20 °C. After the addition was complete, the reactor mixture was heated and refluxed for 10 hours. The solvent was removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 21,600 daltons, Pd 2.12.

[0140] Example 14

[0141] Synthesis of Copolymer of HSQ, 3-Hydroxyadamantan-1-yl Bicyclo[2.2.1]hept-5-ene-2-carboxylate, (2-Methyl-2-adamantyl) Bicyclo[2.2.1]hept-2-ene-5-carboxylate, 8,8,8-Trifluoro-7-hydroxy-7-(trifluoromethyl)octyl Bicyclo[2.2.1]hept-5-ene-2-carboxylate and Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic Anhydride:

[0142] A 500 mL jacketed glass vessel was equipped with a condenser, a mechanical overhead stirrer, and an N2 purge. A mixture of (2-Methyl-2-adamantyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate (14.3 g, 0.05 mol), 3-Hydroxyadamantan-1-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate (5.77 g, 0.02 mol), 8,8,8-Trifluoro-7-hydroxy-7-(trifluoromethyl)octyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (3.88, 0.01 mol), bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (4.92 g, 0.03 mol), and toluene (90 g) was added to the vessel, followed by the addition of a 400 ppm "Pt" complex catalyst. A mixture of toluene (200 g) and hydrogen silsesquioxane (HSQ from Example 1) (76.32 g, 0.18 mol) was slowly added to the stirred reaction vessel over 1 hour to maintain the internal mixture temperature at about 20 °C. After completion of the addition, the reactor mixture was heated and refluxed for 10 hours. The solvent was removed and replaced with other solvents such as PGMEA, PGME, MIBK, cyclohexanone, or EL. GPC: Mw 22,500 daltons, Pd 2.56.

[0143] Example 15

[0144] Formulation and Photopatterning of Double-Layer Photoresist

[0145] The double-layer siloxane copolymer of the present invention was mixed with 5 wt% photoacid generator (based on 100% copolymer in PGMEA) and 0.04 wt% organic base (based on 100% copolymer) as a quencher, then filtered through a 0.1 µm filter and spin-coated onto layer (2) at a speed of about 2000 to about 3000 rpm Figure 1 ) for a period of about 10 seconds to about 20 seconds. Then, it was exposed to 10 to 100 mj / cm 2Before the dose range of ArF, the photoresist / hard mask (PR / SiHM) coating is thermally baked at a temperature of about 100 °C to about 250 °C for a period of about 30 seconds to about 90 seconds. Then, the coating is post-exposure baked at 100 °C to about 250 °C and finally developed with 0.263 N tetramethylammonium hydroxide (TMAH) to remove the exposed areas. A high-resolution positive image with high contrast and low LER is produced.

Claims

1. A photoresist coating composition for a double-layer photoresist coating, comprising: (I) A siloxane copolymer (A) formed by hydrosilylation of a hydrogenated silsesquioxane polymer with one or more functional cycloolefins having reactive groups in a single process, wherein the siloxane copolymer (A) has the following formula: [R 1 SiO 1.5 a [R 2 SiO 1.5 b [Si(OH)O 1.5 c [SiO2] d [R 3 SiO 1.5 e [R 4 SiO 1.5 f ​​​​​ where 0.1 < a < 0.5, 0.1 < b < 0.50, 0.05 < c < 0.30, 0.01 < d < 0.20, 0.05 < e < 0.40, 0.05 < f < 0.40, R 1 is a methacrylate-derived structural unit containing an organic ester group of adamantyl, methyladamantyl, ethyladamantyl, propyladamantyl, butyladamantyl or norbornyl, R 2 is H, R 3 is adamantyl, methyladamantyl, ethyladamantyl, propyladamantyl, butyladamantyl or norbornyl containing a hydroxyl group, R 4 is a methacrylate-derived structural unit containing a lactone group or having a lactone-containing group, and the lactone group is a γ-butyrolactone group; (II) An organic solvent; (III) A photo-generated catalyst; and (IV) A base.

2. The photoresist coating composition for a double-layer photoresist coating according to claim 1, wherein one or more functional cycloolefins having reactive groups are selected from (2-methyl-2-adamantyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-methylcyclopentyl bicyclo[2.2.1]hept-5-ene-2-carboxylate, 1-methylcyclohexyl bicyclo[2.2.1]hept-5-ene-2-carboxylate, tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate, 3-hydroxyadamantan-1-yl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, (2-methyl-2-adamantyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and 8,8,8-trifluoro-7-hydroxy-7(trifluoromethyl)octyl-bicyclo[2.2.1]hept-5-ene-2-carboxylate, norbornene sulfonamide, and combinations thereof.

3. The photoresist coating composition for a double-layer photoresist coating according to claim 1, wherein the organic solvent is selected from ketones, ethers, esters, and diols and combinations thereof, and the amount of the organic solvent is 80% to 99% by weight, based on the total coating composition.

4. The photoresist coating composition for a double-layer photoresist coating according to claim 3, wherein the ketones, ethers, esters, and diols are selected from propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, cyclohexanone, N-methylpyrrolidone, N,N-dimethylacetamide, propylene glycol methyl ether, dibutyl ether, methoxy-2-propanol, dipentyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, 2-butanone, tetrahydrofuran, 1,2-diethoxyethane, 1,2-dimethoxymethane, diethyl oxalate, butyl lactate, dimethoxyethane, γ-butyrolactone, and methyl tert-butyl ether and combinations thereof.

5. The photoresist coating composition for a double-layer photoresist coating according to claim 1, wherein the photo-generated catalyst is selected from ionic photoacid generators, or non-ionic photoacid generators, and combinations thereof.

6. The photoresist coating composition for a double-layer photoresist coating according to claim 5, wherein the ionic photoacid generator is triphenylsulfonium perfluoro-1-butanesulfonate; the non-ionic photoacid generator is 2-[2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutanesulfonyloxyimino)-pentyl]-fluorene (ONPF).

7. The photoresist coating composition for a bilayer photoresist coating according to claim 5, wherein an ionic photoacid generator and / or a non-ionic photoacid generator is used in a total amount of 0.1 to 5% by weight, based on the total weight of the formulation.

8. The photoresist coating composition for a bilayer photoresist coating according to claim 1, wherein the amount of Si in the starting monomer mixture ranges from 8 mol% to 45 mol%.

9. The photoresist coating composition for a bilayer photoresist coating according to claim 1, wherein the amount of Si in the starting monomer mixture ranges from 30 to 40 mol%.

10. The photoresist coating composition for a bilayer photoresist coating according to claim 1, wherein the base is selected from amines, amides, imides, nitrogen-containing compounds, and combinations thereof.

11. The photoresist coating composition for a bilayer photoresist coating according to claim 10, wherein the amines, amides, imides, and nitrogen-containing compounds are selected from methylamine, dimethylamine, dimethanolamine, trimethylamine, trimethanolamine, methanolamine, ethylamine, ethanolamine, diethylamine, triethylamine, triethanolamine, isopropylamine, isopropanolamine, diisopropanolamine, diisopropylamine, triisopropylamine, triisopropanolamine, n-butylamine, n-butanolamine, di-n-butylamine, di-n-butanolamine, tri-n-butanolamine, tri-n-butylamine, tert-butylamine, tert-butanolamine, di-tert-butylamine, di-tert-butanolamine, tri-tert-butanolamine, tri-tert-butylamine, 1-tert-butoxycarbonyl-4-piperidone, 3-tert-butoxycarbonyl-amino-1-propanol, 1-tert-butoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonyl-L-proline, N-tert-butoxycarbonyl-diethanolamine, N-tert-butoxycarbonyl-2-(2-hydroxyethyl)piperidine, and combinations thereof.

12. The photoresist coating composition for a bilayer photoresist coating according to claim 1, wherein the silicone copolymer in the photoresist coating composition has an Mw of 800 to 30,000.

13. The photoresist coating composition for a bilayer photoresist coating according to claim 1, wherein the silicone copolymer in the photoresist coating composition has an Mw of 1,000 to 20,000.

14. A method for coating a microelectronic device, comprising: (i) preparing the photoresist coating composition for a bilayer photoresist coating according to any one of claims 1-13, (ii) providing an organic solvent, (iii) providing a photoacid catalyst, (iv) providing a base quencher, (v) providing an additive, (vi) coating a solution mixture comprising (i), (ii), (iii), (iv), and (v) on a substrate, (vii) evaporating the solvent from the coating using a pre-bake, (viii) subjecting the film to ArF exposure to produce a photopattern, (ix) post-baking the film, (x) developing the film to produce a photopattern.

15. The method according to claim 14, wherein the solution mixture is spin-coated on the substrate in step (iv).

16. The method according to claim 14, wherein the solvent is evaporated during the spin-coating process in step (vii).

17. The method according to claim 14, wherein in step (vi), drying is carried out by heating at 100 °C to 250 °C for 30 to 120 seconds.

18. The method according to claim 14, wherein in step (x), the thickness of the film is 100 nm to 500 nm.

19. A method of forming a patterned device, comprising: a) coating a photoresist coating composition of the bilayer photoresist coating according to any one of claims 1-13 on a device substrate to form a Si-rich photoresist, b) ArF photopatterning the bilayer photoresist, post-baking and developing to form a resist pattern, c) transferring the resist pattern to the underlying layer using RIE, d) removing the exposed area by etching and producing a patterned device.

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