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 .
Claims 1-3 and 5-13 are pending
Applicant amendment filed on 06/29/2026 has been entered. In the amendment claim 1 was amended and claim 4 was canceled.
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.
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.
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
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 1-2, 5 and 8-10 are rejected under 35 U.S.C. § 103 as being unpatentable over Das et al. (US 2020/0255770 A1) in view of Mitani et al. (US 6,568,995 B1).
Regarding claim 1, Das teaches a cleaning liquid for removing a cerium compound, the cleaning liquid comprising:
a component (A), which is a six-membered ring compound having two or more hydroxy groups, wherein the component (A) is at least one selected from the group consisting of pyrogallol, hydroxyhydroquinone, catechol, resorcinol, hydroquinone, and derivatives thereof (Das teaches a composition for removing ceria particles and chemical mechanical polishing contaminants from microelectronic devices, wherein the composition comprises a cerium-oxygen bond-breaking compound; the cerium-oxygen bond-breaking compound may be a reducing agent, and the expressly identified reducing agents include hydroquinone and catechol, each of which is a six-membered aromatic ring compound having two hydroxy groups; paragraphs [0001], [0009]-[0017], and [0021]);
a component (B), which is an inorganic acid compound, wherein the inorganic acid compound contains at least one selected from the group consisting of sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, nitric acid, and hydrochloric acid (Das teaches that the composition comprises a pH adjustor and expressly identifies nitric acid and sulfuric acid as suitable pH adjustors; paragraphs [0011]-[0016] and [0023]); and
a component (C), which is water (Das teaches that the ceria-removal composition comprises water; paragraph [0016]).
Das further teaches that the cleaning liquid is for removing a cerium compound (Das teaches removing ceria particles and chemical mechanical polishing contaminants from microelectronic devices; defines ceria particles as cerium-based abrasive particles, including Ce₂O₃ and CeO₂, used in chemical mechanical polishing slurries; and teaches contacting a microelectronic device with the aqueous removal composition to remove the ceria particles; paragraphs [0001], [0009]-[0010], [0029]-[0031], and [0053]-[0062]).
Das does not expressly teach wherein a mass ratio of the component (B) to the component (A) is 0.05 to 0.6.
Mitani teaches washing a substrate polished using a cerium-oxide-containing abrasive with a washing solution containing an acid and a reducing agent (Mitani teaches that an abrasive containing cerium oxide as a main component is used for polishing and that, subsequent to polishing, the substrate is washed with a washing solution containing an acid and a reducing agent; column 3, lines 24-39).
Mitani further teaches that the acid may be nitric acid, sulfuric acid, hydrochloric acid, or phosphoric acid and that the acid concentration is preferably 0.001 to 10 mol/L, more preferably 0.001 to 0.5 mol/L (Mitani teaches that the preferred acids include nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid and relates the acid concentration to washing effectiveness and excessive substrate etching; column 3, lines 35-50).
Mitani further teaches that the reducing agent may be a chelating agent of the catechol genus possessing reducing properties and that the concentration of a reducing agent other than hydrogen peroxide is preferably 0.0001 to 0.1 mol/L (Mitani teaches catechol-genus chelating reducing agents and relates the reducing-agent concentration to dissolving ability, reducing-agent precipitation, and washing-solution service life; column 4, lines 1-14 and 19-32).
Mitani teaches acid and reducing-agent concentration ranges that encompass concentrations capable of producing a component (B)-to-component (A) mass ratio within the claimed range of 0.05 to 0.6. For example, a composition containing 0.05 mol/L nitric acid and 0.10 mol/L catechol, both within Mitani’s disclosed concentration ranges, has a nitric-acid-to-catechol mass ratio of approximately 0.286:
0.05
M
×
63.01
g
/
m
o
l
0.10
M
×
110.11
g
/
m
o
l
=
0.286
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to select the relative amounts of the inorganic acid compound and the catechol or hydroquinone reducing agent in the ceria-removal composition of Das within the concentration ranges taught by Mitani so that the mass ratio of the inorganic acid compound to the reducing agent is 0.05 to 0.6.
One of ordinary skill in the art would have been motivated to make this selection because Mitani teaches that the acid and reducing agent act together to promote dissolution of cerium-containing lanthanoid oxides and expressly teaches that their concentrations affect washing effectiveness, lanthanoid-oxide dissolution, substrate etching, reducing-agent solubility, and washing-solution service life. Thus, the relative amounts of the acid and reducing agent were result-effective variables, and selecting amounts within the disclosed ranges to obtain effective cerium-compound removal while avoiding excessive substrate attack or reducing-agent precipitation would have involved no more than routine optimization of a known ceria-removal composition.
See MPEP § 2144.05(I) and (II)(B).
Regarding claim 2, modified Das teaches the limitations of claim 1 above. Das further teaches wherein the component (A) contains at least one selected from the group consisting of catechol, resorcinol, hydroquinone, pyrogallol, and methylcatechol (Das expressly identifies catechol and hydroquinone as reducing agents that may be used as the cerium-oxygen bond-breaking compound; paragraph [0021]).
Regarding claim 5, modified Das teaches the limitations of claim 1 above. Das further teaches wherein the component (B) contains sulfuric acid (Das expressly identifies sulfuric acid as a suitable pH adjustor in the ceria-removal composition; paragraph [0023]).
Regarding claim 8, modified Das teaches the limitations of claim 1 above. Das further teaches wherein the cleaning liquid has a pH of 1 to 4 (Das teaches a ceria-removal composition having a pH of about 1 to about 6, which encompasses the claimed pH range of 1 to 4; paragraphs [0010]-[0016]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to select Applicant’s claimed pH range of 1 to 4 because Das teaches a ceria-removal composition having an overlapping pH range of about 1 to about 6, and in the case where the claimed range overlaps or lies inside a range disclosed by the prior art, a prima facie case of obviousness exists. See MPEP § 2144.05(I).
Regarding claim 9, modified Das teaches the limitations of claim 1 above. Das further teaches which is used for cleaning after chemical mechanical polishing (Das teaches using the ceria-removal composition to clean post-chemical-mechanical-polishing residue and contaminants from a microelectronic device; paragraphs [0001], [0004]-[0009], and [0053]-[0055]).
Regarding claim 10, modified Das teaches the limitations of claim 1 above. Das further teaches which is used for removing the cerium compound on a silicon oxide film and/or a silicon nitride film (Das teaches removing ceria particles from microelectronic devices having silicon oxide and silicon nitride surfaces, including devices having silicon oxide and silicon nitride substrates; paragraphs [0006]-[0009]).
Further, the recitations that the cleaning liquid is used for cleaning after chemical mechanical polishing and is used for removing the cerium compound on a silicon oxide film and/or a silicon nitride film merely state intended uses of the claimed cleaning liquid and do not further distinguish its composition from the cleaning liquid taught by Das as modified by Mitani. See MPEP § 2111.02.
Claim 3 is rejected under 35 U.S.C. § 103 as being unpatentable over Das et al. in view of Mitani et al., as applied to claim 1 above, and further in view of Taniguchi et al. (US 2020/0017801 A1).
Regarding claim 3, modified Das teaches the limitations of claim 1 as set forth above.
Modified Das does not expressly teach wherein the component (A) contains pyrogallol.
Taniguchi teaches wherein the component (A) contains pyrogallol (Taniguchi teaches a cleaning solution composition for removing residual cerium compounds from a semiconductor or glass substrate after chemical mechanical polishing using a cerium-compound-containing slurry and expressly identifies pyrogallol as a particularly preferred five- or six-membered cyclic reducing agent having two or more hydroxy groups; paragraphs [0019] and [0049]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the cleaning liquid of modified Das to use pyrogallol as the component (A) because Taniguchi teaches pyrogallol as a preferred reducing agent having the claimed cyclic structure and hydroxy groups for use in a cleaning composition that removes residual cerium compounds after chemical mechanical polishing. The substitution of pyrogallol for another known hydroxy-containing reducing agent, such as catechol or hydroquinone, for the same cerium-removal purpose would have been a simple substitution of one known element for another to obtain predictable results. See MPEP § 2143(I)(B).
Claims 6 and 7 are rejected under 35 U.S.C. § 103 as being unpatentable over Das et al. in view of Mitani et al. as applied to claim 1 above, further in view of An et al. (US 2022/0298456 A1).
Regarding claims 6 and 7, Das as modified by Mitani teaches the limitations of claim 1 as set forth above.
Das as modified by Mitani does not expressly teach further comprising a component (C), component (C): a water-soluble organic polymer, wherein the component (C) contains at least one selected from a polycarboxylic acid and a salt thereof.
An teaches further comprising a component (C), component (C): a water-soluble organic polymer (An teaches that a cleaning liquid for removing a cerium compound preferably further contains a water-soluble organic polymer because the water-soluble organic polymer disperses the cerium compound and improves removability of the cerium compound; paragraphs [0072]-[0073]).
An further teaches wherein the component (C) contains at least one selected from a polycarboxylic acid and a salt thereof (An teaches that the water-soluble organic polymer may include a polycarboxylic acid or a salt thereof, including polyacrylic acid, polymethacrylic acid, and salts thereof, and teaches that a polycarboxylic acid or a salt thereof is preferred because it readily dissolves in an acidic aqueous solution; paragraphs [0074]-[0076]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to further include the water-soluble organic polymer of An, including a polycarboxylic acid or a salt thereof, in the cleaning liquid of Das as modified by Mitani because An teaches that the water-soluble organic polymer disperses cerium compounds, improves cerium-compound removability, and is compatible with an acidic aqueous solution. The modification would have involved combining known components according to their established functions to predictably improve dispersion and removal of the cerium compound. See MPEP § 2143(I)(A).
Claim 11 is rejected under 35 U.S.C. § 103 as being unpatentable over Das et al. in view of Mitani et al.
Regarding claim 11, modified Das teaches the limitations of claim 1 above. Das further teaches a cleaning method comprising removing a cerium compound using the cleaning liquid according to claim 1 (Das teaches a method in which an aqueous ceria-removal composition is contacted with a microelectronic device having ceria particles thereon to remove the ceria particles and chemical mechanical polishing contaminants from the device; paragraphs [0009], [0010], and [0053]-[0056]).
Claims 12-13 are rejected under 35 U.S.C. § 103 as being unpatentable over Das et al. in view of Mitani et al.
Regarding claim 12 modified Das teaches the limitations of claim 1 above. Das further teaches a method for producing a semiconductor wafer, the method comprising: removing a cerium compound using the cleaning liquid according to claim 1 (Das teaches that microelectronic device wafers are used to form integrated circuits, describes cleaning the wafer during semiconductor-device fabrication, and teaches improved microelectronic devices made according to the disclosed ceria-removal methods; paragraphs [0002]-[0005] and [0053]-[0057]).
Regarding claim 13, modified Das teaches the limitations of claim 12 as set forth above. Modified Das further teaches further comprising: performing chemical mechanical polishing using an abrasive containing a cerium compound (Das teaches chemical mechanical polishing of a microelectronic device wafer using an abrasive slurry and teaches that ceria particles are cerium-based abrasive particles used in chemical mechanical polishing slurries, including Ce₂O₃ and CeO₂; paragraphs [0004], [0006], and [0029]-[0031]).
Response to Arguments
Applicant’s arguments filed 06/29/2026 have been considered but are not
persuasive of allowance.
Applicant argues that Taniguchi does not teach or suggest the presently claimed inorganic acid compound because Taniguchi principally employs a fluorinated acid, while the sulfuric acid and hydrochloric acid compositions identified by the Examiner are comparative examples. Applicant further argues that Moriya is directed to etching ceramic materials rather than removing cerium compounds after chemical mechanical polishing and, therefore, does not provide a sufficient reason to modify Taniguchi to obtain the claimed cleaning liquid. Applicant also argues that An does not cure the deficiencies asserted with respect to the rejection of independent claim 1.
Applicant’s arguments are persuasive with respect to the rejection previously presented. In view of Applicant’s amendment to claim 1 and the arguments concerning the teachings of Taniguchi and Moriya, the previous rejection of claims 1–6 and 8–13 under 35 U.S.C. § 103 over Taniguchi in view of Moriya, and the previous rejection of claims 6 and 7 under 35 U.S.C. § 103 over Taniguchi in view of Moriya and further in view of An, are withdrawn.
However, the claims remain unpatentable for the reasons set forth in the new grounds of rejection above.
In particular, the present rejection does not rely on the comparative acid compositions of Taniguchi or on the ceramic-material etching composition of Moriya to establish claim 1. Instead, Das expressly teaches a composition for removing ceria particles and chemical mechanical polishing contaminants from microelectronic devices, wherein hydroquinone or catechol may be used as a cerium-oxygen bond-breaking reducing agent and nitric acid or sulfuric acid may be used as a pH adjustor. Mitani further teaches washing a substrate polished with a cerium-oxide-containing abrasive using a solution containing an acid and a reducing agent, including the claimed acids and a catechol-genus reducing agent, and teaches concentration ranges encompassing concentrations capable of producing the claimed component (B)-to-component (A) mass ratio. Thus, the presently applied Das and Mitani combination addresses the amended composition and mass-ratio limitations on a different evidentiary basis from the withdrawn Taniguchi and Moriya rejection.
With respect to claims 6 and 7, An is applied only after the limitations of claim 1 have been established by modified Das. An expressly teaches adding a water-soluble organic polymer to a cleaning liquid for removing a cerium compound because the polymer disperses the cerium compound and improves removability, and further teaches that the polymer may be a polycarboxylic acid or a salt thereof that is readily soluble in an acidic aqueous solution. Accordingly, Applicant’s arguments concerning deficiencies in the former Taniguchi and Moriya combination do not overcome the present rejection of claims 6 and 7.
Conclusion
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/JONATHAN L CARTER/Examiner, Art Unit 1713 /ERIN F BERGNER/Primary Examiner, Art Unit 1713
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