DETAILED ACTION
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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after allowance or after an Office action under Ex Parte Quayle, 25 USPQ 74, 453 O.G. 213 (Comm'r Pat. 1935). Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, prosecution in this application has been reopened pursuant to 37 CFR 1.114. Applicant's submission filed on 6/23/2026 has been entered.
Allowable Subject Matter
The indicated allowability of claims 1-16 and 19-23 is withdrawn in view of the newly discovered reference(s) to Liu et al (US 10,176,979); provided with the IDS dated 4/22/2025). Rejections based on the newly cited reference(s) follow.
Claim Rejections - 35 USC § 103
Claim(s) 1-6,10-16 and 19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liu et al (US 10,176,979) in view of Mishra et al (US 2021/0292685).
Regarding claims 1-2, 4-5 and 10-11, Liu et al disclose a (first) composition comprising at least one oxidizing agent, at least one complexing agent, at least one basic compound, at least one buffering agent, and water. Optionally, the first composition may further comprise at least one solvating agent, at least one surfactant, or a combination thereof (col.7, lines 48-65), wherein the oxidizing agent comprises potassium nitrate, ammonium nitrate, strontium nitrate, sulfuric acid, and combinations thereof (col.8, lines 51- col.9, lines 21); and aforesaid ammonium nitrate or potassium nitrate reads on the claimed “first ruthenium removal rate enhancer”;
Liu et al disclose that the buffering agents contemplated include, but are not limited to, dipotassium phosphate, potassium carbonate, boric acid, lysine, proline, β-alanine, ethylenediamine tetraacetic acid (EDTA) (col.9, lines 22-30); and aforesaid EDTA reads on the claimed “second ruthenium removal rate enhancer” and also required in the instant claim 5.
Liu et al disclose that the composition further comprises cleaning additives such as polyelectrolytes (e.g., polyacrylic acid, poly(acrylic-co-maleic acid), 1,2,4-triazole and derivatives thereof) (col. 11, lines 32-35); and aforesaid “1,2,4-triazole” reads on the claimed “copper removal rate inhibitor”; and also required in the instant claims 10 and 11.
Liu et al also disclose that the composition comprises surfactants such as non- ionic surfactant (col.9, lines 63-67); and aforesaid non-ionic surfactant reads on the claimed “low-k removal rate inhibitor”., wherein such may comprise alcohol alkoxylates (col.10, lines 12-32).
Liu et al also disclose that the composition is substantially devoid of abrasive material typically used in chemical mechanical polishing processes, fluoride-containing sources, amines, quaternary ammonium bases, and any combination thereof (col. 11, lines 19-25).
Liu et al disclose that the pH range of the first composition is in a range from about 2.5 to about 12; and the preferred range is from 7 to about 12 (col.8, lines 1-2); and aforesaid range overlaps the claimed range of about 7 to about 14; and overlapping ranges are prima face obvious, see MPEP 2144.05.
Unlike the instant invention, Liu et al fail to disclose the composition is free of polymers and organic solvents.
However, in the same field of endeavor, Mishra et al disclose a post-CMP cleaning composition, which is substantially free of one or more of certain ingredients, such as abrasives, organic solvent, polymers [0043].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to employ Mishra et al's teaching of excluding polymers form the cleaning composition into the teaching of Liu et al because such exclusion would have been simple substitution of known materials for predictable results.
Regarding claim 3, Liu et al disclose that the oxidizing agent (corresponding to the first ruthenium removal rate enhancer) is about 0.01 wt% to about 10 wt% (see the Table at col 13); and aforesaid ranges overlaps the claimed range and overlapping ranges are prima face obvious, see MPEP 2144.05.
Regarding claim 4, Liu et al disclose above that the oxidizing agent comprises potassium nitrate, ammonium nitrate, strontium nitrate, sulfuric acid, and combinations thereof (col.8, lines 51- col.9, lines 21); and
With regards to claim 12, without showing any criticality of the claimed concentration, it has been held that, generally, differences in concentration will not support the patentability of subject matter encompassed by the prior art in the absence of evidence indicating that said concentration is critical. See MPEP 2144.05.II.A.
Regarding claims 13-14, Liu et al also disclose that the composition comprises surfactants such as non- cysteine ionic surfactant (col.9, lines 63-67); and aforesaid non-ionic surfactant reads on the claimed “low-k removal rate inhibitor”., wherein such may comprise alcohol alkoxylates (col.10, lines 12-32).
Regarding claim 15, Liu et al also disclose that about 0.001 wt % to about 1 wt % of surfactant(s) (see the Table at col.13); and aforesaid ranges overlaps the claimed range of 0.001 to about 10 wt% and overlapping ranges are prima face obvious, see MPEP 2144.05.
Regarding claim 16, Liu et al also disclose that the pH range of the first composition is in a range from about 2.5 to about 12; (col.8, lines 1-2); and aforesaid range overlaps the claimed range of about 9 to about 13; and overlapping ranges are prima face obvious, see MPEP 2144.05.
Regarding claim 19, Liu et al disclose a (first) composition comprising at least one oxidizing agent, at least one complexing agent, at least one basic compound, at least one buffering agent, and water. Optionally, the first composition may further comprise at least one solvating agent, at least one surfactant, or a combination thereof (col.7, lines 48-65), wherein the oxidizing agent comprises potassium nitrate, ammonium nitrate, strontium nitrate, sulfuric acid, and combinations thereof (col.8, lines 51- col.9, lines 21); and aforesaid “sulfuric acid” reads on the claimed “at least one acid”.
Liu et al disclose that the composition further comprises cleaning additives such as polyelectrolytes (e.g., polyacrylic acid, poly(acrylic-co-maleic acid), 1,2,4-triazole and derivatives thereof) (col. 11, lines 32-35); and aforesaid “1,2,4-triazole” reads on the claimed “heterocyclic compound selected from an azole”.
Liu et al also disclose that the composition comprises surfactants such as non- ionic surfactant (col.9, lines 63-67).
Liu et al disclose that the pH range of the first composition is in a range from about 2.5 to about 12; and the preferred range is from 7 to about 12 (col.8, lines 1-2); and aforesaid range overlaps the claimed range of about 7 to about 14; and overlapping ranges are prima face obvious, see MPEP 2144.05.
Liu et al also disclose that the composition is substantially devoid of abrasive material typically used in chemical mechanical polishing processes, fluoride-containing sources and quaternary ammonium bases, and any combination thereof (col 11, lines 19-25).
Unlike the instant invention, Liu et al fail to disclose the composition is free of polymers and organic solvents.
However, in the same field of endeavor, Mishra et al disclose a post-CMP cleaning composition, which is substantially free of one or more of certain ingredients, such as abrasives, organic solvent, polymers [0043].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to employ Mishra et al's teaching of excluding polymers form the cleaning composition into the teaching of Liu et al because such exclusion would have been simple substitution of known materials for predictable results.
Claim(s) 7-9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liu et al (US 10,176,979) in view of Mishra et al (US 2021/0292685) as applied to claim 1 above, and further in view of Thomas et al (US 2020/0071642).
Regarding claims 7-8, modified Liu et al disclose above for the claim 1 but fail to disclose the composition further comprises at least one metal oxide remover (as to claim 7) and which may include listed as to the instant claim 8.
However, in the same field of endeavor, Thomas et al disclose a post-CMP cleaning composition comprises a complexing agent comprises monoethanolamine (MEA), triethanolamine (TEA), etc. [0018], which reads on the claimed “at least one metal oxide remover”.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to employ Thomas et al's teaching of introducing surfactant into the teaching of modified Liu et al for effectively removing the residues/contaminants as suggested by Thomas et al [0009].
With regards to claim 9, Thomas et al disclose that the at least one complexing agent comprises a species chosen from monoethanolamine, triethanolamine, sulfuric acid, citric acid and combinations thereof. In one embodiment, the amount of complexing agent(s) in the removal composition is in a range from about 0.01 wt % to about 10 wt %, based on the total weight of the removal composition [0018]; and aforesaid range overlaps the claimed range of about 0.01 to about 40 wt %.
Claim(s) 20-23 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liu et al (US 10,176,979) in view of Mishra et al (US 2021/0292685) as applied to claims 1 and 19 above, and further in view of Ivanov et al (US 2016/0201016; Ivanov herein after).
With regards to claim 20, Liu et al modified with Mishra et al disclose above except the composition further comprises at least one compound comprising nitrogen and at least one of oxygen and sulfur.
However, Ivanov teaches a composition for cleaning a substrate following chemical -mechanical polishing (post-CMP cleaning), wherein the cleaning composition comprises at least one compound, such as strong chelating ligand in the form of an organic amine generally has a high chelating effect, atoms with a very high electron density donating ability (e.g., nitrogen, phosphorus, sulfur, and oxygen) [0043].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to employ Ivanov's teaching of introducing the strong cleating agent for providing improved cleaning ability of the composition into the teaching of modified Liu et al for improving the cleaning ability of the composition as taught by Ivanov.
With regards to claims 21-22, Liu et al modified with Mishra et al disclose above a post-CMP composition and a process of removing particularly process for cleaning post-chemical mechanical polishing (CMP) residue and contaminants from a microelectronic device having said residue and contaminants thereon [abstract]; and also teach that the microelectronic device comprises barrier material and conventional barrier layer materials include tantalum or titanium, their nitrides and silicides, and alloys thereof. Candidate materials that could serve as directly plateable diffusion barriers include ruthenium (Ru), cobalt (Co), tungsten (W), molybdenum (Mo), rhenium (Rh), and alloys thereof (col.5, lines 57-65); and so, the substrate may comp[rises ruthenium or it’s alloy.
Liu et al may not explicitly teach the composition being used to clean a polished substrate comprising ruthenium or an alloy thereof in a polishing tool; and a pad is in contact with the surface of the polished surface and moving the pad in relation to the substrate to form a rinsed polished substrate.
However, Ivanov discloses a cleaning method comprises, consists of, or consists essentially of (a) providing a semiconductor wafer having contaminants resulting from chemical-mechanical polishing of the semiconductor wafer and (b) contacting the surface of the semiconductor wafer with a cleaning composition in accordance with embodiments of the invention to remove at least some of the contaminants from the surface of the semiconductor wafer; the contaminants can include, for example, abrasive particles, organic residue, metal ions, pad debris and CMP-byproducts, or any combination thereof. The wafer can include metal conductors and/or a low-k dielectric material in various embodiments [0104]; The method includes applying a cleaning composition in accordance with embodiments of the invention to selectively remove contaminants, while the metal conductors and/or low-k dielectric material remain substantially intact. In some embodiments, are formed from at least copper, tungsten, cobalt, and/or ruthenium [0105].
Ivanov also discloses that a method for polishing and cleaning the surface of a semiconductor wafer. The method comprises, consists of, or consists essentially of: (a) providing a polishing pad, a chemical-mechanical polishing composition, and a semiconductor wafer; (b) contacting the semiconductor wafer with the polishing pad and the polishing composition; (c) moving the polishing pad relative to a surface of the semiconductor wafer with the polishing composition therebetween to abrade the surface of the semiconductor wafer and thereby polish the surface of the wafer such that the polished surface of the wafer contains contaminants from the chemical-mechanical polishing composition; and (d) contacting the polished surface of the semiconductor wafer that contains contaminants with a cleaning composition as described herein to remove at least some of the contaminants from the polished surface of the semiconductor wafer [0106]; and aforesaid teaching above easily recognized that cleaning process is performed using the polishing tool; bringing a pad in contact with the polished substrate and moving the pad in relation to the substrate to form a rinsed or cleaned polished substrate.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to employ Ivanov's teaching of cleaning a polished substrate into the teaching of modified Liu et al for achieving a clean surface and free of contaminants as taught by Ivanov.
With regards to claim 23, Liu et al a process of removing particularly process for cleaning post-chemical mechanical polishing (CMP) residue and contaminants from a microelectronic device having said residue and contaminants thereon [abstract].
Therefore, one of ordinary skill in the art before the effective filing date of the claimed invention would easily recognize that the modified teaching of Liu et al with Ivanov from the microelectronic device (semiconductor device) using the rinsed or cleaned semiconductor substrate as discusses above.
Conclusion
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SHAMIM AHMED
Primary Examiner
Art Unit 1713
/SHAMIM AHMED/ Primary Examiner, Art Unit 1713
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