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 .
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 10/21/2025 has been entered.
Response to Amendment
Applicant’s Amendment to the claims as set forth in 10/21/2025 has been entered and is being considered in this office action. Claim 1 has been amended. Claims 15-17 are added. No new matter has been added with these amendments.
Response to Arguments
Applicant’s Amendments and arguments based thereon have placed the scope of the claims outside that of the primary reference used to set forth the rejections in the prior office action. These rejections are withdrawn.
After further search and consideration, the Examiner makes a new grounds of rejection over Yamaguchi, and regarding claim 13 – Yamaguchi and further in view of Aqad, as set forth in the body of the office action below.
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, 3-13, and 15-17 is/are rejected under 35 U.S.C. 103 as being unpatentable over Yamaguchi (US 20120264054 A1).
Regarding Claim 1, 5-10, 12, 15, and 17, Yamaguchi discloses a pattern forming method and composition therefor, wherein the composition comprises a resin (A) and a compound (B) that has a polymerizable group and generates an acid upon irradiation with actinic rays or radiation (Abstract). The composition is used to generate a negative pattern.
Yamaguchi does not disclose a particular experimental embodiment that meets the sum total of the claim limitations. Rather, these limitations are met by the general disclosure of the reference.
The base resin (A) is described from [0054]-[0193], where the resin is acid degradable and comprises monomer subunits such as those of formula (A1) at [0070]-[0082], formulas (1) and (2) at [0083]-[0094], and (but not only) lactone subunits such as those at [0119]-[0140]. The resin is dissolved, along with other components, in a solvent as described at [0406]-[0412], such as a mixed solvent of hydroxy-bearing and non-hydroxy-bearing solvents – such as a but not limited to propylene glycol monomethyl ether acetate and ethyl lactate (claim 4). The resin is present in 30% to 99% by mass of the solid content of the composition ([0192]).
The composition also may comprise a surfactant (F) as described from [00518]-[0527] (claim 7).
The composition may also comprise a crosslinking agent (G) as described from [0528]-[0605] (claim 6).
The composition may also comprise a basic compound as described from [0489], such as a primary, secondary, or tertiary aliphatic amine (A), or a compound having a nitrogenous functional group (B)-€ as described from [00488]-[0517], or conforms to the carbamate of formula (e1). The basic compound is described as inhibiting the reduction in resolution caused by elapsing time after exposure (after the release of acid), and as such the basic compound is interpreted as a quencher (Applicant’s specification also describes primary/secondary/tertiary amines and carbamates as quenchers at page 104-105) (claim 5).
The compound (B) is described from [0194]-[0361], where compound (B) has a polymerizable group preferably represented by the structure General Formula (ZI) (paragraph [0197]) and from the viewpoint of inhibiting diffusion of the generated acid, it is preferable the Z- has a polymerizable group (paragraph [0203]). The number of polymerizable groups in the compound (B) is not particularly limited and may be 1 to 10 and more preferably 1 to 3 (paragraph [0207]). Yamaguchi discloses specific but non-limiting examples of the compound (B) that has a polymerizable group and generated an acid after irradiation (paragraph [0360]). For example – Compounds A12 and A53 are as below
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The compound A12 meets the limitations of the claim where:
On the Anion
X2 is a C6 cyclohexyl group (hydrocarbyl group) (k=0)
X3 is an ester bond
Rf is a CF3 group
Rf2 is a H atom
Rf3-Rf4 are each F
On the cation
R1-R3 are each H
X4 is a single bond
Subscript q is 0
Subscript m is 3 (claim 15, claim 17)
Subscript n and r are 0
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This compound A53 meets the limitations of the claim where:
On the Anion
R1-R3 are each H
X1 is a single bond (k=1)
X2 is a C2 hydrocarbyl group having an oxygen heteroatom
X3 is an ether bond
Rf1 is a CF3 group
Rf2 is a H atom
Rf3-Rf4 are each F
On the cation
R1 is a H or methyl
R2-R3 are each H
X4 is an ester bond group
Subscript q is 0
Subscript m is 3 (claim 15, claim 17)
Subscript n and r are 0
The content of the sulfonium compound (B) may range from 0.1-20% by mass based on the total solid content of the composition. The base resin, as mentioned above, may range from 30% to 99% of the solid content of the composition by mass. As such, the sulfonium salt may be present in 0.1 to 66.6 mass% relative to 100 parts by mass of the base resin – or 10 parts by mass to 66.6 parts by mass relative to 100 parts of the base resin (claim 12).
The composition is processed in a pattern-forming method as described from [0616]-[0678 ], where the composition is applied to a substrate to form a film, then exposed to radiation, then developed with an organic solvent developer (claim 8). A prebake and a post-exposure bake may also be performed. The radiation used in the exposure is not particularly limited, but may include KrF, ArF, and F2 excimer laser radiation (claim 10). The developer comprising organic solvent may be a developer including 2-octanone, 2-nonanoe, 2-heptanone, butyl acetate, amyl acetate, or any other solvent discussed from [646]-[0661] (claim 9).
The negative resist composition of the reference bears the components of the claims and the reference asserts that the composition and resultant products exhibit improved resolving power such as through improved line edge roughness and development time dependency by the polymerization of acid generator (B) in the resist film due to exposure so as to decrease the solubility of the exposed resin in the organic developer relative to unexposed resin – increasing the dissolution contrast between the exposed and unexposed portions. A person having ordinary skill in the field of endeavor would have found it obvious to arrive at the claimed invention from the general disclosure of the reference in order to arrive at a resist composition exhibiting higher processing performance and improved pattern resolution.
Regarding Claim 3, Yamaguchi discloses a pattern forming method and composition therefor as discussed above regarding claim 1.
Yamaguchi does not disclose a particular experimental embodiment that meets the sum total of the claim limitations. Rather, these limitations are met by the general disclosure of the reference.
The base resin (A) is described from [0054]-[0193], where the resin is acid degradable and comprises monomer subunits such as those of formula (A1) at [0070]-[0082], formulas (1) and (2) at [0083]-[0094], and (but not only) lactone subunits such as those at [0119]-[0140].
Unit A1 has the following formula:
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Wherein
Xa1 is a hydrogen, methyl, or monovalent organic group discussed in [0071].
T is a single bond or divalent linking group, where preferred divalent linking groups are ester linkages and/or C1-C5 alkyl/cycloalkyl groups
Rx1-Rx3 are groups described in [0074]-[0078]
The above unit reads upon the claimed subunit for where:
RA is H or methyl
Y is a single bond or a C1-C5 alkyl/cycloalkyl group and/or an ester group
R21 is an acid labile group (the ester linkage to the tertiary organic group is aid labile)
More than one embodiment of (A1) may be used ([0079]. When using subunits conforming to the structure thereof, the reactivity of the resin and developability of the composition may be more adjustable – allowing tunability of resist performance.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by incorporating the resin (A) having subunits (A1) therein to the composition to better tune the reactivity and developability of the resin.
Regarding Claim 11, Yamaguchi discloses a pattern forming method and composition therefor as described above regarding claim 1.
Yamaguchi does not explicitly disclose an experimental embodiment of a component that meets all of the limitations of the claim.
These limitations are met by the general disclosure of the reference.
Yamaguchi discloses at [0179]-[0180] that which the composition of the reference is exposed to KrF, EB, X-Ray, or EUV (or other high energy) rays having wavelengths of 50nm or less, the resin preferably contains a hydroxystyrene-based unit, such as a hydroxystyrene based unit, and a hydroxystyrene-based units that is protected with an acid degradable group. As distinction is drawn between units that are protected and those that are not, the “hydroxystyrene-based units” not explicitly protected are interpreted as having phenolic hydroxyl groups.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by incorporating the resin (A) having subunits (A1) therein to the composition to better tune the reactivity and developability of the resin.
Regarding Claim 14, Yamaguchi discloses a pattern forming method and composition therefor as described above regarding claim 1.
Yamaguchi does not explicitly disclose an experimental embodiment of a compound that meets all of the limitations of the claim.
These limitations are met by the general disclosure of the reference.
Yamaguchi discloses that the sulfonium cations of the compound (B) comprise at least one polymerizable unsaturated group, and such groups are preferably ethylenically unsaturated groups and/or oxetanyl groups – more preferably these groups may include methacrylate groups.
Yamaguchi discloses the compound A53:
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This compound A53 meets the limitations of the claimed formula PAG-2 except where the reference’s anion has an acrylate group (versus the claimed anion having a methacrylate group) and the reference’s cation has 2 methacrylate groups and one acrylate group (versus the claimed cation having 3 methacrylate groups).
The reference compound A53 meets the limitations of the claimed compound PAG-1 except where the reference’s anion has an acrylate group (versus the claimed anion having a methacrylate group) and the reference’s cation has 1 acrylate group and 2 methacrylate groups (versus the claimed cation having 3 acrylate groups).
Acrylate and methacrylate differ in structure by one carbon atom – and the reference comprises multiple embodiments using each interchangeably (such as Compound A5, Compound A2, Compound A1, Compound A15, Compound A19, Compound A30, Compound A55, – non-exhaustively mentioned herein). The art appears to recognize these groups as equivalent, and they are substantially chemically similar and thus should be expected to behave similarly (see MPEP 2144.09). As such, a person having ordinary skill in the art would consider the substitution of acrylate groups for methacrylate groups (or vice-versa) to be an obvious modification(s) of the compound of the reference and arrive at the claimed invention from the general disclosure of the reference in order to arrive at a resist composition exhibiting higher processing performance and improved pattern resolution.
Regarding Claim 16, Yamaguchi discloses a pattern forming method and composition therefor as described above regarding claim 1.
Yamaguchi does not explicitly disclose an experimental embodiment of a compound that meets all of the limitations of the claim.
These limitations are met by the general disclosure of the reference.
The compound (B) is described from [0194]-[0361], where compound (B) has a polymerizable group preferably represented by the structure General Formula (ZI) (paragraph [0197]) and from the viewpoint of inhibiting diffusion of the generated acid, it is preferable the Z- has a polymerizable group (paragraph [0203]). The number of polymerizable groups in the compound (B) is not particularly limited and may be 1 to 10 and more preferably 1 to 3 (paragraph [0207]). In a further embodiment, the formula (Z1-4) as described in [0324]-[0360] encompasses embodiments wherein polymerizable groups R13 and R14 are present on one aromatic ring group, and a number of polymerizable groups R14 may range from 0-8. Groups R15 may be aryl groups. Z- is an anion such as the anions discussed above regarding claim 1 and further discussed in the body of the reference, such as an organic fluorosulfonic acid anion.
The reference discloses various embodiments of cations and anions across the compounds (A1-A60) and these compounds are all established to be embodiments that function equivalently by their presentation as embodiments together. For example – the cations of A5 and A4 are both mono-substituted with a polymerizable group (an acrylate and a vinyl group, respectively) on a single phenyl ring. The plain language of the disclosure states that embodiments where the phenyl ring is disubstituted (claimed subscript p=2, m=1) are envisioned. An embodiment of a bis-vinylphenyl or bis-acrylphenyl diphenylsulfonium salt present with an anion that also has a polymerizable functional group such as the anion of A12 (claimed k = 1) arrives at an embodiment that meets a preferred structural feature of the reference – the reference prefers the acid generating compound (B) to have 1-3 polymerizable groups. Incorporating additional polymerizable functional groups to the cation would arrive at increased incorporation of the cation into the polymer matrix upon irradiation, improving the resultant pattern resolution upon negative development with organic solvent by lowering the solubility of exposed portions in the solvent,
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the filing date by incorporating an additional polymerizable group to a mono-functionalized sulfonium cation in order to improve its incorporation into polymer upon exposure and improving resultant resist pattern resolution.
Claim(s) 13 is rejected under 35 U.S.C. 103 as being unpatentable over Yamaguchi (US 20120264054 A1) as applied to claim 1 above, and further in view of Aqad et al (US 20190155152 A1).
Regarding Claim 13, Yamaguchi discloses a pattern forming method and composition therefor as described above regarding claim 1.
Yamaguchi does not explicitly disclose an experimental embodiment of a compound that meets all of the limitations of the claim.
These limitations are met by Aqad.
Aqad discloses a composition comprising a sulfonium salt having a sulfonium cation and an iodophenyl-substituent-bearing anion (Abstract), such as a sulfonic acid derivative anion.
The photoacid generator is generally described at [0058] – [0080]:
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Where Y- is an anionic group such as sulfonate, carboxylate, sulfonylimide, or oxide.
Exemplary anions include those at [0083], and anions displayed as part of the salts at [0085]:
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The above anions meet the limitations of the claimed formula for where:
Subscript y is 2-3
Subscript x is 1
R11 is a hydroxy group
Subscript z is 1
X1 is an ester bond
X12 is an ethyl group
X13 is a single bond
Rf11-Fr14 are each F
Also described are resins having acid-deprotectable groups as described at [0086]-[0103]. The photoresist of the reference is preferably a negative resist ([0109]).
Both Yamaguchi and Aqad are directed to negative resists comprising acid-degradable resins and sulfonium sulfonate salts, such as Yamaguchi’s’ A12 and A53 compounds
Aqad ascribes improved sensitivity to EUV in resists that comprise iodine-rich components such as the anion of the sulfonium salt. A person having ordinary skill in the art would have found it obvious to exchange the anion of a compound from A53 or A12 of Yamaguchi for an iodinated anion of Aqad so as to improve the sensitivity of the resultant composition to EUV radiation.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ANDREW PRESTON TRAYWICK whose telephone number is (571)272-2982. The examiner can normally be reached Monday - Friday 8-5.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Mark Huff can be reached at 571-272-1385. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/A.P.T./Examiner, Art Unit 1737
/JONATHAN JOHNSON/Supervisory Patent Examiner, Art Unit 1734