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 .
Claims Status
Claims 1-21 and 23 are pending. Claims 1, 11 and 12 have been amended.
Applicant’s arguments, filed 06/23/2026, with respect to 112 rejection have been fully considered and are persuasive. The rejection of claim 14 has been withdrawn.
Applicant’s arguments, filed 06/23/2026, with respect to the rejection(s) of claim(s) 1-21 and 23 under 35 USC 102 and 103 have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Roeger-Gopfert et al. US 20110290659 A1.
Applicant's arguments filed 06/23/2026, with respect to double patenting rejections have been fully considered and are persuasive in part. The rejection over copending application 18/534819, has been withdrawn. The remaining double patenting rejections have been modified in view of Applicant’s remarks.
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claim Rejections - 35 USC § 102
Claim(s) 1-5, 8-10 and 14 is/are rejected under 35 U.S.C. 102(a) as being anticipated by Roeger-Gopfert et al. (US 20110290659 A1).
Considering claim 1, Roeger-Gopfert discloses a copper electroplating solution comprising: a) a copper salt [0074]; b) a source of halide ions [0074]; and c) an additive, wherein the suppressor is a reaction product - alkoxylated polyalkanolamine obtainable by alkoxylating the resulting polyalkanolamine glycidol (2,3-epoxy-1-propanol) ([0016] and [0066]).
With respect to the limitation reciting the copper electrolyte is capable of depositing copper, wherein the copper deposit exhibits greater than about 80% nanotwinned columnar copper grains, the electrolyte of Roeger-Gopfert will be capable of the claimed function, because it meets all the claim limitations and the instant specification teaches that electroplating conditions will result in a high density of nanotinned copper, without the need for a special/particular electrolyte [0015]. With respect to the claimed compound being a suppressor, the amine-containing compound of Roeger-Gopfert has the same chemical composition as claimed therefore will inherently have the claimed property.
Considering claim 2, Roeger-Gopfert discloses the copper salt is copper sulfate [0074].
Considering claim 3, Roeger-Gopfert discloses sulfuric acid or methane sulfonic acid [0080].
Considering claim 4, Roeger-Gopfert discloses an accelerator comprising an organic sulfur compound [0090] and a leveler comprising a quaternary nitrogen compound [0082].
Considering claim 5, Roeger-Gopfert discloses the reactant comprises an amine compound, the amine compound is triethanolamine ([0009]-[0011]).
Considering claim 8, Roeger-Gopfert discloses the accelerator is for example 3-mercapto-1-propanesulfonic acid [0141].
Considering claim 9, Roeger-Gopfert discloses both the accelerator and the leveler are present in the composition [0078].
Considering claim 10, with respect to the limitations reciting the amounts of reactants used to make the suppressor are considered a product by process without bringing any substantial structural or compositional limitation to the claim. The amounts of components used in the reaction between 2,3-epoxy-1-propanol and the reactant comprising an amine or a sulfur-containing compound will depend on reaction conditions. The claim does not require any particular ratio of the two components in the final product nor what the final product is, but merely the relative amounts used for the reaction. The product after the reaction may be further processed and purified, the reaction condition may be selected to further include other components leading to a for example co-polymerization, or the reaction may not proceed completely, therefore the relative amounts as claimed do not positively recite the final product used as the suppressor.
Considering claim 14, Roeger-Gopfert teaches that besides the metal ions and at least one of the suppressing agents and acid the electroplating compositions includes optionally halide ions, and optionally other additives like accelerators and/or levelers [0077]. Therefore, Roeger-Gopfert teaches meets the claimed copper electroplating solution is at least substantially free of any accelerator, brightener, carrier, wetter, or leveler or any compound that can function as an accelerator, brightener, carrier, wetter, or suppressor, because Roeger-Gopfert teaches these components merely as optional. Note that both suppressors and levers inhibit the rate of deposition therefore they often share very similar compositions, e.g. PEG, amines. Therefore, the function assigned is not expressly defining the compound itself.
Claim(s) 1 is/are rejected under 35 U.S.C. 102(a) as being anticipated by Murakami et al. (JP 2012211369 A, translation provided with IDS).
Considering claim 1, Murakami discloses a copper electroplating solution comprising: a) a copper salt [0025]; b) a source of halide ions [0025]; and c) an additive, wherein the suppressor is a reaction product of polyalkanolamine and glycidol (2,3-epoxy-1-propanol) [0011].
With respect to the limitation reciting the copper electrolyte is capable of depositing copper, wherein the copper deposit exhibits greater than about 80% nanotwinned columnar copper grains, the electrolyte of Roeger-Gopfert will be capable of the claimed function, because it meets all the claim limitations and the instant specification teaches that electroplating conditions will result in a high density of nanotinned copper, without the need for a special/particular electrolyte [0015]. With respect to the claimed compound being a suppressor, the amine-containing compound of Murakami has the same chemical composition as claimed therefore will inherently have the claimed property.
Claim Rejections - 35 USC § 103
Claim(s) 11-13 is/are rejected under 35 U.S.C. 103 as being unpatentable over Kienle et al. (US 20190309429 A1).
Considering claims 11 and 12, Roeger-Gopfert discloses the copper electroplating solution comprises: copper typically present in an amount in the range of from about 1 to about 300 g/l [0076], with overlaps the claimed range of from about 40 to about 60 g/L copper ions; acids are typically present in an amount in the range of from about 1 to about 300 g/ [0080], which overlaps the claimed range of from about 80 to about 140 g/L sulfuric acid; halide ion concentrations may be used from about 0 to about 500 ppm (500 mg/L) [0081], which overlaps the claimed range of form about 30 to about 120 mg/L chloride ions; suppressors are typically used in an amount of about 1 ppm to about 10,000 ppm (1-10,000 mg/L) [0086], which overlaps the claimed range of from about 300 to about 600 mg/L linear or branched polyhydroxyl; wherein the polyhydroxyl comprises a poly(2,3-epoxy)-1-propanol directly bonded to a nitrogen-containing species.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have the recited range because a prima facie case of obviousness exists in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art”. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). Furthermore, "[ A ] prior art reference that discloses a range encompassing a somewhat narrower claimed range is sufficient to establish a prima facie case of obviousness." In re Peterson, 315 F.3d 1325, 1330, 65 USPQ2d 1379, 1382-83 (Fed. Cir. 2003). See MPEP 2144.05.
Considering claims 13, Roeger-Gopfert discloses the copper electroplating solution further comprises:
leveling agent typically from 1 to 100 ppm (1-100 mg/L) [0149], which overlaps the claimed range of from about 0.5 to about 10 mg/L of the leveler, the leveler comprising a polymer quaternary nitrogen species [0086]; and preferable amount of accelerators is 2-100 ppm (2-100 mg/L) [0101], which overlaps the claimed range of from about 1 to about 50 mg/L of the accelerator.
Claim(s) 15, 16, 18-20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Roeger-Gopfert et al. as applied to claim 1 and further in view of Banik et al. (WO 2020092244 A1).
Considering claim 15, Roeger-Gopfert discloses a method of electrodepositing copper on a substrate comprising: contacting a surface of a substrate and at least one anode with the copper electrolyte solution [0027].
Roeger-Gopfert does not disclose depositing a high density of nanotwinned columnar copper grains.
However, Banik discloses a copper structure having a high density of nanotwinned copper deposited on a substrate. Banik does not describe any particular electrolytic copper plating bath but instead describes electroplating conditions, including applying a pulsed current waveform that alternates between constant current and no current, where the duration of no current being applied is substantially greater than a duration of a constant current being applied [0008]. Furthermore, Banik teaches that nanotwinned copper (nt-Cu) exhibits excellent mechanical and electrical properties and may be used in a wide variety of applications in wafer level packaging and advanced packaging designs [0029].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to apply the method of forming high density nanotwinned copper in the method of Roeger-Gopfert, because Banik discloses a copper structure having a high density of nanotwinned copper deposited on a substrate by applying a pulsed current waveform that alternates between constant current and no current because nanotwinned copper (nt-Cu) exhibits excellent mechanical and electrical properties and may be used in a wide variety of applications in wafer level packaging and advanced packaging designs .
Considering claim 16, in Roeger-Gopfert as modified by Banik, Banik discloses the nanotwinned copper deposit is in a (111) orientation [0008].
Considering claims 18 and 19, Richardson discloses a copper seed layer provided by physical vapor deposition (polycrystalline copper seed) [0116].
Considering claim 20, in Roeger-Gopfert as modified by Banik, Banik discloses the nanotwinned copper deposit is in a (111) orientation [0008].
Considering claim 23, Roeger-Gopfert discloses current density of between about 1-60 mA/cm2 (0.1-6 ASD) [0111], which overlaps the claimed range of 1-8 ASD.
Claim(s) 17 and 21 is/are rejected under 35 U.S.C. 103 as being unpatentable over Roeger-Gopfert et al. and Banik et al. as applied to claims 1 and 15 above, and further in view of Chang et al. (US 20200135680 A1).
Considering claim 17, in Roeger-Gopfert as modified by Banik, Banik discloses high density nanotwinned copper deposited as shown in Fig. 1.
Bainik is silent about the greater than 90% nanotwinned columnar copper grains.
However, Chang discloses twinned copper volume percentage in the entire conductive layer ranges from about 95 vol % to about 99.9 vol % [0049].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention that the high density nanotwinned copper deposit of Banki in the method of Roeger-Gopfert as modified by Banik, because Bank only discloses qualitatively showing high density nanotwinned copper, and Chang discloses twinned copper volume percentage in the entire conductive layer ranges from about 95 vol % to about 99.9 vol % for the same purpose of for example filling vias. Therefore, it would have been obvious that the high density nanotwinned copper of Banik has greater than 90% nanotwinned columnar copper grains in order to have the benefits of greater Young's modulus and a tensile strength thus preventing the conductive lines from cracking [0059].
Considering claim 21, Roeger-Gopfert discloses a method of electrodepositing copper on a copper seed layer provided by physical vapor deposition (polycrystalline copper seed) [0116], using an aqueous electrolyte solution of claim 1, the method comprising: a) contacting the substrate having the seed layer with the electrolyte solution, and b) applying electric voltage.
Roeger-Gopfert is silent about the greater than 80% nanotwinned copper.
However, Banik discloses a copper structure having a high density of nanotwinned copper deposited on a substrate. Banik does not describe any particular electrolytic copper plating bath but instead describes electroplating conditions, including applying a pulsed current waveform that alternates between constant current and no current, where the duration of no current being applied is substantially greater than a duration of a constant current being applied [0008]. Furthermore, Banik teaches that nanotwinned copper (nt-Cu) exhibits excellent mechanical and electrical properties and may be used in a wide variety of applications in wafer level packaging and advanced packaging designs [0029].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to apply the method of forming high density nanotwinned copper in the method of Kienle, because Banik discloses a copper structure having a high density of nanotwinned copper deposited on a substrate by applying a pulsed current waveform that alternates between constant current and no current because nanotwinned copper (nt-Cu) exhibits excellent mechanical and electrical properties and may be used in a wide variety of applications in wafer level packaging and advanced packaging designs.
Furthermore, Chang discloses twinned copper volume percentage in the entire conductive layer ranges from about 95 vol % to about 99.9 vol % [0049].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention that the high density nanotwinned copper deposit of Banki in the method of Roeger-Gopfert as modified by Banik, because Banik only discloses qualitatively showing high density nanotwinned copper, and Chang discloses twinned copper volume percentage in the entire conductive layer ranges from about 95 vol % to about 99.9 vol % for the same purpose of for example filling vias. Therefore, it would have been obvious that the high density nanotwinned copper of Banik has greater than 90% nanotwinned columnar copper grains in order to have the benefits of greater Young's modulus and a tensile strength thus preventing the conductive lines from cracking [0059].
Double Patenting
Claims 1-5, 15-21 and 23 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 5, 6, 13 and 15 of U.S. Patent No. 11873568. Although the claims at issue are not identical, they are not patentably distinct from each other because all the limitations of the instant claims are met by the claims of the U.S. Patent.
Claims 1-5, 15-21 and 23 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-12 of U.S. Patent No. 11384446. Although the claims at issue are not identical, they are not patentably distinct from each other because all the limitations of the instant claims are met by the claims of the U.S. Patent.
Claim 1, 5 and 15 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 5 and 7 of copending Application No. 18/578049 (reference application). Although the claims at issue are not identical, they are not patentably distinct from each other because all the limitations of the instant claims are met by the claims of copending Application.
This is a provisional nonstatutory double patenting rejection because the patentably indistinct claims have not in fact been patented.
This is a provisional nonstatutory double patenting rejection because the patentably indistinct claims have not in fact been patented.
Allowable Subject Matter
Claims 6 and 7 objected to as being dependent upon a rejected base claim, but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
The following is an examiner’s statement of reasons for allowance: the prior art of record does not disclose a copper electrolyte with a suppressor formed by reaction product of glycidol and a sulfur containing compound as claimed.
Any comments considered necessary by applicant must be submitted no later than the payment of the issue fee and, to avoid processing delays, should preferably accompany the issue fee. Such submissions should be clearly labeled “Comments on Statement of Reasons for Allowance.”
Conclusion
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 Wojciech Haske whose telephone number is (571)272-5666. The examiner can normally be reached M-F: 9:30 am - 6:00 pm.
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/WOJCIECH HASKE/ Examiner, Art Unit 1794
