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 .
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Response to Amendment
Applicant’s Amendment filed 12/25/2025 has been accepted and is being considered. Claims 1, 2, 4, 5, and 8 have been amended. Claim 10 has been canceled. New claims 13-21 have been added.
Response to Arguments
Applicant’s Amendments to the claims have been considered and have changed the scope of the claims so as to overcome the prior art rejections made in the previous office action. As such, the rejections over 35 USC 103 made in the previous office action are withdrawn.
After further search and consideration, however, the Examiner makes a new grounds of rejection over 35 USC 103 as set forth in the body of the action below. Applicant’s amendments necessitated the new grounds of rejection.
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) 1-9, 11-17 and 19-21 is/are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama et al (US 20180335696 A1) and Hatakeyama (JP 3790649 B2, incorporated by reference in Hatakeyama et al, hereafter Hatakeyama-2).
Regarding claim 1-3, 5-8 and 11-12, Hatakeyama discloses a polymer-bound acid generating compound specifically an acid-generating subunit derived from a sulfonium or iodonium salt having an unsaturated bond and a fluorosulfonic acid anion (Abstract).
Hatakeyama discloses the composition comprises an acid generator that is not polymer bound as described from [0070]-[0101], where the preferred cations are the same as those bound to the base resin as described at [0045]), and anions are not-bound to a polymer backbone. Sulfonium and iodonium salts may conform to formulas (1-1) and (1-2) as depicted in [0072]-[0086], or to formula (2) as described from [0087]-[0094], or to formulas (3-1)-(3-4) in [0095]-[0101. Exemplary anions include those in [0100]:
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The above anions read upon claim 1 and 6 for where they bear iodo substitution on aryl rings and are sulfonate anions, and the iodonium cation reads upon the claim 1 and 7 for where it is a fluorinated aryliodonium.
The resist composition also comprises a base polymer resin having a polymer-bound acid generator (claim 2 – an additional onium salt), wherein the bound acid generator conforms to formulas (a1) and (a2), more preferably (a1-1) and (a2-1) ([0039]-[0043]):
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Exemplary anions (monomer form displayed) include those in [0044]:
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Exemplary cations are displayed in [0045].
Experimentally-used PAG Monomers are displayed in [0131]:
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The above compound reads upon the claim for where:
It is an onium salt that is polymer-bound (claim 2)
Fluorosulfonates are organic acid anions
The anion is iodo-substituted on a phenylene ring and alpha-fluorinated (claims 2, 5, 8)
Iodonium cations are onium cations
The cation is fluorosubstituted (claims 2, 5)
This component is also used in Polymer 3:
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Where the above units include acid-labile groups (the methylpentyl methacrylate and the lactone-bearing methacrylate) and a unit having a phenolic hydroxy group (claim 3)
Further discussion of the base resin and polymeric units present therein is presented in [0048]-[0068], where such units include styrene and styrene derivatives, as well as methacrylate, acrylate, and other units that have an ester sidechain capable of being cleaved by the action of an acid.
The compositions of Hatakeyama are dissolved into an organic solvent as described from [0103]-[0104].
Compositions are processed by applying the compositions to a substrate that may or may not have other features already formed thereupon. The composition is baked to form a resist film, then exposed to light and developed as discussed from [0122]-[0129], where the radiation exposure may be to UV, EUV, EB, x-ray, or other radiation types outlined in [0124] (claims 11 and 12).
There is no explicit recitation by Hatakeyama of an experimental example comprising a compound having a structure in which an alkoxy carbonyl group is bonded to a nitrogen atom.
This limitation is met by the general disclosure of the reference and incorporated references therein.
An additional component included in the composition is a quencher, where exemplary quenchers may be amines, aromatic amines, nitrogen-containing compounds with carboxyl groups, or carbamate compounds. Hatakeyama incorporates by reference the subject matter of Hatakeyama-2 (JP 3790649 B2), which discloses a resist composition incorporating a basic compound so as to improve pattern shape, where the basic compound is preferably a carbamate conforming to formula (1):
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Where R1 and R2 are each independently H, or may be an alkyl group of 1-20 carbons or aryl group of 6-20 carbons that may be further substituted. R3 may be a C1-C20 alkyl, C6-C20 aryl. R1 and R2 may be bonded together, or R1 and R3, or R2 and R3 may be bonded together to form a ring. Some example compounds are given on Page 20 of Hatakeyama-2:
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While the above compound does not read specifically on the claimed compound of claim 10, it does meet the limitations of claim 1 for having a structure in which an alkoxy carbonyl group is bonded to a nitrogen atom. The general formula, in combination with the specific teachings of the t-butyl group for R3 as presented in the example compound, reads upon claim 1 for where R1 and R2 are hydrocarbons having 1-20 carbons and/or may be bonded together and where R3 is a C4-C20 hydrocarbon that may be a branched alkyl group such as t-butyl.
The inclusion amount of this component ranges from 0.01 to 2 parts by weight per 100 parts by weight of base resin (wt%). The acid generator of Hatakeyama-2 is present in a range from 0.2 to 50 parts by weight relative to 100 parts of the base resin (wt%). As such, the basic components of Hatakeyama-2 may be present in a range from 0.01/50 to 2/0.2 wt%, or 0.0002 to 10wt% based on the amount of the acid generator (this range also touches the range of “10% or more” in claim 15 and overlaps the range of “50% or less” in claim 16). Alternatively, the non-polymeric acid generator of Hatakeyama is present in 0-200 parts by weight per 100 parts of the base polymer – in which case the calculation changes from 0.01/200 to 2/”0” (for mathematical purposes the Examiner will consider 0 as 0.001), wherein the range of inclusion is 0.005% to 2000%.
The addition of a basic compound is performed so as to suppress the diffusion rate of acid in the resist film or correct pattern profile.
A person of ordinary skill in the art would have found it obvious to arrive at the claimed invention from the disclosed compounds and formulas of the acid generating resin and the disclosed teachings of the carbamate acid generator in order to arrive at a composition having improved pattern profile and suppressed diffusion rate of acid during processing.
Regarding Claims 4, 9, and 20, Hatakeyama and Hatakeyama-3 meet the limitations of the claims as described regarding claims 1 and 2 above.
However, as claims 1 and 2 are not embodied in an experimental example, none of claims 4, 9, and 20 are explicitly embodied in an experimental example.
These claim limitations are met by the general disclosure of the reference and teachings therein.
Hatakeyama discloses an onium salt quencher at [0013]-[0119], where the quencher is a carboxylate salt having a sulfonium , iodonium, or ammonium countercation (claim 4 and 9), as bounded by formula (5):
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The quencher is present in 0-5 parts by weight per 100 parts of base resin in the base polymer. The non-polymeric acid generator of Hatakeyama is present in 0-200 parts by weight per 100 parts of the base polymer. As such, the onium quencher may be present in an amount ranging from 0% to ‘at least’ 200% (the Examiner will not divide by 0).
Concerning the phenolic-subunit language of claim 4, this limitation is met in the reference where the base resin comprises a phenolic subunit (See discussion above regarding claim 1 and 3, Polymer 3).
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the time of filing in view of the teachings of Hatakeyama and Hatakeyama-2, incorporating the onium quencher (acid diffusion control agent) into the composition as taught so as to improve the pattern profile.
Regarding Claim 14, Hatakeyama and Hatakeyama-2 meet the limitations of the claim as discussed above regarding claim 1. As was discussed above regarding claim 1, Hatakeyama incorporates by reference the subject matter of Hatakeyama-2 (JP 3790649 B2), which discloses a resist composition incorporating a basic compound so as to improve pattern shape, where the basic compound is preferably a carbamate conforming to formula (1):
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Where R1 and R2 are each independently H, or may be an alkyl group of 1-20 carbons or aryl group of 6-20 carbons that may be further substituted with groups such as a hydroxyl group, carboxyl group. R3 may be a C1-C20 alkyl, C6-C20 aryl. R1 and R2 may be bonded together, or R1 and R3, or R2 and R3 may be bonded together to form a ring. Some example compounds are given on Page 20 of Hatakeyama-2:
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While the above compound does not read specifically on the claimed compound of claim 1 due to the additional hydroxy, it does meet the limitations of claim 1 for having a structure in which an alkoxy carbonyl group is bonded to a nitrogen atom. The general formula, in combination with the specific teachings of the t-butyl group for R3 as presented in the example compound, reads upon claim 1 for where claimed R3 and R2 are hydrocarbons having 1-20 carbons and/or may be bonded together and where claimed R1 is a C4-C20 hydrocarbon that may be a branched alkyl group such as t-butyl. Hatakeyama clearly contemplates branched alkyl groups as a part of the Markush group to describe reference R3 – if it did not, t-butyl would not be present in the specification of the reference. A person having ordinary skill in the art would consider the use of another tertiary or otherwise branched alkyl group, especially one bearing a similar number of carbons to tBu such as a C5 or C6 branched alkyl group, a matter of chemical similarity to the examples of the reference as guided by the specification. Such an ordinarily skilled artisan would consider the chemical structural similarity to beget similar properties and thus similar performance.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention from the disclosed formula and taught branched alkyl embodiments with the expectation that similar chemical features would result in a similarly-performing embodiment.
Regarding Claim 13 and 17, Hatakeyama and Hatakeyama-2 meet the limitations of the claim as discussed above regarding claim 1.
Hatakeyama and Hatakeyama-2 do not explicitly teach an experimental embodiment of the resin of claim 1 as discussed above and thus do not explicitly meet the limitations of the claim 13 and 17 with an experimental embodiment.
However, the claim limitations of the instant claim 17 are met by the general disclosure of the reference Hatakeyama.
As was discussed above regarding claim 1, Hatakeyama discloses the composition comprises an acid generator that is not polymer bound as described from [0070]-[0101], where the preferred cations are the same as those bound to the base resin as described at [0045]), and anions are not-bound to a polymer backbone. Sulfonium and iodonium salts may conform to formulas (1-1) and (1-2) as depicted in [0072]-[0086], or to formula (2) as described from [0087]-[0094], or to formulas (3-1)-(3-4) in [0095]-[0101].
For instance, formulas (3-1) and (3-2):
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R31 is H, OH, CN, carboxyl, F, Cl, Br, amino, or a straight/branched/cyclic C1-C20 alkyl/alkoxy group, or another group mentioned in [0096].
Subscript t is 0-3
X1 is a single bond or C1-C2 divalent linking group when r=1 or C10-C20 tri or tetravalent linking group when r=2 or 3, where the group may contain C or N or S
Rf11-Rf14 are each independently H, F, or CF3, where at least one of Rf11-Rf14 are F or CF3 or Rf11 and Rf12 together may form a carbonyl group
R32- R36 are each independently a C1-C12 straight/branched/cyclic alkyl group, C2-C12 straight/branched or cyclic alkenyl group, or C1-C20 aryl group, C1-C12 aralkyl group, or another group mentioned in [0096], wherein at least one hydrogen (one or more or all) are substituted by OH, carboxyl, CN, halogen, oxo, nitro, or other moeity mentioned in [0096]
Subscript r is 1-3, subscript s is 1-5
The above formula meets the limitations of the claim for where, in Formula (A-2):
Subscript q is 1-3, r is 0-3, and p is 1-3
L1 is an ester linkage
R1 is OH, CN, carboxyl, F, Cl, Br, amino, or a straight/branched/cyclic C1-C20 alkyl/alkoxy group, or another group mentioned in [0096].
R2 is a single bond or C1-C2 divalent linking group when p=1 or C10-C20 tri or tetravalent linking group when p=2 or 3, where the group may contain C or N or S
Rf1-Rf4 are each independently H, F, or CF3, where at least one of Rf1-Rf4 are F or CF3 or Rf1 and Rf2 together may form a carbonyl group
For where at least one of reference R13 and R14 (claimed R3 and R4) is F or CF3, the limitations of claim 13 requiring F or fluoroalkyl are met.
R32- R36 are each independently a C1-C12 straight/branched/cyclic alkyl group, C2-C12 straight/branched or cyclic alkenyl group, or C1-C20 aryl group, C1-C12 aralkyl group, or another group mentioned in [0096], wherein at least one hydrogen (one or more or all) are substituted by OH, carboxyl, CN, halogen, oxo, nitro, or other moeity mentioned in [0096]
Exemplary species are depicted in [0100]. Hatakeyama describes the addition of a second acid generator such as the ones bounded by (3-1) and (3-2) (and/or 3-3 and 3-4), among other components, as improving the sensitivity of the composition ([0070])
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the time of filing from the teachings of Hatakeyama and Hatakeyama-2, using the taught acid generating species as part of the composition therein to improve the sensitivity.
Regarding Claim 19, Hatakeyama and Hatakeyama-2 disclose the limitations of the claim as discussed above regarding claim 1.
The quencher of Hatakeyama is present in 0-5 parts by weight per 100 parts of base resin in the base polymer. The quencher of Hatakeyama-2 is present in no more than 2 parts per 100 parts of base resin. The reference Hatakeyama uses more acid-generating embodiments than Hatakeyama-2 – Hatakeyama recites an acid-generating resin and a non-polymeric acid generating compound may be present, while Hatakeyama-2 only recites a non-polymeric acid generating compound. A person having ordinary skill in the art would consider the totality of the compositions referenced when considering the amount of an ingredient to include – compositions having more acid generated therein would naturally need more of a basic compound/quencher to maintain similar degree of acid diffusion control than a composition that generates less acid. As such, even if Hatakeyama-2 teaches away from using more than 2wt% of the basic compound, the teachings of Hatakeyama, where this compound is applied, suggest that including an amount as directed by the reference (0-5wt%) would not be deleterious to performance.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the time of filing in view of the teachings of the references to arrive at a composition having improved resolution and acid control imparted by the quencher component(s) therein.
Regarding Claim 21, Hatakeyama and Hatakeyama-2 disclose the limitations of the claim as discussed above regarding claim 1.
However, neither Hatakeyama reference discloses an experimental embodiment that meets the claim limitations.
These limitations are met by the general disclosure of the references.
As was discussed above regarding claim 1, Hatakeyama incorporates by reference the subject matter of Hatakeyama-2 (JP 3790649 B2), which discloses a resist composition incorporating a basic compound so as to improve pattern shape, where the basic compound is preferably a carbamate conforming to formula (1):
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Where R1 and R2 are each independently H, or may be an alkyl group of 1-20 carbons or aryl group of 6-20 carbons that may be further substituted with groups such as a hydroxyl group, carboxyl group. R3 may be a C1-C20 alkyl, C6-C20 aryl. R1 and R2 may be bonded together, or R1 and R3, or R2 and R3 may be bonded together to form a ring.
When R1 or R2 comprise a hydroxyl substitution and are bonded together, the resultant ring is hydroxyl-substituted. R1 and R2 in the reference map onto the claimed structure for R2 and R3 respectively.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention from the disclosed formula and taught heterocyclic embodiments with the expectation that similar chemical features would result in a similarly-performing embodiment, resulting in a composition having improved pattern features imparted by the inclusion of an acid diffusion inhibitor.
Claim(s) 19 is rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama et al (US 20180335696 A1) and Hatakeyama (JP 3790649 B2, incorporated by reference in Hatakeyama et al, hereafter Hatakeyama-2) as applied to claim 1 above, and further in view of Taniguchi et al (US 20200301274 A1, published 09/24/2020).
Regarding Claim 19, Hatakeyama and Hatakeyama-2 disclose the limitations of the claim as discussed above regarding claim 1.
Neither reference teaches the specific quencher of claimed 18. Rather, a generic formula for an onium salt quencher is given by Hatakeyama but such formula and limitations thereon are insufficiently descriptive as to effectively read upon the limitations of the claim. The onium salt of Hatakeyama is a carboxylic acid salt that may be fluorinated, and may be a sulfonium, iodonium, or ammonium salt.
The claim limitations are met by Taniguchi.
Taniguchi teaches a composition comprising a quencher containing an onium salt (A-1), described from [0013]-[0014] and [0043]-[0055].
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Where:
R1 is a hydrogen, fluorine, chlorine, bromine, hydroxy, amino, a linear/branched/cyclic C1-C20 alkyl group that may be further substituted with one of the aforementioned groups, a C1-C20 alkoxy group, acyloxy group of 1-20 carbons, or an amido group as presented in [0044].
Subscript p may be 0 or 1
When p is 1, R2 and R3 are each independently H or a linear/branched/cyclic alkyl group having 1-20 carbons
When p is 1, Rf1 and Rf2 are each independently H, F, or CF3
Subscript m is 1-5, subscript n is an integer that when summed with m presents m+n is greater than 0 and less than or equal to 5.
R4-R6 may each be C1-C12 alkyl or oxoalkyl group, or an oxo alkenyl or aryl group having up to 20 carbons therein, or another group described in [0044], where the groups are substituted with OH, carboxy, fluorine or another halogen, nitro, cyano, or another moeity described in [0044].
Specific examples of anions and cations are presented in [0053]-[0055]
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The quencher of formula (A-1) of Taniguchi meets the limitations of the claim for claimed formula (S-1) where:
R1 is a hydrogen, fluorine, chlorine, bromine, hydroxy, amino, a linear/branched/cyclic C1-C6 alkyl group that may be further substituted with one of the aforementioned groups, a C1-C6 alkoxy group, acyloxy group of 2-6 carbons, or an amido group as presented in the reference’s [0044]
L1 is a single bond or a divalent group having an ester linkage and 2-20 carbons
Subscript m is an integer of 1-5
Subscript n is an integer of 0-3, to the balance of m+n is between 0 and 5, including 0 and 5.
Taniguchi ascribes improved acid diffusion and EUV performance during processing to the compositions comprising the quencher disclosed.
A person having ordinary skill in the art would have been able to arrive at the claimed invention prior to filing from the disclosure of the reference – incorporating the quencher of Taniguchi into the composition of Hatakeyama and Hatakeyama-2 so as to improve acid diffusion properties in the resultant resist 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
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