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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 5 May 2026 has been entered.
Response to Arguments
Applicant’s addition of claims 32-33 is acknowledged.
Applicant’s arguments filed 5 May 2026 have been fully considered but they are not persuasive.
Applicant has amended independent claim 28 to recite that the content of the metal component is between 0.001 to 5 mass ppt (with respect to the total mass of the chemical liquid), the content of the acid component is between 1 mass ppt to 0.9909 mass ppm (with respect to the total mass of the chemical liquid), and the organic solvent is propylene glycol monomethyl ether acetate (PGMEA). Independent claim 30 recites similar features, but the content of the acid component is 0.251 mass ppm to 0.9909 mass ppm instead. Independent claim 31 recites the exact same limitations as claim 30. Claim 29 has been amended to recite that the content of the metal component is between 0.001 to 10 mass ppt (with respect to the total mass of the chemical liquid), the content of the acid component is between 1 mass ppt to 0.9909 mass ppm (with respect to the total mass of the chemical liquid), and the organic solvent is butyl acetate. Claim 29 further recites that the acid component includes an inorganic acid and the inorganic acid content is up to 1 mass ppb. Claims 32 and 33, which have been added in the most recent amendment, recite a chemical liquid comprising isoamyl acetate as the organic solvent, a metal component having a content of 0.001 to 100 mass ppt (with respect to the total mass of the chemical liquid), and an acid component. The difference between claims 32 and 33 is the content of the acid component, wherein claim 32 includes the acid component in an amount of 1 mass ppt to 0.9909 mass ppm (with respect to the total mass of the chemical liquid) and claim 33 includes the acid component in an amount of 0.251 mass ppm to 0.9909 mass ppm (with respect to the total mass of the chemical liquid).
Applicant argues that claims 28, 30, and 31 are allowable over the previously cited prior art because Examples A2, A3, and A14-A16 of the instant application’s specification, which fall within the scope of the claims, demonstrate unexpectedly superior results compared to the other examples utilizing PGMEA as the solvent. The Examiner notes that each of the named examples contain PGMEA and a mixture of acetic acid, propionic acid, butanoic acid, maleic acid, fumaric acid, and SO3- ions as the acid component. The named examples further include metal ions and metal particles. The difference between each example is the contents of the various species. The named examples contain a total acid content of 0.1005 mass ppm (Example A3) to 0.124 mass ppm (Example A2), or a value in between. The metal content of the examples ranges from 1.02 mass ppt (Example A14) to 4.03 mass ppt (Example A15), or is a value in between. The Examiner does not believe that the examples provided by the Applicant sufficiently support allegations of unexpected results, per the requirements of MPEP 716.02, particularly MPEP 716.02(d). Firstly, the examples provided do not include the acid component in an amount within the range recited by instant claims 30 and 31. The results shown for Examples A2, A3, and A14-A16 therefore cannot support allegations of unexpected results in regards to claims 30 and 31, as the acid content recited by the claims is not satisfied. Secondly, the examples provided only include the acidic species recited above (acetic, propionic, butanoic, maleic, and fumaric acids, as well as ions derived from sulfuric acid). The Examples therefore do not provide evidence that the alleged unexpected results are observed when different acidic components are utilized. For instance, claims 28 and 30-31 recite species such as lactic acid, adipic acid, benzoic acid, salicylic acid, etc. The results provided by the Applicant only provide support for the specific acidic species included in the examples (and particularly, supports the particular combination of acidic species rather than each species independently). Additionally, the demonstrated acid content of the aforementioned examples fails to establish a criticality of the range recited by instant claim 28, as the acid content of the aforementioned examples fails to demonstrate advantageous effects across the entire range of the claimed range. Rather, the aforementioned examples demonstrate advantageous results in a narrow range that falls within the much broader range recited by claim 28. Therefore, the Applicant’s inventive examples do not reasonably establish that the claimed invention achieves unexpected results compared to the prior art. Furthermore, the courts have established that a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. When the claimed range and the prior art are mathematically close, the difference between the claimed range and the prior art has been held to be virtually negligible absent of evidence that the claimed range shows unexpected results or criticality. Refer to MPEP 2144.05 I. In this case, the prior art teaches an acid content of 1 mass ppm, which is 0.0091 mass ppm away from the claimed upper limit of acid content for claims 28 and 30-31. As stated above, the Applicant has not sufficiently demonstrated unexpected results or criticality of the claimed range. Therefore, the Applicant’s arguments in regards to claims 28 and 30-31 are not found persuasive and accordingly the previous rejection is not withdrawn at this time.
Applicant makes similar arguments in regards to claim 29, citing Examples B1, B2, and B5. These examples are analogous to those discussed above, with the primary difference being the use of n-butyl acetate as the solvent instead of PGMEA. The Examiner notes that the acid content of Examples B1 and B2 are 1.88 mass ppm and 1.27 mass ppm, respectively. Thus, Examples B1 and B2 have acid contents that are outside the range recited by claim 29. Similarly, Examples B1 and B2 have metal contents of 10.1 mass ppt, which is also outside the metal content range recited by claim 29. Therefore, these examples cannot support allegations of unexpected results because Examples B1 and B2 fails to satisfy the limitations of instant claim 29. Furthermore, Examples B1 and B2 demonstrate better defect inhibition performance after the passage of time (per Table 2-2 of the instant application’s specification) than Example B5. Thus, Examples B1 and B2, which are outside the scope of claim 29, demonstrate equal or better results than Example B5, which is inside the scope of claim 29. Furthermore, each of the Examples B1, B2, and B5 include inorganic acid via sulfuric acid ions and/or hydrochloric acid ions. The amounts of the inorganic acid in each of these examples is greater than 1 mass ppb, which is the upper limit of inorganic acid content recited by instant claim 29. Therefore, these examples fail to demonstrate criticality of the claimed range or unexpectedly superior results. Additionally, the issues discussed above regarding the results being commensurate in scope with the claimed invention are present in these examples as well. Therefore, Applicant’s arguments in regards to claim 29 are not found to be persuasive.
Regarding the newly added claims 32 and 33, Applicant makes similar arguments, citing Example C1 as evidence. The total acid content of Example C1 is 2.15 mass ppm, which is above the upper limit of the claimed acid content recited by claims 32 and 33. Thus, Example C1 fails to support allegations of unexpected results and does not demonstrate criticality of the claimed ranges. Furthermore, there is no comparable examples disclosed by the Applicant, as this is the only example utilizing isoamyl acetate as the solvent. Therefore, the unexpected results allegations regarding claims 32 and 33 is not found to be persuasive.
Claim Objections
Applicant is advised that should claim 30 be found allowable, claim 31 will be objected to under 37 CFR 1.75 as being a substantial duplicate thereof. When two claims in an application are duplicates or else are so close in content that they both cover the same thing, despite a slight difference in wording, it is proper after allowing one claim to object to the other as being a substantial duplicate of the allowed claim. See MPEP § 608.01(m).
In particular, claim 30 is directed towards a chemical liquid comprising an acid component in an amount of 0.251 mass ppm to 0.9909 mass ppm, a metal component in an amount of 0.001 to 5 mass ppt, propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent, and an acid component selected from a list of species. Claim 31 is directed towards a chemical liquid comprising an acid component in an amount of 0.251 mass ppm to 0.9909 mass ppm, a metal component in an amount of 0.001 to 5 mass ppt, propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent, and an acid component selected from a list of species. The list of acidic species recited by instant claims 30 and 31 are identical. As far as the Examiner can tell, claims 30 and 31 are indistinguishable in scope and therefore are functionally duplicates.
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.
Claim(s) 28 and 30-33 are rejected under 35 U.S.C. 103 as being obvious over US 20130330927 A1 (hereby referred to as Kumagai) in view of US 20100129758 A1 (hereby referred to as Maemori) and WO 2017188296 A1 (hereby referred to as WO ‘296), citing the corresponding US Application US 20190064672 A1 (hereby referred to as Murayama).
Regarding Claims 28 and 30-33, Kumagai discloses a cleaning liquid for lithography. The cleaning liquid contains an alkali or an acid, a solvent, and a silicon compound (Kumagai, paragraph 0018). As the acid, any acid that can remove residue materials remaining after etching can be used, such as hydrofluoric acid (Kumagai, paragraph 0027). The acid may be a single acid or a combination of two or more acids (Kumagai, paragraph 0027). The amount of the acid is preferably 1 ppm by mass to 10% by mass, based on the total amount of the cleaning liquid (Kumagai, paragraph 0028). Including the acid component in such an amount allows for an effective removal of residue materials that remain after etching, whilst also inhibiting corrosion of low-k materials (Kumagai, paragraph 0028). As the range of the acid component content in Kumagai’s cleaning liquid is close with the range of the acid component content recited by the instant claims, a prima facie case of obviousness exists for the acid component content, per MPEP 2144.05 I. As a solvent, organic solvents and water may be used (Kumagai, paragraph 0029). The solvent may be a single solvent or a combination of solvents (Kumagai, paragraph 0029). Examples of suitable organic solvents include polyols such as ethylene glycol, propylene glycol, and diethylene glycol and glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol, monoethyl ether, and propylene glycol monopropyl ether (Kumagai, paragraph 0030).
However, Kumagai is silent in regards to the acid species recited by instant claims 28 and 30-31. Maemori teaches a resist surface modifying liquid, which is used as a surface treatment liquid of a resist film prior to a post exposure baking step (Maemori, Abstract). The resist surface modifying liquid (hereby referred to as “RSML”) contains an acidic component and at least one of an alcohol-based solvent and an ether-based solvent (Maemori, paragraph 0022). The acidic component may be an inorganic acid or an organic acid (Maemori, paragraph 0023). The inorganic acid may include conventionally well-known inorganic acids (Maemori, paragraph 0224), and the organic acid may be chosen from the group of formic acid, propionic acid, pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, oxalic acid, maleic acid, malic acid, citric acid, salicylic acid, benzoic acid, or phthalic acid, amongst others not recited by the instant application’s claims (Maemori, paragraph 0025).
However, Kumagai and Maemori are silent in regards to the inclusion of a metal component in the RSML or the use of PGMEA as a solvent. Murayama teaches a treatment liquid and a housing body for said treatment liquid. The treatment liquid includes at least one organic solvent selected from the group consisting of ethers, ketones, and lactones; water; and a metal component including at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn (Murayama, paragraph 0057). The content of the metal component in the treatment liquid is 10 ppq (equivalent to 0.01 ppt) to 10 ppb (equivalent to 10,000 ppt) by mass (Murayama, paragraph 0057). Thus, a prima facie case of obviousness exists for the metal component content recited by instant claims 28 and 30-31, per MPEP 2144.05 I. As the organic solvent, ethers, ketones, and lactones may be used (Murayama, paragraph 0069). Murayama, Kumagai, and Maemori therefore utilize similar solvent systems, as each references utilize ether solvents either alone or in combination with other solvents (see Murayama, paragraph 0069-0070, Kumagai, paragraph 0030, and Maemori, paragraph 0033 and 0046). In particular, Murayama teaches that propylene glycol monomethyl ether (PGME), which is a solvent taught by Kumagai for the cleaning liquid (Kumagai, paragraph 0031), is a functional equivalent to propylene glycol monomethyl ether acetate (PGMEA) or isoamyl acetate (iAA) (Murayama, paragraph 0071-0072 and 0229).
Kumagai, Maemori, and Murayama are analogous art because each reference pertains to treatment liquids for semiconductor manufacturing and/or lithographic applications. It would have been obvious to one having ordinary skill in the art before the filing date of the instant application to use an organic acid, such as formic acid, propionic acid, pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, oxalic acid, maleic acid, malic acid, citric acid, salicylic acid, benzoic acid, or phthalic acid, as taught by Maemori, in place of the hydrofluoric acid in the cleaning liquid disclosed by Kumagai because well-known inorganic acids (such as hydrofluoric acid) are stated to be functionally equivalent to the organic acids taught by Maemori (see Maemori, paragraph 0023-0025) for the purposes of treatment liquids. Refer to MPEP 2143 I. B. It would have been obvious to one having ordinary skill in the art before the filing date of the instant application to include a metal component in an amount of 0.001 to 100 mass ppt with respect to the total mass of the chemical liquid, as taught by Murayama, in the cleaning liquid obtained by combining the teachings of Kumagai and Maemori because the inclusion of a metal component in such amounts in a treatment liquid allows for the suppression of defects in a semiconductor device (Murayama, paragraph 0060-0062). Lastly, it would have been obvious to one having ordinary skill in the art before the filing date of the instant application to use propylene glycol monomethyl ether acetate (PGMEA) or isoamyl acetate (iAA) as the solvent, as taught by Murayama, in the cleaning liquid obtained by combining the teachings of Kumagai, Maemori, and Murayama because Murayama teaches that PGMEA and iAA are both functional equivalents to one or more of the solvents utilized by Kumagai (Murayama, paragraph 0071-0072 and 0229). Refer to MPEP 2144.06 II.
Claim(s) 29 is rejected under 35 U.S.C. 103 as being obvious over US 20130330927 A1 (hereby referred to as Kumagai) in view of US 20100129758 A1 (hereby referred to as Maemori), WO 2017188296 A1 (hereby referred to as WO ‘296), citing the corresponding US Application US 20190064672 A1 (hereby referred to as Murayama), and US 20110287234 A1 (Tsuchihashi).
Regarding Claim 29, Kumagai discloses a cleaning liquid for lithography. The cleaning liquid contains an alkali or an acid, a solvent, and a silicon compound (Kumagai, paragraph 0018). As the acid, any acid that can remove residue materials remaining after etching can be used, such as hydrofluoric acid (Kumagai, paragraph 0027). The acid may be a single acid or a combination of two or more acids (Kumagai, paragraph 0027). The amount of the acid is preferably 1 ppm by mass to 10% by mass, based on the total amount of the cleaning liquid (Kumagai, paragraph 0028). Including the acid component in such an amount allows for an effective removal of residue materials that remain after etching, whilst also inhibiting corrosion of low-k materials (Kumagai, paragraph 0028). As the range of the acid component content in Kumagai’s cleaning liquid overlaps with the range of the acid component content recited by the instant claims, a prima facie case of obviousness exists for the acid component content, per MPEP 2144.05 I. As a solvent, organic solvents and water may be used (Kumagai, paragraph 0029). The solvent may be a single solvent or a combination of solvents (Kumagai, paragraph 0029). Examples of suitable organic solvents include polyols such as ethylene glycol, propylene glycol, and diethylene glycol and glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol, monoethyl ether, and propylene glycol monopropyl ether (Kumagai, paragraph 0030).
However, Kumagai is silent in regards to the acid species recited by instant claim 29. Maemori teaches a resist surface modifying liquid, which is used as a surface treatment liquid of a resist film prior to a post exposure baking step (Maemori, Abstract). The resist surface modifying liquid (hereby referred to as “RSML”) contains an acidic component and at least one of an alcohol-based solvent and an ether-based solvent (Maemori, paragraph 0022). The acidic component may be an inorganic acid or an organic acid (Maemori, paragraph 0023). The inorganic acid may include conventionally well-known inorganic acids (Maemori, paragraph 0224), and the organic acid may be chosen from the group of formic acid, propionic acid, pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, oxalic acid, maleic acid, malic acid, citric acid, salicylic acid, benzoic acid, or phthalic acid, amongst others not recited by the instant application’s claims (Maemori, paragraph 0025).
However, Kumagai and Maemori are silent in regards to the inclusion of a metal component in the RSML, as well as the inorganic acid content. Murayama teaches a treatment liquid and a housing body for said treatment liquid. The treatment liquid includes at least one organic solvent selected from the group consisting of ethers, ketones, and lactones; water; and a metal component including at least one metal element selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn (Murayama, paragraph 0057). The content of the metal component in the treatment liquid is 10 ppq (equivalent to 0.01 ppt) to 10 ppb (equivalent to 10,000 ppt) by mass (Murayama, paragraph 0057). Thus, a prima facie case of obviousness exists for the metal component content recited by instant claims 28 and 30-31, per MPEP 2144.05 I. As the organic solvent, ethers, ketones, and lactones may be used (Murayama, paragraph 0069). Murayama, Kumagai, and Maemori therefore utilize similar solvent systems, as each references utilize ether solvents either alone or in combination with other solvents (see Murayama, paragraph 0069-0070, Kumagai, paragraph 0030, and Maemori, paragraph 0033 and 0046). Murayama further teaches that when an acid component is present in the treatment liquid, the acid component content is preferably 0.1 ppb by mass to 1 ppb by mass (Murayama, paragraph 0114). The acid component may be organic or inorganic (Murayama, paragraph 0113). Thus, Murayama suggests an inorganic acid component included in the treatment liquid having a content less than 1 mass ppb.
However, Kumagai, Maemori, and Murayama are silent in regards to the use of butyl acetate as the organic solvent in the treatment liquid. Tsuchihashi teaches a developer composition for resist compositions. Tsuchihashi teaches that the developer contains an organic solvent (Tsuchihashi, paragraph 0064). The organic solvent is at least one kind of solvent selected from ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents (Tsuchihashi, paragraph 0066). As the alcohol-based solvent, solvents such as 1-hexanol and 1-octanol are preferred (Tsuchihasi, paragraph 0070). These are solvents utilized by Maemori, as discussed above. Propylene glycol monomethyl ether (PGME), which is utilized by Kumagai and Murayama (Kumagai, paragraph 0030 and Murayama, paragraph 0071-0072) may also be used (Tsuchihasi, paragraph 0070). Alternatively, butyl acetate may be chosen as the organic solvent (Tsuchihasi, paragraph 0068).
Kumagai, Maemori, Murayama, and Tsuchihasi are analogous art because each reference pertains to treatment liquids for semiconductor manufacturing and/or lithographic applications. It would have been obvious to one having ordinary skill in the art before the filing date of the instant application to use an organic acid, such as formic acid, propionic acid, pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, oxalic acid, maleic acid, malic acid, citric acid, salicylic acid, benzoic acid, or phthalic acid, as taught by Maemori, in place of the hydrofluoric acid in the cleaning liquid disclosed by Kumagai because well-known inorganic acids (such as hydrofluoric acid) are stated to be functionally equivalent to the organic acids taught by Maemori (see Maemori, paragraph 0023-0025) for the purposes of treatment liquids. Refer to MPEP 2143 I. B. It would have been obvious to one having ordinary skill in the art before the filing date of the instant application to include a metal component in an amount of 0.001 to 100 mass ppt with respect to the total mass of the chemical liquid, as taught by Murayama, in the cleaning liquid obtained by combining the teachings of Kumagai and Maemori because the inclusion of a metal component in such amounts in a treatment liquid allows for the suppression of defects in a semiconductor device (Murayama, paragraph 0060-0062). It would have been obvious to one having ordinary skill in the art before the filing date of the instant application to include an inorganic acid component in an amount of less than 1 mass ppb with respect to the total mass of the chemical liquid, as taught by Murayama, in the cleaning liquid obtained by combining the teachings of Kumagai, Maemori, and Murayama because such an inorganic acid content suppresses interaction between the metal component and the acid component and provide better performance of the treatment liquid (Murayama, paragraph 0114). Furthermore, it would have been obvious to one having ordinary skill in the art before the filing date of the instant application to use butyl acetate as the organic solvent, as taught by Tsuchihashi, in the treatment liquid obtained by combining Kumagai, Maemori and Murayama because butyl acetate is taught to be a functional equivalent to the solvents utilized by Kumagai, Maemori, and Murayama for the purposes of a treatment liquid composition (see Tsuchihashi, paragraph 0068-0070; Kumagai, paragraph 0030; Maemori, paragraph 0037; and Murayama, paragraph 0071-0072).
Conclusion
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/JAYSON D COSGROVE/Examiner, Art Unit 1737
/JONATHAN JOHNSON/Supervisory Patent Examiner, Art Unit 1734
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