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 .
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Response to Amendment
Applicant’s Amendment filed 03/16/2026 has been entered and is being considered. Claims 1-3 have been amended. Claims 12-16 have been added. No new matter appears to have been added with these claims.
Response to Arguments
Applicant’s amendments to the claims and the arguments based thereon have changed the scope of the claims so as to render the prior art proffered in the previous office action moot. As such, all 35 USC 103 rejections set forth in the prior office action are withdrawn.
However, after further search and consideration, a new grounds of rejection are made as set forth below.
Concerning the arguments made for unexpected superior results, while the results to appear to have demonstrated practical significance, examples used to abet an assertion of superior unexpected results must be commensurate with the scope of the claims. The examples pointed to use TMAH, monoethanolamine, 1-methylimidazole, N,N-diethylformamide, propylene glycol, N,N-diethylhydroxylamine, 1,2,4-triazole, 1,2,3-benzotriazole, and 3-mercapto-1,2,4-triazole. The independent claim, in contrast, recites genera of compounds such as alkanolamine, pyrazoles, imidazoles, and fatty acid amines. The scope of the independent claim is much broader than that of the set of examples pointed to. The most effective composition in the examples appears to be Example 9, which includes TMAH, MEA, 1-MI, PG, DEF, PG, DEHA, and 1,2,4-TAZ.
The examiner points out that many of the specific embodiments in the compositions Applicant has pointed to in order to advance a claim of unexpected results are in the dependent claims, not the independent claim – 1-methyimidazole is in new claim 12, propylene glycol is in claim 6 and in new claim 13, N,N-diethyl formamide is in new claim 15, monoethanolamine is claim 7, and TMAH is in claim 4.
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) 1-5, 7, 12, 14, and 16 are rejected under 35 U.S.C. 103 as being unpatentable over Klipp (US 20120058644 A1) and Eto et al (US 2011/0129998 A1).
Regarding Claim 1-7, 12-14, and 16, Klipp discusses a liquid composition for resist stripping and methods for manufacturing electrical devices.
The composition(s) of Klipp comprise (A) polar organic solvent, present in 40-99% by weight, that is capable of dissolving 0.06 to 4% by weight of dissolved tetramethylammonium hydroxide, among other properties; (B) tetramethylammonium hydroxide (claim 4) or another quaternary ammonium hydroxide in 0.05 to less than 0.5% by weight; (C) water in less than 5%. See [0052]
The solvent (A) is described from [0111]-[0114], such as N-methyl imidazole (1-methylimidazole, claim 12). The solvent (A), or a mixture of solvent including (A), may be present in 40 to 99% by weight of the composition (claim 14)
The quaternary ammonium compound is described from [0103]-[0105], such as tetramethylammonium hydroxide.
An additional polar organic solvent (D) different than the solvent (A) may be included as per ([0118]-[0124]. Additional components further include corrosion inhibitors (E), Fluoride salts (F), and surfactants (G). The additional polar solvent is preferably one having a boiling point greater than 150 degrees Celsius ([0123]. The second solvent may be included, when present, in a broad range of concentrations, though more preferably in a ratio of A:D being 2:1 to 1:2 or 0.5 to 2 ([0126]) (claim 16).
Klipp does not disclose a fatty acid amide solvent. This limitation is met by Eto et al (US 20110129998 A1).
Eto discloses a cleaning liquid for lithography comprising a solvent or mixed solvent, a corrosion inhibitor, and a quaternary ammonium hydroxide compound, wherein the composition is asserted to suppress copper and tungsten corrosion. The solvents of Eto are alkanolamine or another water-soluble organic solvent (polar organic solvent) such as N,N-dimethylformamide ([0027]-[0035]), as well as ethylene glycol and ethanolamine (monoethanolamine). The amount of solvent in the composition is 1-82% by mass, wherein the alkanolamine solvent (such as monoethanolamine) is present in 1-50% mass of the composition when a mixed solvent is used.
The reference ascribes improved corrosion suppression of copper, low dielectric materials, and tungsten to the composition when the solvents mentioned above and in the cited paragraphs are present in an amount ranging from 1-82% by mass of the composition.
Further corrosion inhibition is ascribed to the composition when an imidazole compound (1) and a benzotriazole compound (3) is present.
N,N-dimethylformamide (DMF) has a boiling point of 153 degrees Celsius and is a polar organic solvent. Ethanolamine has a boiling point of 172 degrees Celsius and is a polar organic solvent. Proplyene glycol has a boiling point of 188 degrees Celsius and is a polar organic solvent. All of these solvents meet the Boiling Point parameter of Klipp. The composition of Eto covers embodiments wherein, in a mixed solvent, the balance of 1-82% by mass of the composition may be DMF, ethanolamine, and propylene glycol (claim 5)– for example, DMF in a range of 45%, ethanolamine in 1%, and ethylene glycol in 1%. The art suggests any number of permutations of solvent concentrations so long as the balance is between 1 and 82%. The solvent content of Klipp ranges from 45-99%, where a second solvent (such as a DMF) may be incorporated in a ratio of A:D ranging from 1:2 to 2:1 (0.5 to 2 - claim 16) .
A person having ordinary skill in the art would consider the incorporation of a mixture of DMF, ethanolamine, and ethylene glycol into the composition of Klipp in order to improve the copper corrosion suppressing ability of the composition.
Claim(s) 8- 10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Klipp (US 20120058644 A1) and Eto et al (US 2011/0129998 A1) as applied to claim 1 above, and further in view of Egbe et al (US 20140100151 A1).
Regarding Claim 8, Klipp and Eto disclose the limitations of the claim as discussed above regarding claim 1.
Klipp and Eto do not provide for an alkylhydroxylamine compound as a component of the compositions contemplated therein.
This limitation is met by Egbe.
Egbe discloses stripping and cleaning compositions for the removal of thick film resists, wherein the compositions comprise at least one alkanolamine or morpholine or a mixture thereof, water, and at least one organic solvent (Abstract).
The alkanolamine of Egbe may be monoethanolamine ([0013]), and the composition may also include quaternary ammonium hydroxides such as tetraethylammonium hydroxide and triazoles such as dihydroxypropylbenzotriazole ([0013]-[0049]). Eto also embodies a triazole. Further components included include hydroxylamines ([0022]) such as diethylhydroxylamine ([0050]). Diethylhydroxylamine is a preferred corrosion inhibitor embodiment.
A person of ordinary skill in the art would have found it obvious to arrive at the claimed invention by incorporating the diethylhydroxylamine of Egbe into the composition of Klipp and Eto to improve corrosion inhibition during composition use.
Regarding Claim 10, Klipp and Eto disclose the limitations of the claim as discussed above regarding claim 1.
Klipp and Eto do not disclose a dry film, but Klipp does disclose negative resist processes at [0214]-[0217].
These limitations are met by Egbe.
Egbe discloses stripping and cleaning compositions for the removal of thick film resists, wherein the compositions comprise at least one alkanolamine or morpholine or a mixture thereof, water, and at least one organic solvent (Abstract).
The alkanolamine of Egbe may be monoethanolamine ([0013]), and the composition may also include quaternary ammonium hydroxides such as tetraethylammonium hydroxide and triazoles such as dihydroxypropylbenzotriazole ([0013]-[0049]). Further components included include hydroxylamines ([0022]) such as diethylhydroxylamine ([0050]). Diethylhydroxylamine is a preferred corrosion inhibitor embodiment. These are ingredients common to the disclosures of Zi and Egbe.
The compositions of Egbe are suitable for the removal of negative film photoresists ([0064]), including those that are used on substrates that have metallic components such as copper layer or other layers. When describing a stripping method embodiment in [0065], a dry film resist is stripped using the reference’s composition(s) by contacting or dipping into a bath containing the composition. Both Egbe and Klipp are directed to removing negative photoresists.
A person of ordinary skill in the art would have found it obvious to arrive at the claimed invention by incorporating the composition of Klipp and Eto into the processing considerations of Egbe and using Klipp and Eto’s composition to strip a dry photoresist post-development, recognizing that the similar component additives of Egbe, Klipp, and Eto would impart similar performance in removing a dry negative resist.
Claim(s) 11 is rejected under 35 U.S.C. 103 as being unpatentable over Klipp (US 20120058644 A1) and Eto et al (US 2011/0129998 A1) as applied to claim 1 above, and further in view of Egbe et al (US 20140100151 A1) and Irie et al (US 20180259850 A1)
Regarding Claim 11, Klipp and Eto disclose the limitations of the claim as discussed above regarding claim 1.
Klipp and Eto do not disclose a dry film, but Klipp does disclose negative resist processes.
These limitations are met by Egbe.
Egbe discloses stripping and cleaning compositions for the removal of thick film resists, wherein the compositions comprise at least one alkanolamine or morpholine or a mixture thereof, water, and at least one organic solvent (Abstract).
The alkanolamine of Egbe may be monoethanolamine ([0013]), and the composition may also include quaternary ammonium hydroxides such as tetraethylammonium hydroxide and triazoles such as dihydroxypropylbenzotriazole ([0013]-[0049]). Further components included include hydroxylamines ([0022]) such as diethylhydroxylamine ([0050]). Diethylhydroxylamine is a preferred corrosion inhibitor embodiment. There are ingredients common to the disclosures of Klipp, Eto, and Egbe.
The compositions of Egbe are suitable for the removal of negative film photoresists ([0064]), including those that are used on substrates that have metallic components such as copper layer or other layers. When describing a stripping method embodiment in [0065], a dry film resist is stripped using the reference’s composition(s) by contacting or dipping into a bath containing the composition. Both Egbe and Klipp are directed to removing negative photoresists.
A person of ordinary skill in the art would, in view of the common components of Zi and Egbe and the establishment that both compositions are directed to the removal of negative photoresist, consider that the composition of Klipp and Eto may be used to strip a dry film.
Egbe and Klipp and Eto do not specifically disclose a copper post formation process by electrolytically plating the substrate of a developed photoresist.
This limitation is met by Irie.
Irie discloses a photoresist composition for use in a negative resist process in a thick-film pattern (Abstract).
The resist film composition of Irie is disclosed more specifically from [0026]-[0130], wherein the film composition comprises a photoinitiator, monomers, a base resin having an ethylenically unsaturated group, polymers, and other components such as polymerization inhibitors.
Methods for preparing the composition, such as lamination and dry-film resist formation methods, are described from [00125]-[0130], wherein the resist is coated onto a substrate such as a substrate having a metal surface including a copper wiring pattern is preferable ([0127]). As described from [0135]-[0144], after forming the photosensitive layer on the substrate, the layer is exposed to light, and then developed using conventional negative resist development, including rinse steps. After forming the resist pattern is formed the resist pattern is used as a mold to form a plated shaped article such as connecting terminals including a copper post(s) using copper plating. Conventional plating methods are described as suitable - the reference makes mention of electrolytic plating in the Background section as a conventional plating method. After formation of desired features, the mold (the residual resist of the pattern) is stripped. Irie ascribes satisfactory rectangular shape to the plated article resultant from the patterning and plating process.
A person of ordinary skill in the art would have found it obvious to apply the composition of Klipp and Eto, in view of Egbe, to the dry film and copper plating process of Irie to arrive at a plated article having a copper post thereupon having satisfactory form.
Claim(s) 15 is rejected under 35 U.S.C. 103 as being unpatentable over Klipp (US 20120058644 A1) and Eto et al (US 2011/0129998 A1) as applied to claim 12 above, and further in view of Hara et al (US 2002/0128164 A1).
Regarding Claim 15, Klipp and Eto disclose the limitations of the claim as discussed above regarding claim 12.
Neither Klipp nor Eto disclose an N,N-diethyl formamide solvent. Eto discloses N,N-dimethyl formamide and N, N-diethyl acetamide.
This limitation is met by Hara.
Hara discloses a resist stripper composition, wherein the stripper comprises a peroxide and a quaternary ammonium salt, and an organic solvent such as a sulfoxide solvent, N,N-dimethylformamide, N,N-diethyl acetamide, and N,N-diethyl formamide ([0023]-[0024]). Hara considers these solvents to be alternatives to one another.
A person having ordinary skill in the art would have found it obvious to substitute the N,N-dimethylformamide of Klipp and Eto as described above regarding claim 12 for N,N-diethylformamide, recognizing that the chemical similarities between the two solvents and their status as art-recognized alternatives to one another would abet similar chemical properties and thus similar performance in a resist stripping composition.
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.
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/A.P.T./Examiner, Art Unit 1737
/JONATHAN JOHNSON/Supervisory Patent Examiner, Art Unit 1734