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 .
DETAILED ACTION
Claims 1-23 are pending. Note that, Applicant’s amendment and arguments filed December 16, 2025, and December 15, 2025, have been entered.
Objections/Rejections Withdrawn
The following objections/rejections as set forth in the Office action mailed 9/15/25 have been withdrawn:
The objection to claims 3-6, 12, 14, 15, 18, and 19 due to minor informalities has been withdrawn.
The rejection of claim 13 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inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention, has been withdrawn.
The rejection of claims 1-15 and 18-20 under 35 U.S.C. 103 as being unpatentable over Wu et al (US2019/0048292) or Wu et al (US2016/0300730), has been withdrawn.
The rejection of claims 1-20 on the ground of nonstatutory double patenting as being unpatentable over claims 1-19 of copending Application No. 18/473501 (reference application), has been withdrawn.
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
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.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
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.
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.
Claims 1-15 and 18-20 are rejected under 35 U.S.C. 103 as being unpatentable over Wu et al (US2019/0048292) or Wu et al (US2016/0300730), both in view of Agarwal et al (US2016/0179011) or Lee (US2012/0129345).
With respect to independent, instant claim 1, ‘292 teaches a semiconductor processing composition for removing residues and/or contaminants from substrate containing Cu, barrier metal and low-k dielectric. The processing composition includes at least one quaternary base, at least one organic amine, at least one surface modifier, at least one antioxidant, at least one complexing agent and balance water. The processing composition provides a sufficient corrosion protection to Cu and metal barrier during process queue time without deteriorating reliability of electronic devices. See Abstract. The amount of quaternary base is in the range of about 0.001 wt % to 25 wt %, preferably from about 0.01 wt % to 15 wt % based on the total weight of the disclosed processing composition, and suitable quaternary bases include tris (2-hydroxyethyl) methyl ammonium hydroxide, etc. See para. 16. The amount of organic amine is from about 0.001% to 20% by weight, preferably from about 0.01% to 10% by weight, based on the total weight of the disclosed cleaning composition, and suitable organic amines include N-methyldiethanolamine, monoethanolamine, triethanolamine, etc. See para. 17. The amount of surface modifier is from about 0.001% to 12% by weight, preferably from about 0.01% to 8% by weight based on the total weight of the cleaning composition, and suitable surface modifiers include xanthine, purine, etc. See para. 18. The amount of the complexing agent is from about 0.0001% to 8% by weight, preferably from about 0.0001% to 4% by weight, based on the total weight of the disclosed processing composition, and suitable complexing agents include citric acid, tartaric acid, oxalic acid, tributyl phosphate, dibutyl phosphate, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, etc. See para. 20. The pH of the composition is from 8-14. See claim 2.
With respect to independent, instant claim 1, ‘730 teaches post chemical mechanical planarization cleaning composition of semiconductor substrate for advanced electronics fabrication and packaging. It provides novel corrosion inhibition and quality upmost Cu-low K surfaces to the demanding reliability of nano device and Cu interconnection. See Abstract. Specifically, ‘730 teaches an alkaline aqueous solution in nature with a pH value in the range of 8.5-13.5. An organic base and balance water are used for pH adjustment. The organic bases include, but not limited to, quaternary amine, including tetrahexylammonium hydroxide (THAH), tetramethylammonium hydroxide (TMAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tetraethylammonium hydroxide (TEAH), trimethylphenylammonium hydroxide (TMPAH), tris(2-hydroxyethyl)methylammonium hydroxide, etc., which may be used in amounts from 1 wt% to about 10 wt%. See para. 34. A chelate agent, which helps prevent re-deposition of removed metal onto the wafer or interposer surface through metal complexation, includes, but not limited to, N,N,N'-trimethyl-N'-(2-hydroxyethyl) ethylenediamine, N,N-dimethylethylenediamine, N,N'-dimethylethanolamine, isobutanolamine, isopropanolamine, 2-(diethylamino) ethanol, aminoethylethanolamine, N-methylaminoethanol. aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine, triethanolamine, EDTA, CDTA, HIDA, and N-AEP, 1-methoxy-2-aminoethane, tetraethylenepentamine (TEPA), gluconic acid, tartaric acid, dimethyl glyoxime, formic acid, fumaric acid, glutamic acid, glutamine, glutaric acid, glyceric acid, glycerol, glycolic acid, etc., and combinations thereof. The chelating agents may be used in amounts from 1% to 10% by weight. See para. 35.
A corrosion inhibitor, which protects metal surface from attacking through oxidation and/or galvanic corrosion without compromising interference to atop dielectric deposition from CVD or PECVD, includes, but not limited to, purine compound, such as purine, guanine, hypoxanthine, xanthine, caffeine, uric acid, etc. Corrosion inhibitors are used in amounts up to 5% by weight. See para. 36.
‘292 or ‘730, do not teach the use of hydrazine or a composition containing a purine compound, a compound represented by Formula (A), hydrazine, and the other requisite components of the composition in the specific amounts as recited by the instant claims.
Agarwal et al teach a photoresist or semiconductor manufacturing residue stripping and cleaning composition comprising water, one or more alkaline compounds, one or more corrosion inhibitors, and one or more oxidized products of one or more antioxidants, the method of making the composition and the method of using the composition. See Abstract. The composition of this invention, alone or with any additional aspects of this invention, may have one or more amines selected from the
group consisting of 1,2,3-triaminopropane, hydrazine, monoethanolamine, diethanolamine, triethanolamine, etc. See para. 5.
Lee teaches contaminants from metal or dielectric surfaces comprises
at least one alkyl diphosphonic acid, at least one second acidic substance at a ratio of about 1:1 to about 10: 1 in water, and pH is adjusted to from about 6 to about 10 with a metal ion free base, and a surfactant. See Abstract. The mixture or blend is adjusted to a pH of about 6 to about 10 with a buffering amount of basic compounds such as an
alkanolamine component hydrazine, ethylenediamine, monoethanolamine, N,N diethylamino ethanol, 2-(2-hydroxylethylamino)ethanol, 2-(2-aminoethoxy)ethanol, N,N,
N-tris(2-hydroxyethyl)-ammonia, isopropanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 2-(N-methylamino)ethanol, 2-(2-arninoethylamino )ethanol, tris(hydroxymethyl)aminoethane, or mixtures thereof. See para. 28.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to use hydrazine in the composition taught by ‘292 or’730, with a reasonable expectation of success, because Agarwal et al or Lee teach the equivalence of hydrazine to monoethanolamine in a similar composition and further, ‘292 or ‘730 teach the use of monoethanolamine.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to formulate a composition containing a purine compound, hydrazine, a compound represented by Formula (A), and the other requisite components of the composition in the specific amounts as recited by independent, instant claim 1 and the respective dependent claims, with a reasonable expectation of success and similar results with respect to other disclosed components, because the broad teachings of ‘292 or ‘730 suggest a composition containing a purine compound, hydrazine, a compound represented by Formula (A), and the other requisite components of the composition in the specific amounts as recited by independent, instant claim 1 and the respective dependent claims.
Claims 16 and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Wu et al (US2019/0048292) or Wu et al (US2016/0300730), both in view of Agarwal et al (US2016/0179011) or Lee (US2012/0129345) as applied to claims 1-15 and 18-20 above, and further in view of Heo et al (US2016/0376532).
‘292 or ‘730 are relied upon as set forth above. However, neither reference teaches the use of tetraethylenepentamine in addition to the other requisite components of the composition of the composition as recited by the instant claims.
Heo et al teach a cleaner composition that can be used to remove metal oxides and metal abrasive particles arising during metal polishing, such as chemical mechanical planarization (CMP). See Abstract. The cleaner composition of the present invention may further include a compound that is understood as a complexing agent, a chelating agent and/or a sequestering agent by those skilled in the art. These additional components can chemically bind to or be physically fixed to target metal atoms and metal ions. See para. 49. According to one embodiment, the cleaner composition may further include an organic amine. The organic amine acts on metal oxides to uniformly clean the oxidized metal surface. The organic amine may be selected from the group consisting of primary organic amines, second organic amines, and tertiary organic amines. See para. 54. Suitable organic amines include monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc., and mixtures thereof. See para. 55.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to use tetraethylenepentamine in the composition taught by ‘292 or ‘730, with a reasonable expectation of success, because Heo et al teach the equivalence of triethanolamine to tetraethylenepentamine as an amine in a similar composition and further, ‘292 or ‘730 teach the use of triethanolamine.
Claim 22 is rejected under 35 U.S.C. 103 as being unpatentable over Wu et al (US2019/0048292) or Wu et al (US2016/0300730), both in view of Agarwal et al (US2016/0179011) or Lee (US2012/0129345) as applied to claims 1-15 and 18-20 above, and further in view of Ivanov et al (US 2016/0201016).
‘292 or ‘730 are relied upon as set forth above. However, neither reference teaches the use of adenosine or theobromine in addition to the other requisite components of the composition of the composition as recited by the instant claims.
Ivanov et al teach composition for cleaning contaminants from semiconductor wafers following chemical-mechanical polishing. The cleaning composition contains one or more quaternary ammonium hydroxides, one or more organic amines, one or more metal inhibitors, and water. See Abstract. Any suitable metal inhibitor can be used in the composition. The metal inhibitor serves to protect metals typically found on a semiconductor wafer by interacting with the metal surface. The metal inhibitor of some embodiments is a purine selected from guanine, xanthine, hypoxanthine, theophylline, paraxanthine, theobromine, caffeine, uric acid, adenosine, guanosine, or any combination thereof. See para. 64.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to use adenosine or theobromine in the composition taught by ‘292 or ‘730, with a reasonable expectation of success, because Ivanov et al teach the equivalence of adenosine or theobromine to xanthine in a similar composition and further, ‘292 or ‘730 teach the use of xanthine.
Claim 21 is rejected under 35 U.S.C. 103 as being unpatentable over Wu et al (US2019/0048292) or Wu et al (US2016/0300730), both in view of Agarwal et al (US2016/0179011) or Lee (US2012/0129345) as applied to claims 1-15 and 18-20 above, and further in view of EP3,537,474.
‘292 or ‘730 are relied upon as set forth above. However, neither reference teaches the use of an amine such as N-ethyldiethanolamine in addition to the other requisite components of the composition of the composition as recited by the instant claims.
‘474 teaches an improved stripper solutions for removing photoresists from substrates are provided that typically have flash points above about 95 °C and high loading capacities. The stripper solutions comprise diethylene glycol butyl ether, quaternary ammonium hydroxide, and an alkanolamine having at least two carbon atoms, etc. See Abstract. Suitable alkanolamines have at least two carbon atoms and have the amino and hydroxyl substituents on different carbon atoms. Suitable alkanolamines include, but are not limited to, ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, dimethylethanolamine, diethylethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, etc. See para. 20.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to use N-ethyldiethanolamine in the composition taught by ‘292 or ‘730, with a reasonable expectation of success, ‘474 teaches the equivalence of N-methyldiethanolamine to N-ethyldiethanolamine as an amine in a similar composition and further, ‘292 or ‘730 teach the use of N-methyldiethanolamine.
Claim 23 is rejected under 35 U.S.C. 103 as being unpatentable over Wu et al (US2019/0048292) or Wu et al (US2016/0300730) as applied to claims 1-15 and 18-20 above, and further in view of Tamboli (US11,560,533).
Tamboli teaches formulations that offer a high cleaning effect on inorganic particles, organic residues, chemical residues, reaction products on the surface due to interaction of the wafer surface with the Chemical Mechanical Planarization (CMP) slurry and elevated levels of undesirable metals on the surface left on the semiconductor devices after the CMP. See Abstract. In one aspect, the cleaning composition comprises: water; at least one organic acid or salts thereof, a fluoride compound, a polymeric additive, and optionally a surfactant, corrosion inhibitors, defoaming agent, biological preservatives, pH adjusting agents. See column 2, lines 1-10. Cleaning formulation may comprise a water-soluble polymeric additive. Polymer may be a homopolymer or copolymer. The polymer may contain positively charged species (cationic polymer), negatively charged groups (anionic polymers), nonionic groups (nonionic polymers) or both cationic and anionic groups (zwitterionic polymers). The polymer may be selected from but not limited to a group comprising acrylic acid-acrylamido propane sulfonic acid copolymer, poly(acrylic acid), poly(meth-acrylic acid), poly(2-acry lamido-2-methy 1-1-propanesulfonic acid, carboxymethylcellulose, methyl cellulose, etc. See column 6, lines 1-30. Addition of the polymers to post CMP formulations with appropriate bases leads to great improvement in cleaning performance. Without binding to any particular mechanism, one of the possible mechanism may be physical adsorption on surfaces, which would prevent re-deposition of removed particles and other residues. Another likely mechanism is the strong affinity towards the residues (organics) thereby increasing the driving force on lift-off during the cleaning process. Polymers or mixtures thereof can be added n concentrations from 0.01 to 10 wt. % to the cleaning formulations. See column 6, line 55 to column 7, line 30.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to use a water-soluble polymer in the composition taught by ‘292 or ‘730, with a reasonable expectation of success, because Tamboli teaches that the use of water-soluble polymers in a similar composition provides improved cleaning and re-deposition prevention properties and further, such properties would be desirable in the composition taught by ‘292 or ‘730.
Response to Arguments
With respect to the rejection of the instant claims under 35 USC 103 using under Wu et al (US 2019/0048292) or Wu et al (US 2016/0300730), Applicant states that claim 1 has been amended to add the recitation that the cleaning liquid includes at least one selected from the group consisting of a cyclic amidine compound and a hydrazine compound and that the cited documents do not disclose or suggest these compounds.
In response, note that, the Examiner asserts that a new ground(s) of rejection has been made, as set forth above, which was necessitated by Applicant’s amendment in which Agarwal et al or Lee have been relied upon as secondary references for their teaching of hydrazine. The Examiner asserts that Agarwal et al or Lee are analogous prior art relative to the claimed invention and ‘292 or ‘730 and that one of ordinary skill in the art clearly would have looked to the teachings of Agarwal et al or Lee to cure the deficiencies of ‘282 or ‘730. Additionally, the Examiner asserts that one of ordinary skill in the art clearly would have been motivated to use hydrazine in the composition taught by ‘292 or ’730, with a reasonable expectation of success, because Agarwal et al or Lee teach the equivalence of hydrazine to monoethanolamine in a similar composition and further, ‘292 or ‘730 teach the use of monoethanolamine. Thus, the Examiner asserts that the teachings of Wu et al (US 2019/0048292) or Wu et al (US 2016/0300730), both in view of Agarwal et al (US2016/0179011) or Lee (US2012/0129345), are sufficient to render the claimed invention obvious under 35 USC 103.
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 GREGORY R DEL COTTO whose telephone number is (571)272-1312. The examiner can normally be reached M-F, 8:30am-6:00pm, EST.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Angela Brown-Pettigrew can be reached at (571) 272-2817. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/GREGORY R DELCOTTO/Primary Examiner, Art Unit 1761
/G.R.D/March 16, 2025