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 1-18, 20, 22, and 23. Claims 19 and 21 have been canceled. Note that, Applicant’s amendment and arguments filed October 30, 2025, have been entered.
Applicant’s election of Group I, claims 1-21, in the reply filed on October 30, 2025, is acknowledged. Because applicant did not distinctly and specifically point out the supposed errors in the restriction requirement, the election has been treated as an election without traverse (MPEP § 818.01(a)).
Claim 22 is withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on October 30, 2025.
Objections/Rejections Withdrawn
The following objections/rejections as set forth in the Office action mailed 7/30/25 have been withdrawn:
The objection to claims 3-5, 11, 14, 17, and 21 due to minor informalities has been withdrawn.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.
Claims 1-6 and 11-18 are rejected under 35 U.S.C. 103 as being unpatentable over WO2017/126554 (See English Language Machine Translation).
With respect to independent, instant claim 1, ‘554 teaches a treatment liquid that has corrosion prevention properties for a metal film disposed on a semiconductor substrate, and is also excellent in removability for an organic film on the substrate, or in removability for dry etching residues or dry ashing residues attached to the substrate. See para. 8. The treatment liquid contains water from 1 to 30 mass % relative to the total mass of the treatment liquid, a hydrophilic organic solvent from 40 to 98 mass %, and a quaternary ammonium salt from 0.1 to 30 mass %. See para. 10. The inclusion of a hydrophilic organic solvent can promote solubilization of added components, unnecessary organic matter and residues, and can further improve the corrosion prevention effect. The hydrophilic organic solvent is preferably an organic solvent that can be uniformly mixed with water in any ratio. The hydrophilic organic solvent is not particularly limited, but examples thereof include water-soluble alcohol-based solvents, water-soluble ketone-based solvents, water-soluble ester-based solvents, water-soluble ether-based solvents (e.g., glycol diether), sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents, any of which can be used to obtain the effects desired in the present application. Suitable aliphatic monohydric alcohols include, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol. Examples of sulfone-based solvents include sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane. An example of the sulfoxide solvent is dimethyl sulfoxide. The hydrophilic organic solvents may be used alone or in appropriate combination of two or more kinds. See paras. 19-34. The treatment liquid of the present invention preferably contains a corrosion inhibitor.
The corrosion inhibitor has a function of preventing over-etching of metal (eg, Co, W) that will become the wiring film. The corrosion inhibitor is not particularly limited, and examples thereof include 1,2,4-triazole (TAZ), 5-aminotetrazole (ATA), 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4 -Triazole, naphthotriazole, 1H-tetrazole-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazoline-5-thione, 2-mercaptobenzimidazole (2-MBI), 4-methyl-2-phenylimidazole, etc. Other corrosion inhibitors include citric acid, oxalic acid, glycine, cysteine, etc., or combinations thereof, wherein these compounds fall within the broad scope of the chelating agent as recited by instant claim 1. The corrosion inhibitor is present in amounts from 0.01 to 5% by weight. See paras. 50-62. The treatment liquid of the present invention preferably contains an amine compound.
The amine compound is not particularly limited, and examples thereof include hydroxylamine, hydroxylamine salts, and alkanolamines. Suitable alkanolamines include monoethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino-1-propanol, isobutanolamine, 2-amino-2-ethoxy-propanol, and 2-amino-2-ethoxy-ethanol, also known as diglycolamine. The alkanolamines may be used alone or in combination of two or more kinds. When an alkanolamine is contained, the content thereof is preferably from 0.1 to 60 mass %, more preferably from 0.5 to 50 mass %, and even more preferably from 0.5 to 20 mass %, relative to the total mass of the treatment liquid. See paras. 65-70. The treatment liquid may further contain a chelating agent. The chelating agent chelates with oxidized metals contained in the residue. Therefore, the addition of a chelating agent improves the recyclability of the treatment liquid. The chelating agent is not particularly limited, but is preferably a polyaminopolycarboxylic acid. Polyaminopolycarboxylic acids are compounds that have multiple amino groups and multiple carboxylic acid groups. Polyaminopolycarboxylic acids include, for example, mono- or polyalkylenepolyaminepolycarboxylic acids, polyaminoalkanepolycarboxylic acids, polyaminoalkanolpolycarboxylic acids, and hydroxyalkyletherpolyaminepolycarboxylic acids. Examples of polyaminopolycarboxylic acids include butylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), etc. See paras. 73-75. The lower limit of the pH of the treatment liquid of the present invention is preferably pH 7.0, more preferably pH 7.5, and particularly preferably pH 8.0. The upper limit is preferably pH 14, and more preferably pH 13.4. See para. 77.
‘554 does not teach, with sufficient specificity, a composition containing an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, a chelating agent, water, and the other requisite components of the composition in the specific amounts as recited by independent, instant claim 1 and the respective dependent claims.
Nonetheless 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 an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, water, 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 ‘554 suggest a composition containing an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, water, 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 1-6, 11-18, and 23 are rejected under 35 U.S.C. 103 as being unpatentable over WO08/039730.
With respect to independent, instant claim 1, ‘730 teaches a semi-aqueous composition comprising about 0.1 to 10% by weight of at least one alkali and/or alkaline earth metal basic salt, about 20 to 80% by weight of at least one organic solvent, about 10 to a 80% by weight of water, optionally at least one quaternary ammonium basic salt in amounts from 0 to 5% by weight, optionally at least one metal corrosion inhibitor in amounts from 0 to 20% by weight, and optionally at least one water-soluble polymer surfactant in amounts from 0 to 5% by weight, wherein said semi-aqueous composition is suitable for removing material selected from the group consisting of photoresist, antireflective coating (ARC), polymer-containing buildup, and combinations thereof, from a microelectronic device wafer having said material thereon. See para. 43 and claim 1. Suitable solvents include methanol, ethanol, isopropanol, dimethylsulfoxide (DMSO), sulfolane, monoethanolamine, diethanolamine, triethanolamine, etc., and combinations thereof. See para. 49. Suitable corrosion inhibitors include, but are not limited to: azoles such as benzotriazole (BTA), 1,2,4-triazole (TAZ), 5-aminotetrazole (ATA), 1-hydroxybenzotriazole, citric acid; ascorbic acid; L-cysteine, etc. See para. 51. The pH of the semi-aqueous compositions may be varied to produce a composition optimized for the intended end use. In general, the pH will be basic, e.g., greater than about 10 and less than about 14, more preferably about 12 to about 14. See para. 48.
‘730 does not teach, with sufficient specificity, a composition containing an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, a chelating agent, water, and the other requisite components of the composition in the specific amounts as recited by independent, instant claim 1 and the respective dependent claims.
Nonetheless 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 an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, water, 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 ‘730 suggest a composition containing an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, water, and the other requisite components of the composition in the specific amounts as recited by independent, instant claim 1 and the respective dependent claims.
Claim 20 is rejected under 35 U.S.C. 103 as being unpatentable over WO2017/126554 or WO08/039730 as applied to the rejected claims above, and further in view of WO2014/197808.
‘554 or ‘730 are relied upon as set forth above. However, ‘554 or ‘730 do not teach the use of a phosphonic acid based chelating agent in addition to the other requisite components of the composition as recited by the instant claims.
‘808 teaches useful for the selective removal of titanium nitride and/or photoresist etch residue materials relative to metal conducting, e.g., cobalt, ruthenium and copper, and insulating materials from a microelectronic device having same thereon. Chelating agents are added to increase the etch rate of the TiN, and the photoresist etch residue cleaning performance and are largely oxidation resistant. See Abstract. Suitable chelating agents include hydroxyethylidene diphosphonic acid (HEDP), oxalic acid, glycine, ethylenediaminetetraacetic acid (EDTA), etc. 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 HEDP in the composition taught by ‘554, with a reasonable expectation of success, because ‘322 teaches the equivalence of EDTA to HEDP as a chelating agent in a similar composition and further, ‘554 teaches the use EDTA.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to use HEDP in the composition taught by ‘730, with a reasonable expectation of success, because ‘322 teaches that chelating agents are added to increase the etch rate of the TiN, and the photoresist etch residue cleaning performance and are largely oxidation resistant further, such enhanced properties would be desirable in the composition taught by ‘730.
Claims 7-10 are rejected under 35 U.S.C. 103 as being unpatentable over WO2017/126554 or WO08/039730 as applied to the rejected claims above, and further in view of Hsu (US 2005/0176602).
‘554 or ‘730 are relied upon as set forth above. However, ‘554 or ‘730 do not teach the use of sulfolene in addition to the other requisite components of the composition as recited by the instant claims.
Hsu teach cleaning compositions suitable for cleaning microelectronic structures having silicon dioxide, low-k or high-k di-electrics and copper or aluminum metallizations contain a polar organic solvent selected from amides, sulfones, sulfolenes, selenones saturated alcohols, etc., and a strong alkaline base. See Abstract. Among the preferred solvents there may be mentioned sulfolane (tetrahydrothiopene-1,1-dioxide- ), 3-methylsulfolane, n-propyl sulfone, n-butyl sulfone, sulfolene (2,5dihydrothiopene-1,1-dioxide), 3methylsulfolene, amides such as 1-(2-hydroxyethyl) -2-pyrrolidinone (HEP), dimethylpiperidone (DMPD), N-methyl pyrrolidinone (NMP), etc. The organic solvent component can include one or more of the solvents and is generally present in the composition in an amount of from about 1 to about 99.9 wt %, preferably in an amount of from about 10 to about 90 wt %, and most preferably in an amount of from about 30 to 80 wt %. See para. 12.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to use sulfolene in the composition taught by ‘554 or ‘730, with a reasonable expectation of success, because Hsu teaches the equivalence of sulfolene to sulfolane as an organic solvent in a similar composition and further, ‘554 or ‘730 teaches the use of sulfolane.
Response to Arguments
With respect to the rejection of the instant claims under 35 USC 103 using WO2017/126554, Applicant states that ‘554 does not teach or suggest the specific chelating agent as now recited by instant claim 1.
In response, note that, the Examiner asserts that ‘554 clearly teaches the use of oxalic acid, glycine, cysteine, etc., as corrosion inhibitors, and such compounds would clearly fall within the scope of the chelating agent as recited by instant claim 1 (See paras. 50-62 of ‘554 and paras. 53-57 of the instant specification). Thus, the Examiner asserts that the teachings of ‘554 are sufficient to render the claimed invention obvious under 35 USC 103.
With respect to the rejection of instant claims 7-10 under 35 USC 103 using WO2017/126554, further in view of Hsu (US 2005/0176602), Applicant states that the teachings of ‘554 are not sufficient to suggest the claimed invention and that the teachings of Hsu are not sufficient to remedy the deficiencies of ‘554. In response, note that, the Examiner asserts that the teachings of ‘554 are sufficient to suggest the claimed invention for the reasons set forth above. Additionally, the Examiner asserts that Hsu is analogous prior art relative to the claimed invention and ‘554 and that one of ordinary skill in the art clearly would have looked to the teachings of Hsu to cure the deficiencies of ‘554 with respect to instant claims 7-10. Hsu is a secondary reference relied upon for its teaching of sulfolene. The Examiner asserts that one of ordinary skill in the art clearly would have been motivated to use sulfolene in the composition taught by ‘554, with a reasonable expectation of success, because Hsu teaches the equivalence of sulfolene to sulfolane as an organic solvent in a similar composition and further, ‘554 teaches the use of sulfolane. Thus, the Examiner asserts that the teachings of ‘554, further in view of Hsu, 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.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
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/January 26, 2025