DETAILED ACTION
Status of Claims
Claims 1, 3-8, 10-13, 16-19, 21-28, 31-37, 39-42, 45, 47-49 and 91-94 are pending.
Claims 2, 9, 14-15, 20, 29-30, 38, 43-44, 46 and 50-90 are cancelled.
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 .
Status of Objections and Rejections
The previous grounds of rejection under 35 U.S.C. 112a are withdrawn in view of Applicant’s amendment.
The previous grounds of rejection under 35 U.S.C. 112b are withdrawn in view of Applicant’s amendment.
All other grounds of rejection stand.
New grounds of rejection under 35 U.S.C. 112b are necessitated by amendment.
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 94 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 94, the phrasing “said polyether comprising a block copolymer substituent comprising propylene oxide (PO) repeat units and ethylene oxide (EO) repeats units” in combination with “comprises a polyether substituent comprising propylene oxide (PO) repeat units, ethylene oxide (EO) repeat units, or a combination of PO and EO repeat units” and “wherein the ratio of PO/EO units in each polyether substituent…” is indefinite because the first phrase appears to require both EO and PO, the second phrase appears to indicate that EO or PO repeat units may be present and the third phrase appears to require each polyether substituent to have PO an EO repeat units. It is therefore unclear when chemical composition is present since the claim optionally states the polyether substituent may be EO or PO.
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) 1, 3-8, 10-13, 16-19, 21-24, 31-37, 39-42, 45, 47-49, 91-92 and 94 is/are rejected under 35 U.S.C. 103 as being unpatentable over Paneccasio Jr et al. (US 2007/0289875), in view of Roeger-Goepfert et al. (US 2012/0018310) and in view of Chen et al. (US 6,806,186).
Regarding claims 1, 45, and 94, Paneccasio Jr. discloses copper electrodeposition in microelectronics (title) including an electrolytic plating method of filling semiconductor integrated circuit substrates having submicron-sized interconnect features (abstract, Figure 3) (= a process for electroplating a copper deposit onto a semiconductor integrated circuit device substrate with electrical interconnect features including submicron-sized features having bottoms, sidewalls, and top openings) the process comprising:
immersing the semiconductor integrated circuit device substrate including submicron-sized features having bottoms, sidewalls, and top openings of 100 nm or smaller [0007], [0014] wherein said submicron-sized features (abstract) include high aspect ratio features having dimensions such that the high aspect ratio features have aspect ratios of at least about 3:1 (e.g. at least about 3:1, 4:1 [0021],[0064]) into an electrolytic plating composition comprising a source of copper ions (abstract) in an amount sufficient to electrolytically deposit copper onto the substrate and into the electrical interconnect features and a suppressor comprising a polyether (abstract) bonded to a nitrogen of an oligo(alkylene imine) comprising at least three amine sites [0024], said polyether comprising a block copolymer [0026] substituent comprising propylene oxide and ethylene oxide repeat units [0014]; and
supplying electrical current to the electrolytic composition to deposit Cu onto the substrate and superfill the submicron-sized features by rapid bottom-up deposition (abstract) at a rate of growth in the vertical direction which is greater than a rate of growth in the horizontal direction, wherein said oligo(alkylene imine) corresponds to the structure I [0024],
Wherein x is an integer between 0 and 4, y is an integer between 0 and 4, x+y is an integer between 2 and 6 (e.g. triamine, tetraamine, etc. [0024]; or x+y equals zero as applied to claim 94, see comment below), wherein the weight average molecular weight of the suppressor is between about 1,000 and about 20,000 [0014], [0037].
Regarding the phrase “R1 comprises an alkylene group, at least one of R2 R3 R4 R5 and R6 comprises a polyether substituent comprising a block copolymer of propylene oxide and ethylene oxide, and wherein each of the remainder of R2 R3 R4 R5 and R6 is selected from the group consisting of hydrogen, lower alkyl, aminoalkyl, hydroxyalkyl and a polyether substituent comprising propylene oxide repeat units, ethylene oxide repeat units or a combination of PO and EO repeat units”, Paneccasio Jr. does not indicate the R group of any internally located amine groups (i.e. Paneccasio Jr. does not provide an example of an internally located R group when there are more than two amine functional groups of the suppressor). Since Paneccasio Jr. is silent in regards to the chemical makeup of any internally located amine groups (i.e. when there are more than two amines), one of ordinary skill in the art would necessarily look to the relevant art for guidance regarding structural makeup and arrive at a reference such as Roeger-Goepfert.
In the same or similar field of electrolytic copper plating methods, Roeger-Goepfert discloses a method for copper plating comprising an amine-based suppressor wherein R groups (e.g. R2 of Roeger-Goepfert, Formula I, [0023]) located at a position of an internally located amine group of the suppressor which include a copolymer of ethylene oxide and at least one further C3 to C4 alkylene oxide (e.g. propylene oxide = C3). R2 of Roeger-Goepfert is optionally R1 which is a copolymer of EO and PO repeat units [0014], [0023]-[0028]. Roeger-Goepfert discloses that the copolymers may be in any arrangement including block, alternating or random (as applied to claim 45) [0068]. Additionally, Roeger-Goepfert discloses openings of 30 nm or less and aspect ratios of 4 or more [0043].
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 polyether substituent comprising a block copolymer of EO and PO repeating units for any internally located R group such as the claimed R4 because Roeger-Goepfert discloses a similar suppressor compound and method to Paneccasio Jr. which comprises internally located polyether substituent comprising a block copolymer of EO and PO repeating units as described above. Roeger-Goepfert discloses guidance regarding internally located R groups for a suppressor which may be a triamine, tetraamine, etc. [0032]. The teachings of Roeger-Goepfert and Paneccasio Jr. overlap in multiple instances for example, Roeger-Goepfert discloses a method for metal plating comprising a copper metal ion source [0047] and a suppressor agent obtainable by reacting an amine compound comprising at least three active amino functional groups with a mixture of ethylene oxide and at least one compounds selected from C3 and C4 alkylene oxides (abstract) including block copolymer repeat units (see Comp. Examples, Table 1, [0068]) wherein the molecular weight may be between 500 g/mol and 30,000 g/mol [0036]. The methods of Roeger-Goepfert and Paneccasio Jr. are inclusive of amine-based suppressors and copper ions, (Roeger-Goepfert, [0053]-[0054]). Roeger-Goepfert and Paneccasio Jr. teach the arrangement of copolymers of amine-based suppressors including block, alternating and random as described above. The ranges of feature opening and aspect ratio of Paneccasio Jr. and Roeger-Goepfert overlap with the claimed ranges therefore a prima facie case of obviousness exists.
Paneccasio Jr. and Roeger-Goepfert fail to disclose the claimed ramping of electrical current.
In the same or similar field of copper filling submicron features, Chen discloses an initial film of metal is deposited into micro-recessed structures using at least a first electroplating waveform having a first current density provided to enhance the deposition of the metal at a bottom of the micro-recessed structure. Chen discloses that after the initial plating, deposition of the metal is continued using at least a second electroplating waveform having a second current density, the second current density is provided to assist in reducing the time required to substantially complete the filling of the micro-recessed structure (abstract). Chen discloses the ratio of first current density to second current density is 1:8 (Col. 6 lines 59-65).
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 ramping a current as claimed because Chen teaches a similar copper electroplating method that has a first electroplating step at a first current density and a second electroplating step with a higher current density to shorten plating time and enhance a bottom up filling (abstract). It would have been obvious to modify the similar methods of Paneccasio Jr. and Roeger-Goepfert with the multi-step electroplating of Chen given the overlapping subject matter. Regarding claim 94, given the indefiniteness as described above, it is unclear what chemical structure is required. Moreover, Paneccasio Jr. discloses the suppressor comprising at least one amine functional group [0024], [0031] thus satisfying the claimed one amine structure when x and y are 0. R1 of Paneccasio Jr. optionally comprises EO and PO groups [0033]. Formula 2 of Paneccasio Jr. comprises at least R1 and R3 which optionally comprise polyether groups [0033], [0035] and therefore satisfies the claimed structure. Moreover, the teachings of Paneccasio Jr. unambiguously disclose polyether groups bonded to a nitrogen atom [0023] the nitrogen atom covalently bonded to one, two or three PO/EO polyethers [0031].
Regarding claims 3-6, 12-13 and 47-48, Paneccasio Jr. discloses a ratio of EO and PO units between 1:9 and 9:1 [0025]. Paneccasio Jr. discloses triamines, tetraamine and higher amines [0024]. Paneccasio Jr. discloses a molecular weight between 1,000 and 30,000 ([0014]). The molecular weight of Paneccasio Jr. and the claimed weight overlaps therefore a prima facie case of obviousness exists.
Regarding claims 7-8, 16-19, 21, 33-37, 39-42 and 49, Roeger-Goepfert discloses a method for copper plating comprising an amine-based suppressor wherein R groups (e.g. R2 of Roeger-Goepfert, Formula I, [0023]) located at a position of an internally located amine group of the suppressor which include a copolymer of ethylene oxide and at least one further C3 to C4 alkylene oxide (e.g. propylene oxide = C3). R2 of Roeger-Goepfert is optionally R1 which is a copolymer of EO and PO repeat units [0014], [0023]-[0028]. Paneccasio Jr. discloses a ratio of EO and PO units between 1:9 and 9:1 [0025]. Paneccasio Jr. teaches that cationic indicates that the polyether suppressor contains a positive charge in solution regardless of pH [0023], [0031] (= quaternized suppressor). Paneccasio Jr. discloses triblock copolymers and having between about 1 and about 30 repeat units [0026]. Paneccasio Jr. disclose an accelerator including 1-propanesulfonic acid, 3,3'-dithiobis, disodium salt according to the following formula (11) [0052] in an amount such as 0.5-1000 mg/ L [0053] (as applied to claim 34).
Regarding claim 10, Paneccasio Jr. discloses a suppressor concentration between about 10 to about 1000 mg/L [0044] which overlaps the claimed suppressor concentration.
Regarding claim 11, Paneccasio Jr. discloses the composition comprising an accelerator [0016].
Regarding claim 22, Paneccasio Jr. discloses features including a small diameter of 500 nm or less [0021]. Additionally, Roeger-Goepfert discloses openings of 30 nm or less [0043].
Regarding claim 23, Paneccasio Jr. discloses supplying electrical current [0016] using a seed layer [0029].
Regarding claim 24, Paneccasio Jr. discloses a leveler [0022].
Regarding claim 31, Paneccasio Jr. discloses a current density up to about 100 mA/cm2 [0066]. Roeger-Goepfert discloses diameter including less than 20 nm [0043].
Regarding claims 32 and 91, Chen discloses electroplating at an initial current density of 4 mA/cm2 and a second current density at 32 mA/cm2 (Col. 5 lines 60-65). The current density of Chen does not overlap the claimed ranges, however, they are close enough that one of ordinary skill in the art would have produced the same or similar predictable result. Chen is silent in regards to the duration. Paneccasio Jr. discloses electroplating within the seconds range [0120]. Roeger-Goepfert discloses electroplating within the seconds range (Examples 7-10). Chen discloses using at least a second electroplating waveform (abstract). Chen for example teaches using a third electroplating waveform (claim 20). Regarding any further duplication of applying current density, duplication of any process steps has no patentable significance unless a new and unexpected result is produced (MPEP § 2144.04 VI B).
Regarding claim 92, Chen discloses void-free filling (Col. 6 lines 40-41). Roeger-Goepfert discloses forming copper plating with reduced or no voids [0110] (Figures 7a, 7b).
Claim(s) 25-28 and 93 is/are rejected under 35 U.S.C. 103 as being unpatentable over Paneccasio Jr. et al. (US 2007/0289875), in view of Roeger-Goepfert et al. (US 2012/0018310), in view of Chen (US 6,806,186) and in further view of Paneccasio Jr. et al. (US 2010/0126872).
Regarding claims 25-28 and 93, Paneccasio Jr. (‘875) discloses the composition comprising a leveler [0022], [0045]. Paneccasio Jr., Roeger-Goepfert and Chen fail to disclose the claimed leveler.
In the same field of electrodepositing copper within features, Paneccasio Jr. (‘872) discloses a copper composition comprising levelers such as Structures (IV)-(VIII) and wherein X is at least 2 and B is optionally oxygen [0091]-[0103], [0114]. Paneccasio Jr. teaches that the leveler aids in void-free copper deposits [0028].
Before the effective filing date of the claimed invention, it would have been obvious to one of ordinary skilled in the art to produce a composition comprising a leveler as claimed because Paneccasio Jr. (‘872) teaches that the leveler of Structures (IV)-(VIII) produce void-free deposits. Regarding claims 27-28, the claimed leveler is presented as product-by-process claim language. Product-by-process claims are not limited to the manipulations of the recited steps, only the structure implied by the steps. Moreover, Paneccasio Jr. (‘872) discloses dipyridyl compounds which render the claimed reaction product obvious [0040]-[0044].
Response to Arguments
Applicant's arguments filed 11 December 2025 have been fully considered but they are not persuasive.
The remarks on pages 17-18 directed towards the previous grounds of rejection under 35 U.S.C. 112b which have been withdrawn in view of Applicant’s amendment and therefore will not be specifically addressed at this time.
The argument on pages 18-20 states that the combined teachings of Paneccasio, Roeger-Goepfert and Chen do not disclose the claimed invention. In part, the argument states that one of ordinary skill would not combine the submicron sized features of Chen with Paneccasio and Roeger-Goepfert to arrive at the claimed invention of top openings of 50 nm or less. The Examiner respectfully disagrees with this analysis. In response to applicant's arguments against the references individually, one cannot show nonobviousness by attacking references micronindividually where the rejections are based on combinations of references. See In re Keller, 642 F.2d 413, 208 USPQ 871 (CCPA 1981); In re Merck & Co., 800 F.2d 1091, 231 USPQ 375 (Fed. Cir. 1986). Paneccasio discloses top openings of 100 nm or smaller [0007], [0014]. Roeger-Goepfert discloses openings of 30 nm or less and aspect ratios of 4 or more [0043]. Chen discloses the following sizing concepts including submicron (Col. 5 lines 14-15), 0.5 µm (Col. 4 lines 65-66) and recognizes difficulties and optimizing parameters to overcome the difficulties in submicron copper electroplating (Col. 2 lines 31-54). Chen clearly recognizes the challenges of feature filling and clearly describes a method in which the electroplating waveform is selected to initially deposit copper at the bottom of a feature to produce void-free electroplating (abstract). Therefore it would have been obvious to one of ordinary skill in the art would to combine feature filling with the electroplating waveform of Chen for producing void free copper electroplating into submicron or small features.
On page 19 of the response the argument states that Chen is directed to micro-recessed structures and not submicron copper interconnects. The Examiner respectfully disagrees with this analysis. Chen explicitly discloses submicron features (title).
On page 20 the remarks are directed towards claim 32 and 91 and state that Chen does not describe a ramped electrical current using three different current densities and therefore does not disclose the claimed invention. The Examiner respectfully disagrees with this analysis. Chen explicitly discloses using at least a second electroplating waveform (abstract). Chen for example teaches using a third electroplating waveform (claim 20).
On pages 21-23 the argument is directed towards claim 94 and states that none of the cited references discloses the claimed suppressor. The Examiner respectfully disagrees with this analysis. Paneccasio Jr. discloses primary amine structures [0023]-[0024], [0031]. R1 of Paneccasio Jr. optionally comprises EO and PO groups [0033]. Formula 2 of Paneccasio Jr. comprises at least R1 and R3 which optionally comprise polyether groups [0033], [0035] and therefore satisfies the claimed structure. Moreover, the teachings of Paneccasio Jr. unambiguously disclose polyether groups bonded to a nitrogen atom [0023] the nitrogen atom covalently bonded to one, two or three PO/EO polyethers [0031].
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 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
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