DETAILED ACTION
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 .
Response to Amendment
Applicant’s Amendment filed 11/25/2025 has been entered and is being considered. Claim 1 is amended. No new matter has been added with these amendments.
Response to Arguments
Applicant's arguments filed 11/25/2025 regarding the 35 USC 102(a)(1) rejection have been fully considered and are persuasive in view of the amendments made to Claim 1; therefore the 35 USC 102(a)(1) rejection has been withdrawn.
Applicant’s arguments filed 11/25/2025 regarding the 35 USC 103 rejections have been fully considered but they are not persuasive. Applicant argues that the polymer Ab-16 in Kaneko relied upon in the prior office action contains only 70 mol% of aromatic ring-containing repeat units due to the new amendment which limits the aromatic repeat units to comprise 85% of the overall repeat units of the polymer. In response, the Examiner notes that the teachings of the prior art may come from disclosed examples therein and from the entirety of the disclosure. Regarding the Polymer Ab-16, the only limitation of amended Claim 1 that the example polymer Ab-16 is missing is the new limitation where the aromatic ring-containing repeat units account for at least 85 mol% of overall repeat units of the polymer. Polymer Ab-16 contains a repeating unit containing a lactone group at 20 mol% and a repeating unit having a group being decomposed due to action of an acid and generating a carboxyl group; both of these groups are not aromatic. Regarding the group containing a lactone group, Kaneko further discloses that the repeating unit having a lactone group is preferably 1 to 30 mol% (paragraph [0402]). Regarding the group containing the acid-decomposable group, Kaneko further discloses a number of specific examples of the repeating unit having a group being decomposed due to an action of an acid and generating a carboxyl group, some of which are aliphatic monomers while others are aromatic-containing monomers that satisfy formula A3 as instantly claimed (paragraph [0354-0356], pages 19-20). One of ordinary skill would envisage a facile substitution of the non-aromatic repeating unit having an acid-decomposable group with an aromatic repeating unit having an acid-decomposable group. Additionally, the same rationale may further me applied to the disclosed Example Ab-11 and Ab-13 (page 49-50) which contains two aromatic monomers that satisfy A1 and A2 and two aliphatic acid-decomposable monomers that may be substituted for aromatic acid-decomposable monomers. See the detailed action below.
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.
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 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.
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 1-4, 8, 9, 11, 12, and 15-19 are rejected under 35 U.S.C. 103 as being unpatentable Kaneko (US 2019/0219922, IDS 10/16/2023).
Regarding Claims 1, 2, 4, 8, 9, 11, 12, and 15-19, Kaneko teaches resist compositions containing a resin including repeating units comprising a group that is decomposed due to action of an acid and a phenolic hydroxyl group (abstract). The resist composition is preferably a chemically amplified resist composition and may be a positive or negative resist composition (paragraph [0103-0107]). Some examples of the resins (A) used in the resist compositions are described, but the present invention is not limited thereto, such as resin Ab-11 (paragraph [0673], page 48-49). Resin Ab-11 comprises 4 different repeating units satisfying Formula A1 and A1-1 (Claim 2) where RA is H, X1 is COO and A1 are single bonds, c=0, a=0, b=1, Formula A2 where RA is H, X2 is COO A2 is single bond, d=0, f=0, e=2, R3 is an acid labile group connected with an acetal linkage, Formula A3 and A3-1 where RA is methyl, X3 is a single bond, R4 is a tertiary alkyl acid leaving group and R6 is a C9 alicyclic hydrocarbon (Claim 4), and Formula B2 where h=0 (Claim 8). The content ratio of formula A1 and B2 is 50 mol% (Claim 9). The monomer that satisfies Formula A3 is an acid-decomposable monomer, but is not aromatic. Resin Ab-11 is used in the photoresist composition of Example 1-11 which comprises photoacid generator z1, basic compound N-9, hydrophobic resin B-3, and a combination of solvents S-1 and S-4 (Table 1, page 59-60) (Claims 11, 12). In Example 3, the resist composition was spin-coated onto a support comprising a silicon wafer onto which a Cr oxide vapor deposition was performed to form a resist coated mask blank (paragraph [0722-0727]). The resist film was then patterned using an electron beam drawing device, heated to 110 oC for 90 seconds, and developed with aqueous TMAH to obtain a resist pattern (paragraph [0729]) (Claims 15-19).
The composition Ab-11 of Kaneko comprises 75 mol% of aromatic ring-containing repeat units and is silent to this particular composition having greater than 85 mol% of the aromatic ring-containing repeat unit as instantly claimed.
However, Kaneko further discloses that the group containing the acid-decomposable group may be a number of specific examples of the repeating unit having a group being decomposed due to an action of an acid and generating a carboxyl group, some of which are aliphatic monomers while others are aromatic-containing monomers that satisfy formula A3 as instantly claimed (paragraph [0354-0356], pages 19-20). It would have been obvious for one of ordinary skill in the art to have substituted an aliphatic acid-decomposable monomers for one of the disclosed acid-decomposable monomers since the acid-decomposable monomers are disclosed as performing the same function in the resin composition. One of ordinary skill would reasonably expect this modification to result in a resin having similar acid-decomposable properties. This substitution would result in a resin with 100% of the monomers containing an aromatic group.
However, Kaneko further discloses that in a case where the resin (A) according to the first embodiment contains the repeating unit represented by Formula D3 as the repeating unit (a), a content ratio of repeating units (repeating units excluding the repeating unit D1, and preferably the repeating unit represented by Formula D2) having the phenolic hydroxyl group (b) is preferably 10 to 90 mol %, more preferably 15 to 85 mol %, and even more preferably 20 to 80 mol % with respect to all repeating units in the resin (A) (paragraph [0321]). Additionally, Kaneko discloses other similar resins comprising the repeating unit having the phenolic hydroxyl group being incorporated at 30 mol% (Ab-12), 45 mol% (Ab-13), 40 mol% (Ab-18), and 50 mol% (Ab-20) (pages 49-52).
Kaneko teaches the invention is not to be limited to just the disclosed examples and further modification can be made in view of the disclosure. Kaneko further discloses a range of the content ratio of the repeating unit having the phenolic hydroxyl group to be preferably between 20 to 80 mol% which is further exemplified in various working example resins. Thus, it would have been obvious for one of ordinary skill in the art to have modified the content of the repeating unit comprising the phenolic hydroxyl group to be in the range of 20 to 80 mol% through routine experimentation. The result of this modification would yield a resin polymer having a content ratio range of aromatic ring-containing monomers satisfying the repeating units A1 and A2 between 45 mol% and 100 mol%, which overlaps the instantly claimed range of greater than 65 mol%. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). Applicants can rebut a prima facie case of obviousness by showing the criticality of the range. "The law is replete with cases in which the difference between the claimed invention and the prior art is some range or other variable within the claims.... In such a situation, the applicant must show that the particular range is critical, generally by showing that the claimed range achieves unexpected results relative to the prior art range." In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). See MPEP 2144.05. One of ordinary skill would reasonably expect this modification to result in a similarly working chemically amplified resist polymer based on the disclosure of the resin polymers and their
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content ratios in Kaneko.
Regarding Claim 3, the discussion of Claim 1 is relied upon as above. Kaneko further discloses some examples of the resins (A) used in the resist compositions are described, but the present invention is not limited thereto, such as resin Ab-11 and Ab-16 (paragraph [0673], page 48-50), which both comprise repeating units satisfying Formula A2.
Kaneko is silent to a repeating units in the polymer compositions Ab-11 satisfying Formula A2-1. The main difference is that the monomers comprise more than one hydroxyl group that is protected by an acid-labile group.
However, Kaneko further discloses the resin includes a repeating unit D3a having the OYo group wherein -OYo is a group decomposed due to an action of an acid (paragraph [0235-0239]). In Formula D3a, R3q may be hydrogen, halogen, or alkyl group having 1 to 4 carbons (paragraph [0237]), Ar3a represented an aromatic ring group preferably benzene (paragraph [0238]), n3a represents an integer of 1 or more in Formula D3a, however in a case where n3a is 1, Y3 is a group represented by Formula (iii), which is an acetal group (paragraph [0019] for formula (iii), [0240]). The monomer described by Formula (D3a) satisfies Formula A2-1 where RA is hydrogen, halogen, or methyl, and R5 is an acid labile acetal group having 1-4 carbon alkyl groups or 6 to 15 carbon aromatic groups (paragraph [0151-0153, 0158-0160]. Thus, Kaneko discloses several different embodiments of monomers comprising repeating units each working in the same way to decompose due to the action of an acid.
Kaneko teaches the invention is not to be limited to just the disclosed examples and further modification can be made in view of the disclosure. Kaneko further discloses an alternative embodiments for repeating units that decompose due to the action of an acid, and since the repeating units perform the same function in view of the art, the repeating units are interchangeable for one another. It would have been obvious for one of ordinary skill in the art to have modified or substituted the phenolic monomers comprising an acid labile group in polymer Ab-11 and Ab-16 the alternative embodiments of Formula (iii) disclosed therein. One of ordinary skill would reasonably expect this modification to result in a similarly working chemically amplified resist polymer based on the disclosure of Kaneko.
Claims 5-7 are rejected under 35 U.S.C. 103 as being unpatentable Kaneko (US 2019/0219922, IDS 10/16/2023) as applied to Claim 1 in view of Hatakeyama (US 2013/0084527).
Regarding Claims 5-7, the discussion of Claim 1 is relied upon as above. Kaneko teaches resist compositions comprising a repeating unit containing a carboxy group protected with an acid labile group (paragraph [0342]). Kaneko further discloses that the group containing the acid-decomposable group may be a number of specific examples of the repeating unit having a group being decomposed due to an action of an acid and generating a carboxyl group, some of which are aliphatic monomers while others are aromatic-containing monomers that satisfy formula A3 as instantly claimed (paragraph [0354-0356], pages 19-20).
Kaneko is silent to the repeating unit containing a carboxy group protected with an acid labile group is a repeat unit having the formula A3-2.
However, Hatakeyama discloses positive resist compositions comprising a polymer having carboxyl groups substituted with an acid labile group having formula (1) which exhibit a high contrast of alkaline dissolution rate before and after exposure, a high resolution, a reduced acid diffusion rate, and forms a pattern with good profile, minimal edge roughness, and etch resistance (abstract). Specifically, a polymer comprising recurring units of the general formula (2) is used as the base resin (paragraph [0049]). In General Formula (2), X1 may be a single bond, -C(=O)-O-R5-, phenylene, or naphthylene, R1 and R2 each are a straight, branched or cyclic C1-C8 alkyl, C6-C10 aryl, or C2-C10 alkenyl group, which may contain an oxygen or sulfur atom, R3 is fluorine or trifluoromethyl, R5 is a straight, branched or cyclic C1-C10 alkylene group which may have an ester (—COO—) radical, ether (—O—) radical or lactone ring, and R4 is hydrogen or methyl, and m is an integer of 1 to 5 (paragraph [0047-0049]). Hatakeyama discloses examples of resin polymers comprising repeating units of General Formula (2) (paragraph [0118-0205]). The resin polymers further comprise aromatic phenolic monomers, aromatic monomers with phenolic groups protected by an acid labile group, and aromatic monomers, Polymer 27 and Polymer 28 as examples (paragraph [0198-0199]). The resulting resist compositions comprise a photoacid generator, a base, a dissolution regulator, and an organic solvent (Table 1 and Table 2, page 53 and 54). The main difference between the comparative examples and the inventive examples is the comparative examples do not contain the repeating unit having general formula (3) and only contain aromatic phenolic monomers, aromatic monomers with phenolic groups protected by an acid labile group, aromatic monomers, and carboxy monomers protected by an acid labile group (paragraph [0208-0223]).
The general Formula (2) satisfies the claimed Formulae A3-2 and A3-3 where X3 may be a single bond, -C(=O)-O-R5-, phenylene, or naphthylene and R5 is a straight, branched or cyclic C1-C10 alkylene group which may have an ester (—COO—) radical, ether (—O—) radical or lactone ring, RB and RC may be R1 and R2 each are a straight, branched or cyclic C1-C8 alkyl, C6-C10 aryl, or C2-C10 alkenyl group, which may contain an oxygen or sulfur atom, n3=0, n2=0, n1=1 to 5, and R7 is fluorine or trifluoromethyl (Claims 5-7).
It would have been obvious for one of ordinary skill in the art to have substituted the acid-decomposable aromatic protected with an acid labile group of Kaneko with the fluorine containing carboxy monomers protected with an acid labile group of Hatakeyama through routine experimentation. Both Kaneko and Hatakeyama teach resins for positive photoresist materials which also perform the same function as an acid-labile group. One of ordinary skill would have been motivated to make this modification in order to provide high contrast of alkaline dissolution rate before and after exposure, a high resolution, a reduced acid diffusion rate, and forms a pattern with good profile, minimal edge roughness, and etch resistance as suggested by Hatakeyama.
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Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable Kaneko (US 2019/0219922, IDS 10/16/2023) as applied to Claim 1 in view of Masunaga (US 2018/0039177, IDS 08/23/2023).
Regarding Claim 10, the discussion of Claim 1 is relied upon as above. Kaneko is silent to the resist compositions further comprising a fluorinated polymer with repeat units selected from the group of C1 to C4 and optionally at least one repeat unit of C5 or C6 as instantly claimed.
However, Masunaga discloses positive resist compositions that form a pattern with minimal LER (abstract). The resist composition may further comprise (C) a fluorinated polymer comprising repeating units of C1 to C5 for the purposes of enhancing contrast, preventing chemical flare of acid upon exposure to high-energy radiation, preventing mixing of acid from an anti-charging film in the step of coating an anti-charging film-forming material on a resist film, and suppressing unexpected unnecessary pattern degradation (paragraph [0106]). Since the fluorinated polymer also has a surface-active function, it can prevent insoluble residues from redepositing onto the substrate during the development step and is thus effective for preventing development defects (paragraph [0106]). The structures C1, C2, C3, C4, and C5 are similar to the structures C5, C1, C2, C3, and C4 as instantly claimed (page 18-19). For claimed structures C1, C2, C3, and C4, Masugana discloses where RD is hydrogen, fluorine, methyl, or trifluoromethyl, R101, R102, R104 and R105 are each independently hydrogen or a C1-C10 straight, branched or cyclic alkyl group, and R103, R106, R107, and R108 are hydrogen, C1-C15 straight, branched or cyclic monovalent hydrocarbon group or a monovalent fluorinated hydrocarbon group, or an acid labile group, with the proviso that an ether or carbonyl moiety may intervene in a carbon-carbon bond in the monovalent hydrocarbon or monovalent fluorinated hydrocarbon groups, and where Z1 is a C1-C20 straight, branched or cyclic (m+1)-valent hydrocarbon group or fluorinated hydrocarbon group and m is 1 to 3 (paragraph [0107]). Of the optional repeating units, Masugana further discloses the structure C1 where R110 is a C1-C5 straight or branched monovalent hydrocarbon group in which a heteroatom may intervene in a carbon - carbon bond, R109 is hydrogen or a C1-C5 straight or branched monovalent hydrocarbon group in which a heteroatom may intervene a carbon-carbon bond, x is 1 to 3, y satisfies :0≤5 + 2z - x , and z is 0 or 1 (paragraph [0107]).
It would have been obvious for one of ordinary skill in the art to have modified the positive photoresist compositions of Kaneko with the fluorinated polymers of Masunaga. One of ordinary skill would have been motivated to make this modification to enhancing contrast, preventing chemical flare of acid upon exposure to high-energy radiation, preventing mixing of acid from an anti-charging film in the step of coating an anti-charging film-forming material on a resist film, and suppressing unexpected unnecessary pattern degradation as suggested by Masugana.
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable Kaneko (US 2019/0219922, IDS 10/16/2023) as applied to Claim 12 as evidenced by Shiratani (US 2017/0299962).
Regarding Claim 13, the discussion of Claim 12 is relied upon as above. Kaneko further discloses resin Ab-11 is used in the photoresist composition of Example 1-11 which comprises photoacid generator z1 (Table 1). The photoacid generator z1 comprises a sulfonate anion attached to a perfluoropropane group, as shown below (page 54).
Kaneko is silent to the particular pKa values of the generated acid.
However, Shiratani discloses radiation sensitive compositions including an acid generating agent that is capable of generating an acid upon irradiation with a radioactive ray (abstract). pKa values of similar fluorinated sulfonate salts of triphenylsulfonium are shown (paragraph [0189-0195]). Kaneko demonstrates a trend in pKa values: CC-1 comprises a perfluorobutanesulfonate anion and triphenylsulfonium cation has a pKa of -3.31 ([0189]) and C2-1 comprises a perfluoroethanesulfonate-containing anion and a triphenylsulfonium cation and has a pKa of -2.46 ([0194]).
As evidenced by Shiratani, the photoacid generators containing perfluoroalkyl sulfonate anions of 2 and 4 carbons both have a pKa of -2.0 or less. Thus, as evidenced by the perfluoroalkyl photoacid generators in Shiratani, the perfluoropropanesulfonate-containing photoacid generator z1 of Kaneko would also have a pKa of -2.0 or less, since the number of perfluorinated carbons is intermediate to the two examples relied upon in Shiratani.
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Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable Kaneko (US 2019/0219922, IDS 10/16/2023) as applied to Claim 1 in view of Shimura (US 2020/0150541).
Regarding Claim 14, the discussion of Claim 1 is relied upon as above. Kaneko is silent to the dissolution rate with developer of the resist film after exposure.
However, Shimura teaches the film thickness loss of the resist film by developing may be expressed by a dissolution rate (nm/s) (paragraph [0022]). The higher the dissolution rate in the alkaline developing solution, the greater the film thickness loss in the unexposed portion of the resist film during development; on the other hand, the closer the dissolution rate in the alkaline developing solution to zero, the smaller the film thickness loss in the unexposed portion of the resist film during development (paragraph [0022]). The resin component P1 includes a structural unit derived from an acrylate ester containing an acid decomposable group that exhibits increased polarity by the action of an acid (paragraph [0120]) and that the resist compositions may be a chemically amplified photoresist (paragraph [0130]). Shimura discloses when the dissolution rate of the polymeric compound (p10) in an alkali developing solution is preferably 10 nm/second or more, and more preferably 10 to 100 nm/second, such that the dissolution rate in the exposed portions after exposure may be further enhanced and as a result residue is unlikely to be generated and sensitivity may be further improved (paragraph [0265]).
While the explicit teachings in Shimura relate to a combination of polymer resins, the general teachings may apply to any chemically amplified photoresist.
It would have been obvious for one of ordinary skill in the art to have arrived at a resist composition of Kaneko with a dissolution rate of greater than 50 nm/s through routine optimization based on the teachings of Shimura. Shimura clearly demonstrates that the non-exposed regions should have a dissolution rate of 10 nm/second or more such that in the exposed regions the dissolution rate is even higher such that residue us unlikely to be generated and sensitivity may be further improved. One of ordinary skill would reasonably expect to arrive at the claimed dissolution rate in an overexposed region of 50 nm/s or more based on the teachings of Shimura in order to generate a photoresist pattern with little residue and improved sensitivity as suggested by Kaneko.
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 KEVIN JAMES DRUMMEY whose telephone number is (703)756-5419. The examiner can normally be reached Monday - Friday 7:30am-5:00pm EST.
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/K.J.D./Examiner, Art Unit 1737
/MARK F. HUFF/Supervisory Patent Examiner, Art Unit 1737