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.
Specification
Applicant is reminded of the proper content of an abstract of the disclosure.
In chemical patent abstracts for compounds or compositions, the general nature of the compound or composition should be given as well as its use, e.g., “The compounds are of the class of alkyl benzene sulfonyl ureas, useful as oral anti-diabetics.” Exemplification of a species could be illustrative of members of the class. For processes, the type of reaction, reagents and process conditions should be stated, generally illustrated by a single example unless variations are necessary.
Applicant is reminded of the proper language and format for an abstract of the disclosure.
The abstract should be in narrative form and generally limited to a single paragraph on a separate sheet within the range of 50 to 150 words in length. The abstract should describe the disclosure sufficiently to assist readers in deciding whether there is a need for consulting the full patent text for details.
The language should be clear and concise and should not repeat information given in the title. It should avoid using phrases which can be implied, such as, “The disclosure concerns,” “The disclosure defined by this invention,” “The disclosure describes,” etc. In addition, the form and legal phraseology often used in patent claims, such as “means” and “said,” should be avoided.
The abstract of the disclosure is objected to because it is less than 50 words in length and it does not disclose the general nature of the polymer, i.e. it fails to include Chemical Formula 1 and Chemical Formula 2. A corrected abstract of the disclosure is required and must be presented on a separate sheet, apart from any other text. See MPEP § 608.01(b).
Claim Objections
Claims 1, 6, 12, 15, 16, and 18 are objected to because of the following informalities: Claim 1 recites “(TAG)” which should be omitted. Claim 6 recites the following structural units A1 and A12:
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which are identical and therefore redundant. The Examiner suggests omitting A12. Claim 12 recites “(Mw)” which should be omitted. Claim 15 recites “MIBC (methyl isobutyl carbinol), ether, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), HBM (β-hydroxy β-methylbutyric acid), water, or 2-heptanone” but instead should recite --methyl isobutyl carbinol, ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, β-hydroxy β-methylbutyric acid, water, or 2-heptanone--. Claims 16 and 18 recite “(PEB)” which should be omitted. Claim 18 also recites “(PAG”) which should be omitted. Appropriate correction is required.
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.
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.
Claims 1, 2, 4-6, and 11-17 are rejected under 35 U.S.C. 103 as being unpatentable over Kaur et al. (U.S. 2018/0118968).
Kaur et al. teaches the topcoat compositions of the invention comprise a matrix polymer, a surface active polymer, an ionic thermal acid generator (TAG), a solvent, and can include one or more additional, optional components [0010] (claim 1) in which exemplary polymers useful as the surface active polymer include, for example, the following [0026]:
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[page 7] wherein the repeat unit on the right is equivalent to a first structural unit represented by Chemical Formula 1 of instant claims 1 and 2 when Ra is hydrogen and R1 is a functional group derived from sulfonic acid; and the repeat unit in the middle is equivalent to a second structural unit including at least one fluorine of instant claim 4, specifically of Chemical Formula 3 of instant claim 5, more specifically formula A4 of instant claim 6 when Rc is a methyl group. Kaur et al. also teaches exemplary suitable TAGs include, without limitation the following [0038]:
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[0038] which is equivalent to an onium salt thermal acid generator of instant claims 1 and 11. Kaur et al. further teaches the weight average molecular weight Mw of the additive polymer is typically less than 400,000, preferably from 5000 to 50,000, more preferably from 5000 to 25,000 Daltons [0027] (claim 12) and is typically present in the compositions in an amount of from 0.01 to 20 wt %, more typically from 0.1 to 10 wt % or from 1 to 5 wt %, based on total solids of the topcoat composition [0039] (claims 13 and 14). Kaur et al. also teaches a two-solvent system or a three-solvent system can be used in the topcoat compositions of the invention. The solvent system can include, for example, a primary solvent and an additive solvent and may include a thinner solvent. The primary solvent typically exhibits excellent solubility characteristics with respect to the non-solvent components of the topcoat composition. While the desired boiling point of the primary solvent will depend on the other components of the solvent system, the boiling point is typically less than that of the additive solvent, with a boiling point of from 120 to 140°C such as about 130°C being typical. Suitable primary solvents include, for example, C4 to C8 n-alcohols, such as n-butanol, isobutanol, 2-methyl-1-butanol, isopentanol, 2,3-dimethyl-1-butanol, 4-methyl-2-pentanol, isohexanol and isoheptanol, isomers thereof and mixtures thereof. The primary solvent is typically present in an amount of from 30 to 80 wt % based on the solvent system. The additive solvent is present to facilitate phase separation between the surface active polymer and other polymer(s) in the topcoat composition to facilitate a self-segregating topcoat structure. In addition, the higher boiling point additive solvent can reduce the tip drying effect during coating. It is typical for the additive solvent to have a higher boiling point than the other components of the solvent system. While the desired boiling point of the additive solvent will depend on the other components of the solvent system, a boiling point of from 170 to 200°C such as about 190°C is typical. Suitable additive solvents include, for example, hydroxy alkyl ethers. Exemplary hydroxy alkyl ethers include dialkyl glycol mono-alkyl ethers and isomers thereof, for example, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, isomers thereof and mixtures thereof. The additive solvent is typically present in an amount of from 3 to 15 wt % based on the solvent system [0042] (claim 15). Kaur et al. further teaches 200 mm silicon wafers coated with AR™ 40A antireflectant material (Dow Electronic Materials) to a dried thickness of 80 nm were spin-coated with EPIC™ 2135 photoresist and softbaked at 110°C for 90 seconds to provide a resist layer thickness of 2950 Å. Over the photoresist, each topcoat composition was coated and softbaked at 90°C for 60 seconds to provide a thickness of 385 Å (38.5 nm). Each wafer was exposed at a range of doses ranging from 27 mJ/cm2 to 43 mJ/cm2 using an ASML ArF 1100 scanner with NA=0.75, annular illumination (0.89/0.64 sigma), using a binary mask having dense trench/line pattern with feature size of 90 nm 1:1. The exposed wafers were post-exposure baked at 110° C. for 60 seconds and developed with 0.26N TMAH developer solution to form trench/line photoresist patterns of various critical dimensions (CDs) [0076] (claims 16 and 17). Kaur et al. also teaches the following non-limiting examples are illustrative of the invention [0063] and topcoat compositions of the invention can allow for beneficial water contact angle characteristics that are important in an immersion lithography process, for example, static contact angle, receding contact angle, advancing contact angle and sliding angle at the immersion fluid interface. Topcoat compositions of the invention can further provide topcoat layers having excellent developer solubility for both exposed and unexposed regions of the layer, for example, in an aqueous base developer [0013].
Therefore, it would have been obvious to one ordinary skill in the art before the effective filing date of the claimed invention to modify the specific teachings of Kaur et al. to include additional compositions such as those described above and arrive at the instant claims through routine experimentation of substituting equally suitable components for the sought invention in order to achieve optimum water contact angle characteristics and developer solubility.
Claims 7-10 are rejected under 35 U.S.C. 103 as being unpatentable over Kaur et al. (U.S. 2018/0118968) as applied to claim 4 above, and further in view of Aqad et al. (U.S. 2018/0362752).
With regard to claims 7-10, Kaur et al. teaches the above surface active polymer [page 7] and the photoresist composition (and topcoat composition if photosensitive) is typically photoactivated by a short exposure wavelength, for example, radiation having a wavelength of less than 300 nm such as 248 nm, 193 nm and EUV wavelengths [0060].
Kaur et al. does not teach a third structural unit including at least one element selected from those instantly claimed.
However, Aqad et al. teaches a monomer having formula (I) [0005] and a copolymer including a polymerized product of the monomer and an acid-deprotectable monomer [0015] and a specific example of formula (I) includes the following:
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[page 5] which is the monomeric form of a third structural unit including I of instant claims 7 and 8, specifically Chemical Formula 6 of instant claim 9, more specifically B1 of instant claim 10 when Rd is a methyl group. Aqad et al. also teach iodine has remarkably high absorption cross-section at EUV radiation. Recent patent application JP 2015-161823 discloses iodine-containing monomers and corresponding polymers useful for lithographic processing. However none of these monomers contemplated an extended chain to improve the incorporation of iodine-containing monomers. There is still a need for iodine-rich monomers and corresponding polymers that possess good solubility and that imparts improved sensitivity under EUV exposure [0004]. Further, it should be noted that the selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 65 USPQ 297 (1945). See MPEP 2144.07. In the instant case, it is well known in the resist art to use structural units in either/both resist layers and protective layers.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the teachings of Kaur et al. to include additional structural units such as the iodine-containing structural unit of Aqad et al. and arrive at the instant claims through routine experimentation of combining equally suitable components for the sought invention in order to achieve optimum sensitivity under EUV exposure.
Claims 1-6 and 11-20 are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama et al. (U.S. 2008/0096131) in view of Kaur et al. (U.S. 2018/0118968).
Hatakeyama et al. teaches the resist composition of the invention is defined as comprising a polymer which increases its alkali solubility under the action of an acid as a base resin, and a copolymer comprising recurring units containing a sulfonic acid amine salt and recurring units containing at least one fluorine atom as an additive [0034]. Hatakeyama et al. also teaches the recurring units containing a sulfonic acid amine salt and recurring units containing at least one fluorine atom are represented by the general formula (1) [0035]:
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[0035] wherein examples of suitable polymerizable monomers from which recurring units (a-2) are derived are given below [0043]:
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[0043] wherein R3 is hydrogen or methyl and R4 is hydrogen or a straight, branched or cyclic C1-C20 alkyl group or C2-C20 alkenyl group which may contain a hydroxy, ether, ester, cyano, amino group, double bond or halogen atom, or a C6-C10 aryl group, two, three or four R4 may bond together to form a ring of 3 to 20 carbon atoms [0035] which is the monomeric form of a first structural unit represented by Chemical Formula 1 of instant claims 1-3 when Ra is hydrogen or a methyl group and R1 is a functional group derived from L8SO3-Q+ where L8 is a substituted C6 arylene and Q+ is an ammonium ion. Hatakeyama et al. further teaches a pattern forming process comprising the steps of applying the aforementioned resist composition onto a substrate to form a coating, heat treating the coating and exposing it to high-energy radiation, and developing the exposed coating with a developer. The step of heat treatment may be included after the exposing step and before the developing step. The process may further include subsequent steps such as etching, resist removal and cleaning. Preferably the high-energy radiation has a wavelength of 180 to 250 nm. In preferred embodiments, the exposing step is by immersion lithography involving exposing the coating to high-energy radiation through a liquid. The process may further comprise the step of forming a protective coating so that the protective coating intervenes between the photoresist coating and the liquid during the immersion lithography. The protective coating is typically an alkali-soluble protective film based on a polymer having an α-trifluoromethylhydroxy group [0027-0028] and the polymers having α-trifluoromethylalcohol groups may be obtained through polymerization of monomers similar to the monomers from which recurring units (b-1) in formula (1) are derived. Also, monomers similar to the monomers from which recurring units (b-2) in formula (1) are derived may be copolymerized for preventing water penetration and/or improving a receding contact angle. Moreover, monomers having alkali-soluble groups in the form of α-trifluoromethylalcohol groups as shown below may be polymerized [0327]:
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[0327] which is the monomeric form of a second structural unit including at least one fluorine atom of instant claim 4, specifically Chemical Formula 4 of instant claim 5, more specifically A17 of instant claim 6; examples of suitable monomers from which recurring units (b-1) having an α-trifluoromethylalcohol group in formula (1) are derived are given below [0046]:
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[page 12] wherein R5 is hydrogen or methyl [0035] which is the monomeric form of a second structural unit including at least one fluorine of instant claim 4, specifically of Chemical Formula 3 of instant claim 5, more specifically formula A20 of instant claim 6 when Rc is hydrogen or a methyl group; Examples of recurring units (b-2) in formula (1) are given below [0047]:
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[0047] wherein R8 is hydrogen or methyl [0035] which is the monomeric form of a second structural unit including at least one fluorine of instant claim 4, specifically of Chemical Formula 3 of instant claim 5, more specifically formula A2 of instant claim 6 when Rc is hydrogen or a methyl group; and also, monomers having a water repellent group may be polymerized [0328]. Hatakeyama et al. further teaches although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims [0371] and an object of the invention is to provide a photoresist composition which when coated as photoresists, forms a resist layer having a surface modified so as to contain an amine salt of sulfonic acid, wherein the resist layer prevents intermixing between resist and protective layers when a protective layer is formed on the resist layer, and the resist layer on Its surface is more hydrophilic after exposure and development, thus preventing blob defects from generating, and which composition, when used as electron beam resists, is effective for preventing accumulation of charge on the resist film surface due to charging during e-beam exposure [0008].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the protective film to include additional repeating units such as recurring units (a-2) in formula (1) of the resist polymer and arrive at the instant claims through routine experimentation of combining equally suitable components for the sought invention with a reasonable expectation of success.
Hatakeyama et al. does not teach a thermal acid generator.
However, Kaur et al. teaches the topcoat compositions of the invention comprise a matrix polymer, a surface active polymer, an ionic thermal acid generator (TAG), a solvent, and can include one or more additional, optional components [0010] wherein exemplary suitable TAGs include, without limitation the following [0038]:
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[0038] which is equivalent to an onium salt thermal acid generator of instant claims 1 and 11. Kaur et al. also teaches the weight average molecular weight Mw of the additive polymer is typically less than 400,000, preferably from 5000 to 50,000, more preferably from 5000 to 25,000 Daltons [0027] (claim 12) and is typically present in the compositions in an amount of from 0.01 to 20 wt %, more typically from 0.1 to 10 wt % or from 1 to 5 wt %, based on total solids of the topcoat composition [0039] (claims 13 and 14). Kaur et al. further teaches use of an ionic TAG compound as described herein may provide improvements in pattern collapse properties as compared with topcoat compositions lacking such a compound or other acid source. The TAG, when heated at or above its activation temperature, generates the corresponding conjugate acid. In the case of a positive-acting photoresist composition, the generated acid is believed to provide thickness loss to the generated photoresist pattern in unexposed regions at the surface of the photoresist layer due to acid-catalyzed deprotection reaction in those regions. Such thickness loss is believed to improve (lessen) the occurrence of pattern collapse defects. Use of an ionic TAG is further believed to improve shelf life stability of the topcoat compositions as compared with use of a free acid in the compositions [0029].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the teachings of Hatakeyama et al. to additionally include a thermal acid generator as taught by Kaur et al. and arrive at the instant claims through routine experimentation of combining equally suitable components for the sought invention in order to achieve optimum pattern collapse properties and shelf life stability.
With regard to claim 12, Hatakeyama et al. teaches the polymer for the protective coating should preferably have a weight average molecular weight of 1,000 to 100,000 [0330].
With regard to claim 15, Hatakeyama et al. teaches the solvent used for protective coating is not particularly limited although those solvents in which resist layers can be dissolved should be avoided. It is recommended to avoid the use of conventional resist solvents, for example, ketones such as cyclohexanone and methyl-2-n-amylketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate [0331].
With regard to claims 16-20, Hatakeyama et al. teaches a pattern forming process comprising the steps of applying the aforementioned resist composition onto a substrate to form a coating, heat treating the coating, exposing it to high-energy radiation, and developing the exposed coating with a developer [0334] in which the coating is prebaked on a hot plate at 50 to 150°C for about 1 to 10 minutes, preferably at 60 to 140.degree. C. for 1 to 5 minutes [0336], and after a photoresist layer is formed on a wafer, a water-insoluble, alkali-soluble resist protective coating material is applied to the photoresist layer by suitable techniques, typically spin coating. The coating thickness is preferably in a range of 10 to 500 nm. After spin coating, the resist protective coating is baked at a temperature of 40 to 130°C for 10 to 300 seconds for evaporating off the solvent [0339]. Hatakeyama et al. also teaches in the resist composition of the invention, the polymeric surfactant(s) of formula (1) may be compounded in a total amount of 0.01 to 50 parts by weight, and preferably 0.1 to 10 parts by weight per 100 parts by weight of the base resin [0056] in which the polymeric surfactant is equivalent to the instantly claimed topcoat composition and the base resin is equivalent to the instantly claimed photosensitive polymer (claim 19). Hatakeyama et al. further teaches preferably the resist composition further comprises at least one member selected from among an organic solvent, a basic compound, a dissolution regulator, a crosslinker, and a surfactant [0025] (claim 20).
Claims 7-10 are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama et al. (U.S. 2008/0096131) in view of Kaur et al. (U.S. 2018/0118968) as applied to claim 4 above, and further in view of Aqad et al. (U.S. 2018/0362752).
With regard to claims 7-10, Hatakeyama in view of Kaur teach the above topcoat composition.
Hatakeyama in view of Kaur do not teach a third structural unit including at least one element selected from those instantly claimed.
However, Aqad et al. teaches a monomer having formula (I) [0005] and a copolymer including a polymerized product of the monomer and an acid-deprotectable monomer [0015] and a specific example of formula (I) includes the following:
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[page 5] which is the monomeric form of a third structural unit including I of instant claims 7 and 8, specifically Chemical Formula 6 of instant claim 9, more specifically B1 of instant claim 10 when Rd is a methyl group. Aqad et al. also teach iodine has remarkably high absorption cross-section at EUV radiation. Recent patent application JP 2015-161823 discloses iodine-containing monomers and corresponding polymers useful for lithographic processing. However none of these monomers contemplated an extended chain to improve the incorporation of iodine-containing monomers. There is still a need for iodine-rich monomers and corresponding polymers that possess good solubility and that imparts improved sensitivity under EUV exposure [0004]. Further, it should be noted that the selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 65 USPQ 297 (1945). See MPEP 2144.07. In the instant case, it is well known in the resist art to use structural units in either/both resist layers and protective layers.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the teachings of Hatakeyama and Kaur to include additional structural units such as the iodine-containing structural unit of Aqad et al. and arrive at the instant claims through routine experimentation of combining equally suitable components for the sought invention in order to achieve optimum sensitivity under EUV exposure.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. U.S. 2022/0214619 and U.S. 2018/0120703.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ANNA E MALLOY whose telephone number is (571)270-5849. The examiner can normally be reached 8:00-4:30 EST M-F.
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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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/Anna Malloy/Examiner, Art Unit 1737
/MARK F. HUFF/Supervisory Patent Examiner, Art Unit 1737