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 .
The response of the applicant has been read and been given careful consideration. Rejection of the previous office action not repeated below are withdrawn ion view of the amendments to the claims. Responses to the arguments of the applicant are presented after the first rejection they are directed to. The rejections based at least in part upon Takunaga et al. WO 2020184642 are withdrawn based upon the statements of common ownership made under 102(b)(2)(C), which also is applied under (102(b)(1)(A) based upon inventors and assignees in common.
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
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.
Claims 1 and 3-8 are rejected under 35 U.S.C. 103 as being unpatentable over Enomoto et al. 20090053647, in view of Enomoto et al., 20100081081 and Endo et al. 20180181001.
Enomoto et al. 20090053647 (cited by applicant) in synthesis example 3 forms the polymer (163) [0064].
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from the precursor
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, having a weight average MW of 2500. Example 2 combines the polymer of synthesis example 3 with PGME, tetrabutoxymethylglycol uracil (crosslinkers), pyridinium p-toluene sulfonic acid (thermal acid generator), and PGME and ethyl acetate (BP-154o C) and filtered [0068]. The coatings were baked at 205 to form a resist underlayer/antireflective coating and overcoated with a resist, which was dried, exposed to light, post baked and developed [0074-0076]. The underlayer can be provided with a hardmask, then the resist, which is patterned and used to pattern the hardmask, underlying layers and semiconductor substrate [0056]. The use of high boiling solvents is disclosed including propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate, etc. may be mixed and used. Among these solvents, from viewpoint of improvement of leveling property, the following solvents are preferable: propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate (188o C), and cyclohexanone, etc [0048]. Other polymers exemplified on pages 10-14 include
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which are bounded by the formula 5,
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, where X is a single bond, methylene group, C.sub.2-10 alkylene group, a divalent hydrocarbon group having C.sub.2-10ether bond, or carbonyl group, Z is a linking group of --O-- or --OC(.dbd.O)--, Ar2 is an unsubstituted aromatic ring or an aromatic ring substituted with carboxylic acid, a carboxylic acid ester group, hydroxy group, an alkyl group, an alkoxy group, sulfonic acid group, or a halogen group The aromatic ring (Ar2) includes benzene ring, naphthalene ring, anthracene ring, or heterocyclic ring thereof containing hetero atom such as nitrogen atom or the like [0016,0034]. The phenyl ring in the novolak can be substituted as discussed at [0013,0015]. The MW can be 400-1,000,000, preferably 500-500,000, most preferably 500-300,000 [0032]. As a catalyst for accelerating the above-mentioned crosslinking reaction, an acidic compound such as p-toluene sulfonic acid, trifluoro methane sulfonic acid, pyridinium p-toluene sulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalene carboxylic acid or the like, or/and a thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, other organic sulfonic acid alkyl esters or the like can be added. The addition amount thereof is 0.0001 to 20% by weight, preferably 0.0005 to 10% by weight based on the whole solid content. In the coating-type underlayer coating forming composition for lithography of the present invention, a photoacid generator can be added in order to conform the acidity of an underlayer coating to that of a photoresist provided on the underlayer coating in lithography process. Preferable photoacid generators are for example onium salt type photoacid generators such as bis(4-t-butylphenyl)iodonium trifluoromethane sulfonate, triphenylsulfonium trifluoromethane sulfonate or the like, halogen-containing compound type photoacid generators such as phenyl-bis(trichloromethyl) s-triazine or the like, sulfonic acid type photoacid generators such as benzoin tosylate, N-hydroxysuccinimide trifluoro methane sulfonate or the like. The photoacid generator can be added in an amount of 0.2 to 10% by weight, preferably 0.4 to 5% by weight based on the whole solid content [0040-0041].
Enomoto et al., 20100081081 (cited by applicant) illustrates the polymers of 5-42, 5-43, and 5-45 on page 17.
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These are synthesized in synthesis examples 1 (MW 2500) [0085], 2 (MW 2800) [0086] and 4 (MW 3000) [0088]. These polymers are used in examples 1,2 and 4 [0105,0106,0108), where the polymers are combined with tetrabutoxymethyl uracil (crosslinking agent), pyridinium p-toluene sulfonic acid (thermal acid generator), surfactant PGMEA, PGME and cyclohexanone (BP=155.6o Cand filtered [0105,0106,0108]. These were also used in examples 15 [0119], 16 [0120], 18 [0122]. These were coated upon a silicon wafer and baked as 205 degrees C and tested. In some cases these were overcoated with a resist, which was dried, exposed, post baked and developed [0142-0148]. Other disclosed underlayer polymers include the naphtholic novolacs illustrated on pages 10-12. The exposure can use an electron beam.
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The use of polymers with molecular weights of 500-1,000,000, most preferably 700-300,000 is disclosed [0023,0055].
Endo et al. 20180181001 teaches underlayers which are epoxy adducts with alkyl group substituents. Useful epoxy polymers include those disclosed on page 5 and 6 such as
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.
The adduct can be prepared by alkoxy substituted benzoic acids, such as
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disclosed on page 7. These are evaluated on stepped silicon dioxide substrates for filling ability, where grooves/trenches with widths of 50 nm are arranged at a pitch of 100 nm [0166]. Example 18 uses NC-2000L ( MW 4800, formula 1-13, dense open=56nm), example 19 uses NC-3000L (MW 2300, formula 1-14, dense/open=56nm), example 20 uses NC-7000L (MW 2000, formula 1-15, dense/open=54nm), and example 21 uses NC-7 (MW 1400, formula 1-16, dense/open=28nm) (table 2, [0144-0151,0166])
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Enomoto et al. 20090053647 does not exemplify the polymer of the claims which requires the group
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to be present on both the naphthalene and phenyl rings of the novolak resin with a MW of less than 2200, but doe exemplify a structural isomer where the novolak has two groups attached to the naphthalene ring with the polymer having a MW of 2500.
With respect to claims 1,3-5 and 7, it would have been obvious to modify the polymer formed in synthesis example 3 of Enomoto et al. 20090053647 by replacing the diepoxide of formula 161
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with the epoxy substituted novolak polymer
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of Endo et al. 20180181001 which is known in the resist underlayer art and to form a polymer having a MW of 500-1100 based upon the ranges taught at [0032] of Enomoto et al. 20090053647 with a reasonable expectation of success in forming a useful resist underlayer polymer based upon the disclosure of the polymers with the
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on either phenyl or naphthylene groups in Enomoto et al., 20100081081.
Alternatively with respect to claims 1,3-5 and 7, it would have been obvious to modify the polymer formed in synthesis example 3 of Enomoto et al. 20090053647 by replacing the diepoxide of formula 161
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with the epoxy substituted novolak polymer
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of Endo et al. 20180181001 which is known in the resist underlayer art and to form a polymer having a MW of 500-1100 based upon the ranges taught at [0032] of Enomoto et al. 20090053647 with a reasonable expectation of success in forming a useful resist underlayer polymer based upon the disclosure of the polymers with the
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on either phenyl or naphthylene groups in Enomoto et al., 20100081081, noting the disclosure that the phenyl ring can be substituted or unsubstituted..
With respect to claims 1 and 3-7, further it would have been obvious to modify the layers rendered obvious by the combination of Enomoto et al. 20090053647, Enomoto et al., 20100081081 and Endo et al. 20180181001 by adding high boiling solvents such as butyl lactate (bp 188o C) to improve leveling as discussed at [0048] of Enomoto et al. 20090053647.
With respect to claims 1,3-5 and 7-8, further it would have been obvious to modify the layers rendered obvious by the combination of Enomoto et al. 20090053647, Enomoto et al., 20100081081 and Endo et al. 20180181001 by extending the processing to include using the photoresist to mask the etching of the underlayer and semiconductor substrate based upon the disclosure at [0056] of Enomoto et al. 20090053647.
With respect to claims 1,3-5 and 7 further it would have been obvious to modify the layers rendered obvious by the combination of Enomoto et al. 20090053647, Enomoto et al., 20100081081 and Endo et al. 20180181001 by replacing pyridinum p-toluene sulfonic acid with another of the acids or acid generators disclosed at [0040-0041] of Enomoto et al. 20090053647 based upon their equivalence as catalysts.
In response to the arguments of the applicant, the closest prior art is the polymer of synthesis example 3 of Enomoto et al. 20090053647 which is a structural isomer of the claimed compounds and has a MW only slightly outside the range recited in the claims. The applicant may have data to evidence unexpected results, but currently the data in the instant application and Enomoto et al. 20090053647 do not invite comparison. As the instant application and Enomoto et al. 20090053647 are commonly assigned, the applicant may have data available to them to compare the under layers of the instant application with the underlayers of Enomoto et al. 20090053647 using polymer 163 and amend the claims to be commensurate with any showing.
On page 4 of the response of 3/31/2025, The applicant argues that the polymers of the instant claims having MW below 1100 exhibit unexpectedly improved embeddability and planarizability evidences by the inventive examples with MW of 720-830 compared to the comparative example which has a MW of 4700. The examiner maintains the position that the showing is not commensurate in scope with the coverage sought. The none of the composition claims (1,3-7) and the process claim 8 require a substrate with any topography, such as the pattern of 50 nm grooves arranged at a 100 nm pitch. Additionally, the comparative example has the structure
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, which is not a structural isomer of the claimed polymer resin (the two anthracene containing moieties are both attached to the naphthalene, rather than one to the naphthalene and one to the phenylene as recited in the claims) in the example 3 of Enomoto et al. 20090053647 (reproduced below).
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and the comparative example has a MW almost double that of the resin of example 3 of Enomoto et al. 20090053647. It is not clear that the comparative example relied upon by the applicant represents a comparison or preferable to a direct comparison with the prior art. The applicant is invited to provide declaration evidence comparing the inventive composition and example 3 of Enomoto et al. 20090053647, noting that the assignment is the same.
The examiner also points out that Endo et al. 20180181001 teaches the filling properties in table 2 of similar polymers (without the functionalization/reaction with the carboxylic acids) with a range of MW. Examples 18 and 19, which have MW of 4800 and 2300 have dense/open of 56nm, example 20 has a MW of 54nm and example 21 has a MW of 1400 nm and a dense/open of 28 nm. This illustrates the trend that smaller polymers can more easily fit within the 50 nm grooves, which makes logical sense as longer/larger molecules are more likely to be only partially within the groove/trench with the remainder overhanging/extending beyond the dimensions of the groove
In the response of 9/12/2025, the applicant argues that the use of the polymer recited in the claims is different from that exemplified in Enomoto et al. 20090053647 and although they are structural isomers, the benefits realized by the use of the claimed composition would not have been expected by one skilled in the art. The examiner responds that Enomoto et al. 20090053647 describes Ar2 as including a unsubsttuted aromatic ring and describe naphthalene in the side chain at [0033] and benzene, naphthalene, anthracene, or derivative thereof at [0035] and the chemical formula use a notation where the point of attachment is open (attachment bond is not to a specific carbon, but rather along a side of the ring)
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.and so one skilled in the art would reasonably expect that compositions disclosed in this reference as well as obvious variants on them would function well as resist underlayers. The examiner disagrees with the applicants interpretation of Enomoto et al., 20100081081 regarding the alkyl group. The examiner points out that the disclosure that they can be Ar2 can be unsubstituted at [0063]. The examiner also points out that each of the references are concerned with underlayers. The applicant argues the embedding/filling properties, but this arguments is not commensurate in scope with the coverage sought. The composition is not applied to the substrate having trenches or grooves in any of the claims. The examiner notes that the current claims embrace coating upon a smooth surface, such as that used for the reference region of the substrate used in determining the flatness of the filling of the areas with the trenches in the instant application.
Claims 1 and 3-8 are rejected under 35 U.S.C. 103 as being unpatentable over Enomoto et al. 20090053647, in view of Enomoto et al., 20100081081 and Endo et al. 20180181001, further in view of Takei et al. 20060210915.
Takei et al. 20060210915 teaches the reaction of carboxylic acids with vinyl ethers to form resist underlayers [0056-0059]. The compound having a carboxyl group includes for example benzoic acid, isophthalic acid, terephthalic acid, pyromellitic acid, 1,2,4-trimellitic acid, adipic acid, maleic acid, butanetetracarboxylic acid, tris(2-carboxyethyl)isocyanurate, naphthalene-2-carboxylic acid, naphthalene-2,6-dicarboxylic acid, pamoic acid, pyrene-1-carboxylic acid, 1,6-dibromo-2-hydroxynaphthalene-3-carboxylic acid, 1,1'-binaphthalene-2,2'-dicarboxylic acid, anthracene-9-carboxylic acid, anthracene-9,10-dicarboxylic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, glutaric acid, 1,2-cyclohexanedicarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid, and the like. It is preferable that the compound having a protected carboxyl group of formula (1) produced from these compounds has a molecular weight of 200 or more. In case where the compound has a molecular weight less than the above, it may cause a problem that the compound sublimates during baking for forming the underlayer coating. The molecular weight is for example 200 to 2000, or for example 400 to 2000. The compound having a protected carboxyl group of formula (1) has preferably two or more protected carboxyl groups of formula (1) from the standpoint of formation of tough underlayers [0059].
In addition to the basis above, it would have been obvious to one skilled in the art to modify the compositions and processes of using them rendered obvious by the combination of Enomoto et al. 20090053647, Enomoto et al., 20100081081 and Endo et al. 20180181001 by using other aromatic absorbing carboxylic acids, such as pyrene-1-carboxylic acid based upon their prior use a reactants to form resist underlayers equivalent to naphthalene carboxylic acids and anthracene carboxylic acids in Takei et al. 20060210915 with a reasonable expectation of forming a useful resist underlayer.
The response above is relied upon as no further arguments beyond those addressed above were advanced by the applicant.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Wakamatsu et al. 20180348633 teaches the lower limit of the Mw of the calixarene resin is preferably 500, more preferably 700, and still more preferably 1,000 and thus the resist underlayer film can have further improved flatness. The upper limit of the Mw of the calixarene (structure below)resin is preferably 5,000, more preferably 3,000, and still more preferably 1,500 [0088]. There is no discussion of novolak resin MW at [0034-0046].
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THIS ACTION IS MADE FINAL. 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 Martin J Angebranndt whose telephone number is (571)272-1378. The examiner can normally be reached 7-3:30 pm EST.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Mark F Huff can be reached on 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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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 October 24, 2025