Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
The election by the applicant without traverse of claims 1-15 (group I) on 5/.4/2026 has been received. The restriction of 4/9/2026 is repeated and made final.
Claims 16-21 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 5/4/2026.
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 4 and 15 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
In claim 4, it is not clear what “application” embraces.
In claim 15 the language “the metal film is dry-etched” should be replaced with - - the metal film has been dry-etched- - and the claim should be amended to clearly recite that the silicon-containing resist underlayer is also patterned.
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claims 1-14 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Ishibashi et al. WO 2020138092.
Ishibashi et al. WO 2020138092 in example 1 forms a 50:50 copolymers of tetraethoxysilane and methyltriethoxysialne which is dissolved in propylene glycol monomethyl ether (PGME) to form a 13 wt% solution [0096], table 1 teaches the addition of maleic acid, N-(3-triethoxypropyl)-4,5-dihydroimidazole and PGME, PGEE and deionized water (DIW) [0105]. Example 2 form a 30 wt% solution of vinyltrimethoxysilane polymer in solvent [0097]. Example 3 formed a 75:25 copolymer of tetraethoxysilane and methyltriethoxysilane which is dissolved in PGEE to form a 12.12 wt% solution [0098]. Table 1 teaches the addition of maleic acid, triphenylsulfonium nitrate. Example 4 forms a 30:70 copolymer of tetraethoxysilane methyltrimethoxysilane in 13 wt% in methylisobutylcarbinol [0099]. Table 1 teaches the addition of acetic acid to this. These are spin coated upon silicon wafers, dried and etched [0106-0113]. As the substrate, silicon, glass on which indium tin oxide (ITO) is formed, glass on which indium zinc oxide (IZO) is formed, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics And the like, and a flexible base material having flexibility can also be used [0073]. The solid content in the composition containing polysiloxane (hereinafter, also simply referred to as composition) is, for example, 0.1 to 50 mass %, 0.1 to 30 mass %, 0.1 to 25 mass %, 0.5 to It is 20.0 mass %, or 1.0 to 10.0 mass %. The solid content refers to the ratio of all components of the composition excluding the solvent component [0045].
The presence of acid and water result in hydroxy substitution and the condensation with the PGME solvent results in acetal formation.
The limitation of claims 14 is a process limitation and is considered and intended use. The examiner holds that the hardmask composition is useful irrespective of the wavelength used to expose an unrecited resist useful in patterning the hardmask.
Claims 1-9 and 14 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Ogihara et al. 20150004791
Ogihara et al. 20150004791 teaches 12 wt% solution of a silicon containing polymer polymer A1 [0202], which is combined with triphenylsulfonium nitrate and maleic acid, PGEE and water (table 3) This is coated upon a silicon wafer provided with a spin on carbon film,, then an ArF resist is collated and , dried, exposed, post baked, developed [0227-0240]. Further, the body to be processed may be a material in which any of a metal film, an amorphous metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film or a metal oxynitride film is formed on a semiconductor apparatus substrate on which a part or whole of semiconductor circuits has/have been formed, as a layer to be processed. Further, the metal constitutes the body to be processed may comprise silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof [0047-0048].
Claims 1-14 are rejected under 35 U.S.C. 102(a)(2) as being fully anticipated by Shibayama et al. WO 2022230940.
Shibayama et al. WO 2022230940 (machine translation attached) teaches the synthesis of polymer 3 by the reaction of 22.3 g of tetraethoxysilane, 6.82 g of methyltriethoxysilane, 3.16 g of diallyl isocyanurate propyltriethoxysilane, in 48.4 g of propylene glycol monoethyl ether (PGME) in the presence of nitric acid. PGMEE was then added to yield a 20 solid polysiloxane solution [0273-0274]. This was combined with maleic acid, triphenylsulfonium trifluoroacetate and 10-camphorsulfonic acid (see table at [0292]). These were coated upon silicon wafers.
The hydrolysis/condensation yields ethanol (ethyl alcohol)
Claim 1-11 and 13-14 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Tamura et al. JP 2016063009.
Tamura et al. JP 2016063009 (machine translation attached) teaches the synthesis of a polysiloxane for adhesion improvement. 50:50 of TEOS: vinyltrimethoxysilane was formed as solution of 30 wt% in PGME in the presence of hydrochloric acid, ethanol (ethyl alcohol), water and methanol (methyl alcohol) is disclosed [0086]. Synthesis example 4 and 5 are similar. [0087-0088]. Example 6 reacts TEOS with triethoxysilylpropyl isocyanurate in the process of forming a 30wt% solution of the polymer in PGMEA. The polymer of example 6 is combined with maleic acid and N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole [0093]. These were applied to silicon wafers. The solid content in the adhesion-strengthening film forming composition used in the present invention is, for example, 0.5 to 50% by mass, 1 to 30% by mass, or 1 to 25% by mass. Here, the solid content is a value obtained by removing the solvent component from all the components of the (adhesion reinforcing film) film-forming composition [0037].
Claims 1-14 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Shibayama et al. 20180149977
Shibayama et al. 20180149977 in example 11-2 reacts In a 500 ml flask 91.16 g of water was placed. To the mixed solution 22.23 g of dimethylaminopropyltrimethoxysilane and 8.16 g of triethoxysilylpropylsuccinic anhydride were added dropwise while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 40° C. and the reaction solution was reacted for 240 minutes. Thereafter, the reaction solution was cooled to room temperature and 91.16 g of water was added to the reaction solution. Methanol and water being reaction by-products were removed by distillation under reduced pressure and the reaction solution was concentrated to give an aqueous solution of a hydrolysis condensate (polysiloxane). Water was further added to the aqueous solution to adjust the aqueous solution to a concentration of 20% by mass in terms of solid residue at 140° C. as a solvent ratio of 100% water (water solvent alone). The obtained polymer corresponded to Formula (2-10-2) [0187].
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In a 500 ml flask 92.63 g of water was placed. To the mixed solution 12.51 g of dimethylaminopropyltrimethoxysilane and 18.37 g of triethoxysilylpropylsuccinic anhydride were added dropwise while stirring the mixed solution with a magnetic stirrer. Thereafter, 8.05 g of a 1M nitric acid aqueous solution was added. After the addition, the flask was transferred to an oil bath adjusted to 40° C. and the reaction solution was reacted for 240 minutes. Thereafter, the reaction solution was cooled to room temperature and 92.63 g of water was added to the reaction solution. Ethanol and water being reaction by-products were removed by distillation under reduced pressure and the reaction solution was concentrated to give an aqueous solution of a hydrolysis condensate (polysiloxane). Water was further added to the aqueous solution to adjust the aqueous solution to a concentration of 20% by mass in terms of solid residue at 140° C. as a solvent ratio of 100% water (water solvent alone). The obtained polymer corresponded to Formula (2-10-2) [0188].
Claims 1-11 and 13-14 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Kanno et al. 20150249012.
Kanno et al. 20150249012 teaches the reaction of 25.65 g (70 mol %) of tetraethoxysilane, 7.78 g (24.8 mol %) of methyltriethoxysilane, 1.74 g (5 mol %) of phenyltrimethoxysilane, 0.15 g (0.02 mol %) of 3-(triethoxysilylpropyl)diallyl isocyanurate, and 52.97 g of acetone were charged into a 200 mL flask. While the resultant mixed solution was stirred with a magnetic stirrer, 11.72 g of a 0.1 mol/L hydrochloric acid was added dropwise into the mixed solution. After the addition, the flask was transferred into an oil bath adjusted to 85.degree. C., and under warming-reflux, the reaction was effected for 240 minutes. Then, the reaction solution was cooled down to room temperature, and to the reaction solution, 35 g of propylene glycol monoethyl ether was added. From the resultant reaction solution, ethanol as a reaction by-product, water, and hydrochloric acid were distilled off under reduced pressure, and the resultant reaction mixture was concentrated to obtain a hydrolysis-condensation product (polymer) propylene glycol monomethyl ether acetate solution. To the obtained solution, propylene glycol monoethyl ether was added to adjust the resultant solution to contain a solid residue in a proportion of 15% by mass at 140.degree. C. while the solvent ratio of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether was 20/80. The resultant polymer corresponded to Formula (3-9) and had a weight average molecular weight measured by GPC of Mw 1600 in terms of polystyrene [0162] (comparative synthesis 3).
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This is combined with maleic acid and PGMEA (see table 4). This is coated upon a wafer , dried, overcoated with a resist and patterned [0177]. Examples of the organic acid as the hydrolysis catalyst include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and trifluoromethanesulfonic acid [0112]. Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid [0113].
Claims 1-11 and 13-14 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Shibayama et al. WO 2019124514.
Shibayama et al. WO 2019124514 (machine translation attached) teaches 23.3 g of tetraethoxysilane (containing 70 mol% in total silane), 1.58 g of phenyltrimethoxysilane (containing 5 mol% in total silane), 6.60 g of triethoxysilylpropyl diallyl isocyanurate (containing all silane) A 300 ml flask is charged with 10 mol% of), 4.27 g of methyltriethoxysilane (15 mol% of all silanes contained), 53.6 g of acetone, and 0.01 M hydrochloric acid while stirring the mixed solution with a magnetic stirrer. An aqueous solution of 10.6 g was dropped. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C. and refluxed for 240 minutes. Thereafter, 70 g of propylene glycol monomethyl ether acetate was added, and acetone, methanol, ethanol, hydrochloric acid and water were distilled off under reduced pressure, and the solution was concentrated to obtain a solution of hydrolysis condensate (polymer). Furthermore, propylene glycol monomethyl ether acetate was added, and it adjusted so that it might become 20 mass% in conversion of solid residue in 140 degree C as a solvent ratio of propylene glycol monomethyl ether acetate 100%. The obtained polymer corresponds to the formula (A-12), and the weight average molecular weight by GPC is Mw 1400 in terms of polystyrene [0154] Organic acids as hydrolysis catalysts are, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic acid, methyl malonic acid, adipic acid, sebacine Acid, gallic acid, butyric acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene sulfone Acids, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like can be mentioned. Examples of the inorganic acid as a hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like [0071-0072].
Claims 1-14 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Shibayama et al. KR 20200071739.
Shibayama et al. KR 20200071739 (machine translation attached) in synthesis example 1 reacts 22.3 g of tetraethoxysilane, 6.5 g of methyltriethoxysilane, 3.2 g of triethoxysilylpropyldiallyl isocyanurate, 48.5 g of acetone were placed in a flask of 300 ml and 0.2 M while stirring the mixed solution with a magnetic stirrer. A mixed solution of 19.2 g nitric acid aqueous solution and 0.32 g dimethylaminopropyl trimethoxysilane was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 85°C and refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added, acetone, methanol, ethanol, and water were distilled off under reduced pressure, and concentrated to obtain an aqueous hydrolysis condensate (polymer) solution. Propylene glycol monomethyl ether was added again, and adjusted to a weight ratio of 13% by weight in terms of solid residue conversion at 140°C, using a solvent ratio of 100% of propylene glycol monomethyl ether. The obtained polymer was equivalent to formula (A-1), and the weight average molecular weight by GPC was Mw1500 in terms of polystyrene [0319-0320]. Synthesis example 15 reacts 22.3 g of tetraethoxysilane, 6.6 g of methyl triethoxysilane, 3.2 g of triethoxysilylpropyl diallyl isocyanurate, 48.5 g of acetone were placed in a flask of 300 ml, and 0.2 M while stirring the mixed solution with a magnetic stirrer. A mixed solution of 19.2 g of nitric acid aqueous solution and 0.27 g of aminopropyl trimethoxysilane was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 85°C and refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added, acetone, methanol, ethanol, and water were distilled off under reduced pressure, and concentrated to obtain an aqueous hydrolysis condensate (polymer) solution. Propylene glycol monomethyl ether was added again, and adjusted to a weight ratio of 13% by weight in terms of solid residue conversion at 140°C, using a solvent ratio of 100% of propylene glycol monomethyl ether. The obtained polymer was equivalent to Formula (A-14), and the weight average molecular weight by GPC was Mw2500 in terms of polystyrene [0347-0348]. This is combined with organic solvents and maleic acid (table 1) and coated. A catalyst can be used when hydrolyzing and condensing. As a catalyst, strong acids can be used, and examples of these strong acids include inorganic acids or carboxylic acids having pKa of 5 or less, for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, chloroacetic acid and dichloroacetic acid , Trichloroacetic acid, trifluoroacetic acid, maleic acid, methanesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid and the like [0223].
Claims 1-11 and 13-15 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Watanabe et al. JP 2012068314.
Watanabe et al. JP 2012068314 (machine translation attached) teaches the formation of polysiloxanes in synthesis example 1, where 60 g of methanol, 200 g of ion-exchanged water and 1 g of 35% hydrochloric acid were charged into a 1,000 ml glass flask, and a mixture of 50 g of tetraethoxysilane, 100 g of methyltrimethoxysilane and 10 g of phenyltrimethoxysilane was added at room temperature. The product was subjected to hydrolysis and condensation for 8 hours at room temperature, and then methanol and by-product ethanol were distilled off under reduced pressure. Thereto, 800 ml of ethyl acetate and 300 ml of propylene glycol monopropyl ether were added, the aqueous layer was separated, and hydrochloric acid used in the reaction was removed. To the remaining organic layer, 100 ml of a 1% maleic acid aqueous solution was added, stirred, allowed to stand, and separated. After repeating this twice, 100 ml of ion-exchanged water was added, stirred, allowed to stand, and separated. This was repeated three times. 200 ml of propylene glycol monopropyl ether was added to the remaining organic layer and concentrated under reduced pressure to obtain 300 g of a propylene glycol monopropyl ether solution of silicon-containing compound 1 (polymer concentration 21%). The resulting solution was analyzed for chloride ions by ion chromatography, but was not detected. It was Mw = 2,000 when the polystyrene conversion weight molecular weight of the silicon containing compound 1 was measured [0066]. This was combined with Triphenylsulfonium acetate, solvent and additive (table 1, page 16). This was then coated upon a MoSiN light shielding film of a photomask blank, dried, a photoresist applied, dried, exposed using an electron beam, post baked and developed and then used to dry etch the MoSiN layer. The other silicon hardmask layers were also used in examples [0075-0081]. Further, in order to stably store and use the composition for forming a silicon oxide-based material film, it is preferable to add a stabilizer. Examples of the stabilizer include monovalent or divalent or higher organic acids having 1 to 30 carbon atoms. Acids added at this time include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid , Phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid , Diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid and the like. In particular, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like are preferable. In order to maintain stability, two or more kinds of acids may be mixed and used. The addition amount is 0.001 to 25 parts by mass, preferably 0.01 to 15 parts by mass, more preferably 0.1 to 100 parts by mass of the hydrolyzable / condensate of the hydrolyzable silane compound contained in the composition. -5 parts by mass. The organic acid is blended so that the pH of the composition is preferably 0 ≦ pH ≦ 7, more preferably 0.3 ≦ pH ≦ 6.5, and still more preferably 0.5 ≦ pH ≦ 6. It is also preferable [0046]. Examples of the acid catalyst preferably used for the hydrolysis and condensation by the acid catalyst include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid. Can be mentioned. The amount of the catalyst used is 10 .sup.−6 mol to 10 mol, preferably 10 .sup.−5 mol to 5 mol, more preferably 10 .sup.−4 mol to 1 mol, relative to 1 mol of silicon monomer [0026].
Claims 1-15 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Watanabe et al. 20100248493
Watanabe et al. 20100248493 in synthesis example 1 reacts in 60 g methanol, 200 g de-ionized water and Ig 35% hydrochloric acid. adding 50 g tetraethoxysilane, g of methyl trimethoxy silane and phenyl trimethoxy silane mixture into it under the room temperature. The mixture is kept for 8 hours for hydrolytic condensation under room temperature, then vacuum distilling off the methanol and by-product ethanol. then adding 800 ml of ethyl acetate and 300 ml of propylene glycol monopropyl ether, and separating the water layer, removing the hydrochloric acid used in the reaction. In order to maintain the organic layer, adding 100mll % water solution of maleic acid, followed by stirring, static holding and separation. repeating for 2 times. ml de-ionized water is added into the organic layer, followed by stirring, static holding and separation. repeating for 3 times. in the organic layer is added 200 ml of propylene glycol monopropyl ether, vacuum concentrating to obtain 300 g silicon-containing compound 1 propylene glycol monopropyl ether solution (polymer concentration of 21%). analyzing the solution by ion chromatography, but no chloride ion is detected. relative to polystyrene standards, silicon-containing compounds 1 weight average molar quantity (Mw) of 2000 [0084]. The other synthesis examples are similar, and synthesis example 3 uses nitric acid as the catalyst [0085-0088]. These are combined with a thermal acid generator, solvent and additives [0089]. A photomask blank is coated with a MoSiN layer, a CrN layer, the polysiloxane composition, which are is dried. A photoresist is then coated upon this, dried, exposed using an electron beams, post baked, developed and used to pattern the CrN and MoSiN layers using dry etching. [0090-0101]. In the event that the silicon-containing compound becomes unstable upon solvent exchange, a stabilizer may be added to the reaction mixture. The stabilizer is preferably selected from mono or polyfunctional organic acids of 1 to 30 carbon atoms. Preferred examples of the stabilizer include oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, and citric acid. A mixture of two or more acids may be used to maintain stability. An appropriate amount of the stabilizer is 0.001 to 25 parts, more preferably 0.01 to 15 parts, and even more preferably 0.1 to 5 parts by weight relative to 100 parts by weight of the silicon-containing compound in the composition [0051]. Examples of the acid catalyst used for hydrolytic condensation include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid. An appropriate amount of the catalyst used is in the range of 10 to 10 moles, more preferably 10.sup.-5 to 5 moles, and even more preferably 10 to 1 mole per mole of the silicon monomer [0045] The organic solvent which may be added to the catalyst aqueous solution or with which the hydrolyzable silane compound may be diluted may be selected from well-known solvents, preferably water-soluble solvents. Suitable solvents include alcohols such as methanol, ethanol, 1-propanol and 2-propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, polyhydric alcohol condensed derivatives such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, and ethylene glycol monopropyl ether, acetone, acetonitrile, and tetrahydrofuran. Of these, those solvents having a boiling point lower than or equal to 100.degree. C. are preferred. An appropriate amount of the solvent used is in the range of 0 to 1,000 ml, more preferably 0 to 500 ml per mole of the monomer. A larger amount of the solvent is uneconomical because an extra large reaction system must be used [0048]
The sol of examples 1,2 and 4-5 and the use of it to pattern the photomask banks meet the limitations of claims 1-11 and 13-15
The sol of example 3 5 and the use of it to pattern the photomask banks meets the limitations of claims 1-15.
Claims 1-11 and 13-14 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Kobayashi et al. WO 2018168435
Kobayashi et al. WO 2018168435 (machine translation attached) teaches a polysiloxane (A-1) formed by the reaction of 43.74 g (0.195 mol) of p-styryltrimethoxysilane, 14.06 g (0.06 mol) of γ-acryloylpropyltrimethoxysilane, 11.80 g (0.045 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.173 g of TBC, and 74.58 g of PGME were charged. While stirring at room temperature, 0.348 g of phosphoric acid was added to 17.01 g of water ( An aqueous phosphoric acid solution in which 0.50% by weight of the charged monomer) was dissolved was added over 30 minutes. Thereafter, the three-necked flask was immersed in a 70 ° C. oil bath and stirred for 90 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature (solution temperature) of the three-neck flask reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution. Nitrogen was allowed to flow at 0.05 liter / min during the temperature rise and heating and stirring. During the reaction, a total of 36.90 g of methanol and water as by-products were distilled out. PGME was added to the obtained polysiloxane solution so that the solid concentration was 40% by weight to obtain a polysiloxane (A-1) solution. The molar ratio of the repeating unit having a styryl group, the repeating unit having an acryloyl group, and the repeating unit having a hydrophilic group in the polysiloxane (A-1) was 65 mol%, 20 mol%, and 15 mol%, respectively. The weight average molecular weight of the polysiloxane (A-1) was 4,000 [0089]. Resins A-2 to A-6 are formed in a similar manner [0090-0094]. These are spin coated upon “MAM” substrates (molybdenum/aluminum/molybdenum) and dried. Example 1 Under a yellow light, (B) as radical photopolymerization initiator, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime) (“Irgacure” (registered trademark) OXE-02 (trade name), manufactured by BASF Japan Ltd.) 0.080 g and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure” ( Registered trademark) -819 (trade name), manufactured by BASF Japan Ltd.) 0.160 g, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (“ Irganox ”(registered trademark) -245 (trade name), BASF Japan Ltd.) PGME 10% by weight solution 0.120 g, tetrakis (acetyl) 3.998 g of a 2% by weight PGME solution of Settonate Zirconium (IV) (ZC-150 (trade name), manufactured by Matsumoto Fine Chemical Co., Ltd.), (C) Pentaerythritol acrylate (“Light Acrylate” (registered trademark) as a polyfunctional monomer ) PE-3A (trade name) manufactured by Kyoeisha Chemical Co., Ltd. (0.400 g) was dissolved in a mixed solvent of PGME 1.667 g and PGMEA 3.200 g, and a silicone-based surfactant (trade name “BYK” (registered trademark)) was dissolved. 0.200 g (corresponding to a concentration of 100 ppm) of PGME 1% by weight diluted with PGME (-333, manufactured by Big Chemie Japan Co., Ltd.) and stirred. Then, 6.167 g of polysiloxane (A-1) solution as (A) polysiloxane, (D) phosphoric acid ester amine salt as phosphoric acid derivative compound (d1) P-1M and amine compound (d2) mono 3.998 g of a PGME solution having a concentration of 20% by weight obtained by reacting ethanolamine at a weight ratio of (d2 / d1) = 0.5 / 9.5 was added and stirred. Next, filtration was performed with a 0.45 μm filter to obtain a photosensitive siloxane resin composition (P-1). The resulting photosensitive siloxane resin composition (P-1) was evaluated for pattern processability, substrate adhesion, chemical resistance, hardness, and storage stability by the methods described above [0107]. In the hydrolysis reaction, an acid catalyst such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or its anhydride, or an ion exchange resin can be used. Among these, an acidic aqueous solution containing formic acid, acetic acid and / or phosphoric acid is preferable [0032].
The position of the examiner is that one reading the reference would immediately envision the photosensitive silicon composition of example 1 coated on the MAM substrate
Claims 1-7,10 and 13-15 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Fujimori et al. JP 2008026500
Fujimori et al. JP 2008026500 (machine translation attached) in examples 1 coats a glass substrate with a MoSi film, followed by a sputtered Cr film. A siloxane polymer formed by reacting TMOS and methyltrimethoxysilane is coated form a n-butanol/methyl;-methoxypropionate solution, dried, an electron beams resist was coated, dried, exposed, developed and then used to pattern the layers using dry etching. [0068-0075].
Claims 1-15 are rejected under 35 U.S.C. 103 as being unpatentable over Watanabe et al. 20100248493
Watanabe et al. 20100248493 does not exemplify a composition using acetic acid.
It would have been obvious to one skilled in the art to modify the compositions coated on the photomask blanks of Watanabe et al. 20100248493 by adding acetic acid as a stabilizer based upon the disclosure at [0046] with a reasonable expectation of forming useful hardmask composition with improved stability and patterned photomask.
Claims 1-15 are rejected under 35 U.S.C. 103 as being unpatentable over Yunagami et al. 6326218, in view of Watanabe et al. 20100248493 and Fujimori et al. JP 2008026500
Yunagami et al. 6326218 describes with respect to figure 11a, a substrate including a titanium nitride film (27), a ruthenium film (55), a silicon oxide film (56) and a patterned resist (57). The pattern in the resist is transferred to the silicon oxide film (fig 11b). The resist is removed and the silicon oxide pattern is used as a hardmask patternwise the etch the ruthenium layer (11d, 11e). The silicon oxide film was formed using a plasma CVD using TEOS as the source material, where the silicon oxide is etched using RIE (C4F8) and the ruthenium is etched using an oxygen plasma (col 24/line 31-27/39).
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Yunagami et al. 6326218 does not use a siloxane based composition to form the silicon oxide hardmask used in the etching process.
It would have been obvious to one skilled in the art to modify the process of Yunagami et al. 6326218 by forming the silicon oxide hardmask using solution based silicon oxide hardmask materials, such as those taught by Watanabe et al. 20100248493 and Fujimori et al. JP 2008026500 which does not require the CVD apparatus with a reasonable expectation of forming a patterned silicon oxide hardmask and patterned ruthenium layer similar to that illustrated iun figure 11d of Yunagami et al. 6326218
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 June 9, 2026
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