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 response of the applicant has been read and given careful consideration. Rejection of the previous office action not repeated below are withdrawn based upon the amendments and arguments of the applicant. Responses to the arguments are presented after the first rejection they are directed to.
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 15,22 and 27 are rejected under 35 U.S.C. 103 as being unpatentable over Tokashiki et al. 5624583, in view of Fujimori et al. JP 2008026500, Asakawa et al. 20120097640 and Tsai et al. 20110189847.
Tokashiki et al. 5624583 in example 4 teaches a 200 nm Ru film (11) formed on a silicon wafer, overcoated with a 200 nm spin on glass (SOG) film (13) and overcoated with a resist which is patterned. The SOG film was patterned using an electron cyclotron dry etching apparatus with CHF3 gas (as in example 1), the patterned resist was then removed using an oxygen plasma etch and the patterned SOG film was used as an etch mask during patterning of the Ru film which used an oxygen chlorine etch. The etch selectivity of the Ru/SOG was 2 (col. 5/line 42-col 6/line 6)
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 with a chlorine based gas [0068-0075].
Asakawa et al. 20120097640 teaches inorganic hardmask composition which are resistant to RIE etching using oxygen, argon and chlorine gases which include spin coated siloxane polymers, polysilanes or spin-on-glass [0127].
Tsai et al. 20110189847 teaches a spin-on glass (SOG) materials including a siloxane polymer [0029].
Tokashiki et al. 5624583 teaches the structure except for the composition of the spin-on-glass (SOG) layer or the coating solvent.
It would have been obvious to modify example 4 of Tokashiki et al. 5624583 by using the TMOS/ methyltrimethoxysilane/n-butanol/methyl-methoxypropionate solution hardmask solution of Fujimori et al. JP 2008026500 with a reasonable expectation of success in forming a patterned polysiloxane/ruthenium structure and etch selectivity for the oxygen/chloride etch of more than 1 based upon the equivalence of polysiloxanes and spin-glass at [0127] of Asakawa et al. 20120097640, the acceptance of siloxane polymers as spin on glass materials at [0029] of Tsai et al. 20110189847 and the etch selectivity taught in Fujimori et al. JP 2008026500.
In the response of 7/27/2026, the applicant argues that the prior art does not teach the use of a polysiloxane with more than 30% Si in an alcohol solution. The examiner points out that the siloxane polymer formed by reacting TMOS and methyltrimethoxysilane describes in Fujimori et al. JP 2008026500 meet this and is described as a hard/etch mask The applicant is invited to establish that the etch selectivity is unexpectedly different from that of Tokashiki et al. 5624583, which exemplifies an etch selectivity of 2 in example 4 and describes etch selectivities as high as ~8.75 in figure 6. The equivalence of SOG and siloxane based hardmasks is clearly established in the secondary references and provides a reasonable success in making the substitution described in the rejection.
Claims 15,22 and 24- 27 are rejected under 35 U.S.C. 103 as being unpatentable over Tokashiki et al. 5624583, in view of Ishibashi et al. WO 2020138092, Asakawa et al. 20120097640 and Tsai et al. 20110189847.
Ishibashi et al. WO 2020138092 in example 1 forms a 50:50 copolymers of tetraethoxysilane and methyltriethoxysilane 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]. Useful coating solvents including alcohols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol and propylene glycol monobutyl ether [0042]. Useful hydrolysis acids include organic acids as hydrolysis catalysts include, for example, 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, sebacine. Acid, gallic acid, butyric acid, meritic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic 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 the like. Examples of an inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like [0039]. The etch resistance to halogen gases is disclosed at [0011].
Tokashiki et al. 5624583 teaches the structure except for the composition of the spin-on-glass (SOG) layer or the coating solvent.
It would have been obvious to modify example 4 of Tokashiki et al. 5624583 by using the hardmask compositions exemplified in Ishibashi et al. WO 2020138092 with a reasonable expectation of success in forming a patterned polysiloxane/ruthenium structure and etch selectivity for the oxygen/chloride etch of more than 1 based upon the equivalence of polysiloxanes and spin-glass at [0127] of Asakawa et al. 20120097640, the acceptance of siloxane polymers as spin on glass materials at [0029] of Tsai et al. 20110189847 and the etch selectivity relative to halogen gasses taught in Ishibashi et al. WO 2020138092 at [0011].
Alternatively, it would have been obvious to modify example 4 of Tokashiki et al. 5624583 by using the hardmask compositions similar to those exemplified in Ishibashi et al. WO 2020138092 where the hydrolysable silane is bounded by formula (1) [0009] and or nitric acid is used as the acidic catalyst as taught at [0039] with a reasonable expectation of success in forming a patterned polysiloxane/ruthenium structure and etch selectivity for the oxygen/chloride etch of more than 1 based upon the equivalence of polysiloxanes and spin-glass at [0127] of Asakawa et al. 20120097640, the acceptance of siloxane polymers as spin on glass materials at [0029] of Tsai et al. 20110189847 and the etch selectivity relative to halogen gasses taught in Ishibashi et al. WO 2020138092 at [0011].
In the response of 7/27/2026, the applicant argues that the prior art does not teach the use of a polysiloxane with more than 30% Si in an alcohol solution. The examiner points out that the siloxane polymers of the examples of Ishibashi et al. WO 2020138092 meet this and is described as a hard/etch mask
Claims 15 and 22- 27 are rejected under 35 U.S.C. 103 as being unpatentable over Tokashiki et al. 5624583, in view of Shibayama et al. WO 2022230940, Asakawa et al. 20120097640 and Tsai et al. 20110189847.
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.
It would have been obvious to modify example 4 of Tokashiki et al. 5624583 by using the hardmask composition using polymer 3 of Shibayama et al. WO 2022230940 with a reasonable expectation of success in forming a patterned polysiloxane/ruthenium structure and etch selectivity for the oxygen/chloride etch of more than 1 based upon the equivalence of polysiloxanes and spin-glass at [0127] of Asakawa et al. 20120097640, the acceptance of siloxane polymers as spin on glass materials at [0029] of Tsai et al. 20110189847.
In the response of 7/27/2026, the applicant argues that the prior art does not teach the use of a polysiloxane with more than 30% Si in an alcohol solution. The examiner points out that the siloxane polymers of the example of Shibayama et al. WO 2022230940 meet this and is described as a hard/etch mask
Claims 15 and 22- 27 are rejected under 35 U.S.C. 103 as being unpatentable over Tokashiki et al. 5624583, in view of Kanno et al. 20150249012, Asakawa et al. 20120097640 and Tsai et al. 20110189847.
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 affected 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]. Useful coating solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, methylisobutylcarbinol, propylene glycol monobutyl ether [0114].
Tokashiki et al. 5624583 teaches the structure except for the composition of the spin-on-glass (SOG) layer or the coating solvent.
It would have been obvious to modify example 4 of Tokashiki et al. 5624583 by using the hardmask compositions exemplified in Kanno et al. 20150249012 with a reasonable expectation of success in forming a patterned polysiloxane/ruthenium structure and etch selectivity for the oxygen/chloride etch of more than 1 based upon the equivalence of polysiloxanes and spin-glass at [0127] of Asakawa et al. 20120097640, the acceptance of siloxane polymers as spin on glass materials at [0029] of Tsai et al. 20110189847.
Alternatively, it would have been obvious to modify example 4 of Tokashiki et al. 5624583 by using the hardmask compositions similar to those exemplified in Kanno et al. 20150249012 where nitric acid or acetic acid are used as the acidic catalyst as taught at [0113] and/or propylene glycol monoethyl ether, methylisobutylcarbinol, propylene glycol monobutyl ether are used as the coating solvents as taught at [0114] with a reasonable expectation of success in forming a patterned polysiloxane/ruthenium structure and etch selectivity for the oxygen/chloride etch of more than 1 based upon the equivalence of polysiloxanes and spin-glass at [0127] of Asakawa et al. 20120097640, the acceptance of siloxane polymers as spin on glass materials at [0029] of Tsai et al. 20110189847.
In the response of 7/27/2026, the applicant argues that the prior art does not teach the use of a polysiloxane with more than 30% Si in an alcohol solution. The examiner points out that the siloxane polymers of the example of Kanno et al. 20150249012 meet this and is described as a hard/etch mask
Claims 15 and 22- 27 are rejected under 35 U.S.C. 103 as being unpatentable over Tokashiki et al. 5624583, in view of Shibayama et al. WO 2019124514, Asakawa et al. 20120097640 and Tsai et al. 20110189847.
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].
Useful coating solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether [0113].
It would have been obvious to modify example 4 of Tokashiki et al. 5624583 by using the hardmask compositions exemplified in Shibayama et al. WO 2019124514 with a reasonable expectation of success in forming a patterned polysiloxane/ruthenium structure and etch selectivity for the oxygen/chloride etch of more than 1 based upon the equivalence of polysiloxanes and spin-glass at [0127] of Asakawa et al. 20120097640, the acceptance of siloxane polymers as spin on glass materials at [0029] of Tsai et al. 20110189847 and the etch selectivity relative to halogen gasses taught in Ishibashi et al. WO 2020138092 at [0011].
Alternatively, it would have been obvious to modify example 4 of Tokashiki et al. 5624583 by using the hardmask compositions similar to those exemplified in Shibayama et al. WO 2019124514 where nitric acid or acetic acid are used as the acidic catalyst as taught at [0071-0072] and/or propylene glycol monoethyl ether, methylisobutylcarbinol, propylene glycol monobutyl ether are used as the coating solvents as taught at [0113] with a reasonable expectation of success in forming a patterned polysiloxane/ruthenium structure and etch selectivity for the oxygen/chloride etch of more than 1 based upon the equivalence of polysiloxanes and spin-glass at [0127] of Asakawa et al. 20120097640, the acceptance of siloxane polymers as spin on glass materials at [0029] of Tsai et al. 20110189847 and the etch selectivity relative to halogen gasses taught in Ishibashi et al. WO 2020138092 at [0011].
In the response of 7/27/2026, the applicant argues that the prior art does not teach the use of a polysiloxane with more than 30% Si in an alcohol solution. The examiner points out that the siloxane polymers of the example of Shibayama et al. WO 2019124514 meet this and is described as a hard/etch mask
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Seta et al. 20010029105 teaches an SOG composition formed of silanol (Si(OH)4) dissolved in alcohol, which is spin coated and then baked [0091]
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Martin J Angebranndt whose telephone number is (571)272-1378. The examiner can normally be reached 7-3:30 pm EST.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 August 21, 2026
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