DETAILED ACTION
Status of Claims
Claims 1-33 are pending.
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 final rejection. 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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 18 February 2026 has been entered.
Status of Objections and Rejections
The previous grounds of rejection under 35 U.S.C. 103 are withdrawn in view of Applicant’s amendment.
New grounds of rejection are necessitated by amendment.
Information Disclosure Statement
The information disclosure statements (IDS) submitted on 19 November 2025 and 18 February 2026 were filed before and with the mailing date of the request for continued examination on 18 February 2026. The submission is in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statement is being considered by the examiner.
Claim Rejections - 35 USC § 112
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.
Claim 10 is 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.
Regarding claim 10, the use of the double negative (no, not) renders the claim indefinite because it is unclear what is required in the pretreatment bath.
Claim Rejections - 35 USC § 102
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.
Claim(s) 1, 5, 8, 10, 19, 23, 25, 27-28 and 33 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Verbunt (US 2004/0152303).
Regarding claims 1, 25, and 33, Verbunt discloses an electrolytic copper bath composition and method (title) (= a method of electroplating a metal into features of a substrate), the method comprising:
An aqueous plating solution (abstract, [0044]) with a pH between 10 and 14 [0028] (= an aqueous solution of pH greater than 7),
Copper in the amount of 2 to 20 g/L ([0025], [0044] (= about 0.1 to 60 g/L copper salt dissolved in the aqueous solution),
EDTA [0029] (= a copper (II) complexing ligand),
Thiourea [0013], [0016], [0032] (= an accelerator comprising a thiocyanate salt or a thiourea), and
Hydroxypyridine [0013], [0016], [0031] (= a suppressor that is complementary to the accelerator comprising the thiocyanate salt or the thiourea, wherein the suppressor is selected from a group consisting of polyallylamine, polyacrylamide, a pyridine, an imidazole, or any combination thereof);
Performing a plating operation [0033] to fill openings including vias and trenches [0004], [0035] (= and electroplating copper metal from the electroplating solution into features of the substrate).
All the ranges of Verbunt fall within the claimed ranges. The claimed “a suppressor that is complementary to the accelerator” does not further limit the claimed method or composition. Verbunt discloses the claimed chemical compounds therefore reads on the claimed phrase.
Regarding claim 5, Verbunt discloses flowing the plating solution through the electroplating tank (11) (Figure 1) from the opening [0036].
Regarding claim 8, Verbunt discloses alkaline cleaning and borane solution for 1 minute prior to plating [0045].
Regarding claim 10, Verbunt does not disclose a pretreatment bath that contains constituent chemicals that are not also present in the electroplating solution [0045]. It is unclear what is required in the pretreatment bath as indicated above.
Regarding claim 19, Verbunt discloses initially placing the substrate in the plating solution without current [0045].
Regarding claim 23, Verbunt discloses that the applied current can be pulsed [0036]-[0037].
Regarding claim 27, Verbunt discloses preventing the precipitation using a complexing agent and therefore discloses the ligand present in the solution at a concentration sufficient to prevent copper hydroxide precipitation.
Regarding claim 28, Verbunt discloses the inclusion of hydroxide ions [0012]-[0013] and a pH within the claimed range [0028]-[0029].
Claim Rejections - 35 USC § 103
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 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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim(s) 3, 12-14 and 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303).
Regarding claim 3, Verbunt discloses completely filling the vias and trenches [0045]. Verbunt does not explicitly disclose the method comprising a superconformal fill of the copper metal, however, while Verbunt does not specifically address the claim limitation “superconformal fill”, this is considered to be an intrinsic property resulting from following the method steps taught by the reference(s), which are the same as those instantly claimed, absent any clear and convincing evidence and/or arguments to the contrary. As a prima facie case of obviousness has been set forth on the record, and because the USPTO does not possess the laboratory facilities to test and compare the prior art to the claimed invention, the burden shifts to applicant to demonstrate otherwise.
Regarding claim 12, Verbunt discloses features including 250 nm [0045] and submicron openings 0.5 micron or lower [0004].
Regarding claims 13-14, Verbunt discloses a 25 nm tantalum barrier [0045]. Although the thickness of the tantalum barrier is outside the claimed thickness, they are close enough that one of ordinary skill in the art would expect the same or similar predictable result. Verbunt discloses tantalum nitride [0006].
Regarding claim 20, Verbunt discloses using a current density between 0.01 and about 5 A/dm2 [0033]. The range of Verbunt overlaps the claimed range therefore a prima face case of obviousness exists.
Claim(s) 2, 26 and 29 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303) in view of Shi (CN 107604393).
Regarding claims 2 and 26, Verbunt discloses the inclusion of thiourea. Verbunt fails to disclose the method and composition comprising thiocyanate.
In the same or similar field of alkaline copper electroplating, Shi discloses a method of electroplating copper comprising copper sulfate (15-17 g) [0012], tartrate [0011], pH 9.5-10.5 [0021] and a brightener (i.e. accelerator) including any one of polyethyleneimine, thiocyanate, thiourea, etc. [0014]. Shi discloses that the brightener is an electroplating additive and its main function is to adsorb on the surface of the electrode to form an extremely thin adsorption layer, which increases the number of metal nuclei [0060]-[0061].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to simply substitute one known accelerator for another to produce the same or similar predictable result. The subject matter of Verbunt and Shi overlap in several aspects including the composition of the copper electrolyte.
Regarding claim 29, Shi discloses the copper electroplating solution comprising a leveler [0011], [0088]. A plating leveler provides leveling uniformity to the electroplating method within features according to Shi [0064].
Claim(s) 4 and 24 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303) in view of Josell et al. (“Superconformal Copper Electrodeposition in Complexed Alkaline Electrolyte”, JES, 161, D287, 2014).
Regarding claim 4, Verbunt fails to disclose rotating the substrate.
Josell discloses superconformal copper electrodeposition into trenches of wafers (title, page D288, left column, 2nd paragraph), contacting wafers with an electrolyte (title) comprising an aqueous electrolyte of pH between 12.4 to 12.5 (page D287, Experimental; water based mixtures added together, Experimental), 0.1 mol/L copper surface (appx. 17.7 g/L) (= about 0.1 to 60 g/L copper salt dissolved in the aqueous solution, CuSO4·H2O (~177g/mol) ), tartrate (= a copper (II) complexing ligand), polyethyleneimine (PEI) (= an accelerator), and SPS (= a suppressor that is complementary to the accelerator) (Experimental, page D287-D288, Figure 3); and feature filling copper into trenches of wafers (Figure 6-8). Josell discloses rotating around a vertical axis (D288, left column, last paragraph). Josell discloses the current density varying based on rotation rate (Figure 1b).
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to produce a method comprising rotating a substrate because Josell discloses that the rotation rate controls and/or effects the current density.
Regarding claim 24, Josell discloses controlling the voltage of the substrate (D289, Figure 3).
Claim(s) 6 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303) in view of Ponnuswamy et al. (US 7,964,506).
Regarding claim 6, Verbunt fails to disclose an annealing step as claimed.
In the same or similar field of endeavor, Ponnuswamy discloses a pretreatment step of annealing from 100-400 ℃ for about 1 to 5 minutes in a nitrogen or argon atmosphere. Ponnuswamy discloses annealing to reduce oxides or contaminants on the surface prior to electroplating (Col. 13 lines 6-20).
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to produce a method comprising annealing because Ponnuswamy discloses annealing to reduce oxides or contaminants on the surface prior to electroplating (Col. 13 lines 6-20).
Claim(s) 7 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303) in view of Doubina et al. (US 2015/0299886).
Regarding claim 7, Verbunt fails to disclose the claimed remote plasma.
In the same or similar field of endeavor, Doubina discloses a pretreament step of treating the substrate with a remote plasma at elevated temperatures (e.g. 250 ℃) abstract, [0176]. Doubina teaches that the pretreatment provides a seed layer with higher conductivity. Doubina discloses that the duration of pretreatment can be adjusted by increasing plasma power with a duration in the seconds to minutes range for reducing the oxide on the surface [0088].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to produce a method comprising annealing in the presence of a remote plasma because Doubina discloses pretreatment with a remote plasma power for reducing the oxide on the surface [0088].
Claim(s) 9 and 11 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303) in view of Mayer et al. (US 8,962,085).
Regarding claims 9 and 11, Josell in view of Shi fails to disclose the claimed pretreatment.
In the same or similar field of endeavor, Mayer discloses contacting the substrate with a pre-wetting fluid to form a layer of pre-wetting fluid on the wafer substrate which includes water and copper ions and is substantially free of additives (Col. 3 lines 9-11, Col. 34 lines 37-54). Mayer teaches additionally polarizing the pre-wetted wafer (claim 24) (as applied to claim 9). Mayer discloses sufficient time of pre-wetting process including for example 5 seconds to 1 minute (Col. 23 lines 14-31). Mayer discloses that the pre-wetting prevents corrosion of a seed layer on the wafer and also to improve the filling rate of the features (abstract). Mayer optionally discloses the pre-wetting solution being the same or slightly different than the electroplating solution, thus the slight modification of the pre-wetting solution to obtain the electroplating solution would have been an obvious engineering design choice (Col. 8 line 44 – Col. 9 line 4; as applied to claim 11).
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to produce a method comprising a pretreatment step in a bath because Mayer discloses that the pre-wetting prevents corrosion of a seed layer on the wafer and also to improve the filling rate of the features (abstract).
Claim(s) 15-16, 21 and 30-31 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303) in view of Josell et al. (US 2015/0345039).
Regarding claims 15-16, Verbunt discloses initially forming a Cu seed layer [0001], [0045]. Verbunt is silent in regards to the thickness of the seed layer.
In the same or similar field of copper electroplating, Josell (‘039) discloses a method of electroplating a metal (e.g. copper, [0022]-[0023]) into features (e.g. vias, [0068]) of a substrate (abstract), the method comprising contacting a substrate with an electroplating solution comprising (abstract), an aqueous solution of pH greater than 7 (i.e. alkaline, abstract, [0035]), about 0.1 to 60 g/L copper salt dissolved in aqueous solution (1 to 100 mmol/L) [0054], a copper (II) complexing ligand (e.g. EDTA, [0028], [0032]), thiourea [0038]-[0039] or thiocyanate [0045] and saccharin [0046] and electroplating copper metal from the electroplating solution into features of the substrate (abstract). Josell discloses a cobalt seed layer (as applied to claim 16) comprising 1 to 200 nm which overlaps the claimed range therefore a prima facie case of obviousness exists [0057].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to produce a method comprising a conductive liner that is about 1 to 5 nm thick because in the same field of endeavor, Josell (‘039) discloses a workable thickness range including 1 to 200 nm.
Regarding claims 21, Josell (‘039) discloses pulsed or periodic current waveform which vary from 0 to the set current density [0067].
Regarding claims 30-31, Josell (‘039) discloses the solution comprising iodide, chloride, ([0037], claim 12), imidazole [0043], etc. Since Josell (‘039) discloses the claimed copper complexing ligand, Josell necessarily discloses the copper complexing ligand stabilizes copper (I) thereby causing Cu(II) reduction to occur more readily during electroplating.
Claim(s) 17-18 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303) in view of Reid et al. (US 2010/0032310).
Regarding claims 17-18, Verbunt fails to disclose the claimed copper pseudoreference electrode and holding at an electrical potential as claimed.
In the same or similar field of endeavor, Reid discloses a process of potentiostatic entry wherein the potential between the substrate and a reference electrode (e.g. copper) carrying no current, is maintained at a fixed value and the current increases approximately linearly with increasing wetted area of the substrate [0013]. Reid teaches that the process allows for diverting the current from near-edge regions of the substrate [0015] and avoiding substrate burning [0026]. Reid discloses a potential between 0.35 to about 1.4 V [0104] for a duration in the milliseconds (e.g. 75-300 ms) [0105]. Reid discloses a copper reference electrode [0134]. Reid discloses the current initially zero and then gradually increasing [0012] (Figure 12).
Before the effect filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to produce a method comprising holding an electrical potential as claimed because Reid teaches that the potential controlled process allows for diverting the current from near-edge regions of the substrate [0015] and avoiding substrate burning [0026].
Claim(s) 22 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303), in view of Josell et al. (US 2015/0345039) and in further view of Gonzalez (WO 2011/018478, Cited as Alchimer et al. in the IDS dated 22 December 2022).
Regarding claim 22, Verbunt in view of Josell (‘039) disclose the claimed invention as applied to claim 21. Josell (‘039) discloses pulsed or periodic current waveform which vary from 0 to the set current density [0067] as described above. The combination fails to disclose the claimed period.
In the same or similar field of endeavor, Gonzalez discloses pulsed current in seconds and milliseconds (page 21 lines 16-20). Control of the current necessarily includes control of the voltage according to Ohm’s law (V = iR). Gonzalez discloses 0.6 mA/cm2 – 10 mA/cm2 (page 21, line 19).
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to produce a method comprising applying a current density for a period of about 0.1 to about 10 seconds because Gonzalez discloses pulsed current in the seconds and milliseconds range. As described above, Josell (‘039) discloses a pulsed or periodic waveform [0067].
Claim(s) 32 is/are rejected under 35 U.S.C. 103 as being unpatentable over Verbunt (US 2004/0152303) in view of Brogan et al. (US 2018/0119305).
Regarding claim 32, Verbunt fails to disclose the claimed sacrificial oxidant.
In the same or similar field of endeavor, Brogan discloses that a copper electroplating solution [0028] may comprise a sacrificial oxidant which when present is used to develop a differential current efficiency within a feature compared to the field region (abstract), [0005].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to produce a method comprising a sacrificial oxidant because Brogan discloses that a copper electroplating solution [0028] may comprise a sacrificial oxidant which when present is used to develop a differential current efficiency within a feature compared to the field region to improve the filling (abstract), [0005].
Response to Arguments
Applicant's arguments filed 18 February 2026 have been fully considered. The remarks are directed towards the previous grounds of rejection which have been withdrawn and therefore will not be specifically addressed at this time. New grounds of rejection are necessitated by amendment.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to STEFANIE S WITTENBERG whose telephone number is (571)270-7594. The examiner can normally be reached Monday - Friday, 7:00 am -4:00 pm EST.
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/Stefanie S Wittenberg/Primary Examiner, Art Unit 1795