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 .
Election/Restrictions
Applicant’s arguments, filed 04/01/2026, with respect to restriction requirement have been fully considered and are persuasive. The restriction of claims 1-21 and 23 has been withdrawn.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA 35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA 35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claim 14 is rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends. Claim 14 recites the electrolyte free of any accelerator or lever, while being dependent on claim 1, which requires the both accelerator and lever. Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
Claim Rejections - 35 USC § 102
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.
Claim(s) 1-10 and 14 is/are rejected under 35 U.S.C. 102(a) as being anticipated by Kienle et al. (US 20190309429 A1).
Considering claim 1, Kienle discloses a copper electroplating solution comprising: a) a copper salt [0117]; b) a source of halide ions [0127]; and c) a suppressor, wherein the suppressor comprises a reaction product of a reactant with 2,3-epoxy-1-propanol [0076], for X3 = C1 [0030], wherein the reactant comprises at least one of an amine and a sulfur-containing compound [0075].
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 Kienle 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].
Considering claim 2, Kienle discloses the copper salt is copper sulfate [0117].
Considering claim 3, Kienle discloses sulfuric acid or methane sulfonic acid [0126].
Considering claim 4, Kienle discloses an accelerator comprising an organic sulfur compound [0132] and a leveler comprising a quaternary nitrogen compound [0147].
Considering claim 5, Kienle discloses the reactant comprises an amine compound, the amine compound is triethanolamine [0108].
Considering claims 6 and 7, Kienle discloses in formula III, R31, R32 are independently selected from C2 to C6 polyoxyalkylene group [0027] and X3 is a linear or branched C1 to C12 alkanediyl, which may be interrupted by O and S atoms [0020]. comprises 2,2'-thiodiethanol.
Considering claim 8, Kienle discloses the accelerator is for example 3-mercapto-1-propanesulfonic acid [0141] or 3-(2-benzthiazolylthio)-1-propanesulfonic acid [0142], corresponding to the claimed 3-(benzothizolyl-2-mercapto)-propylsulfonic acid.
Considering claim 9, Kienle discloses both the accelerator and the leveler are present in the composition [0123].
Considering claim 10, Kienle discloses 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, Kienle 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 [0123]. Therefore, Kienle 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 leveler, because Kienle teaches these components merely as optional.
Claim Rejections - 35 USC § 103
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.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
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, Kienle discloses the copper electroplating solution comprises: copper typically present in an amount in the range of from about 1 to about 300 g/l [0120], 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/ [0126], 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) [0127], 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) [0145], 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 [0076].
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, Kienle 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 [0147]; and preferable amount of accelerators is 2-100 ppm (2-100 mg/L) [0143], 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 Richardson et al. (US 20190368064 A1) in view of Banik et al. (WO 2020092244 A1).
Considering claim 15, Richardson discloses a method of electrodepositing copper on a substrate comprising: contacting a surface of a substrate and at least one anode with copper electrolyte solution comprising: a copper salt [0021], a source of halide ions [0023], a suppressor comprising a linear or branch polyhydroxyl [0124], an accelerator comprising an organic sulfur compound [0136] and a leveler comprising a quaternary nitrogen compound [0083].
Richardson 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 Richardson, 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 Richardson 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) [0157].
Considering claim 20, in Richardson as modified by Banik, Banik discloses the nanotwinned copper deposit is in a (111) orientation [0008].
Claim(s) 15, 16, 18-20 and 23 is/are rejected under 35 U.S.C. 103 as being unpatentable over Kienle et al. (US 20190309429 A1) in view of Banik et al. (WO 2020092244 A1).
Considering claim 15, Kienle discloses a method of electrodepositing copper on a substrate comprising: contacting a surface of a substrate and at least one anode with copper electrolyte solution comprising: a copper salt [0117], a source of halide ions [0127], a suppressor comprising a linear or branch polyhydroxyl [0076], an accelerator comprising an organic sulfur compound [0132] and a leveler comprising a quaternary nitrogen compound [0147].
Kienle 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 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.
Considering claim 16, in Kienle as modified by Banik, Banik discloses the nanotwinned copper deposit is in a (111) orientation [0008].
Considering claims 18 and 19, Kienle discloses a method of electrodepositing copper, a copper seed layer provided by physical vapor deposition (polycrystalline copper seed) [0172].
Considering claim 20, in Kienle as modified by Banik, Banik discloses the nanotwinned copper deposit is in a (111) orientation [0008].
Considering claim 23, Kienle discloses current density of between about 1-60 mA/cm2 (0.1-6 ASD) [0168], 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 Kienle 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 Kienle 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 Kienle 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, Kienle discloses a method of electrodepositing copper on a copper seed layer provided by physical vapor deposition (polycrystalline copper seed) [0172], 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.
Kienle 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 Kienle 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
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the conflicting claims are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on nonstatutory double patenting provided the reference application or patent either is shown to be commonly owned with the examined application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. See MPEP § 717.02 for applications subject to examination under the first inventor to file provisions of the AIA as explained in MPEP § 2159. See MPEP § 2146 et seq. for applications not subject to examination under the first inventor to file provisions of the AIA . A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The filing of a terminal disclaimer by itself is not a complete reply to a nonstatutory double patenting (NSDP) rejection. A complete reply requires that the terminal disclaimer be accompanied by a reply requesting reconsideration of the prior Office action. Even where the NSDP rejection is provisional the reply must be complete. See MPEP § 804, subsection I.B.1. For a reply to a non-final Office action, see 37 CFR 1.111(a). For a reply to final Office action, see 37 CFR 1.113(c). A request for reconsideration while not provided for in 37 CFR 1.113(c) may be filed after final for consideration. See MPEP §§ 706.07(e) and 714.13.
The USPTO Internet website contains terminal disclaimer forms which may be used. Please visit www.uspto.gov/patent/patents-forms. The actual filing date of the application in which the form is filed determines what form (e.g., PTO/SB/25, PTO/SB/26, PTO/AIA /25, or PTO/AIA /26) should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to www.uspto.gov/patents/apply/applying-online/eterminal-disclaimer.
Claims 1-6, 11, 12, 16-21 and 23 rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-15 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 1-6, 9, 11, 12 and 16-21 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 1-6, 11, 12, 16-21 and 23 provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-26 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 the U.S. Patent.
This is a provisional nonstatutory double patenting rejection because the patentably indistinct claims have not in fact been patented.
Claim 1-6, 9, 11, 12, 16-21 and 23 provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 15-28 of copending Application No. 18/534819 (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 the U.S. Patent.
This is a provisional nonstatutory double patenting rejection because the patentably indistinct claims have not in fact been patented.
Conclusion
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/WOJCIECH HASKE/ Examiner, Art Unit 1794
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