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
Acknowledgment is made of applicant's claim for foreign priority based on an application filed in Japan on June 10, 2022. It is noted, however, that applicant has not filed a certified copy of the JP2022-094363 application as required by 37 CFR 1.55.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
Claims 7-12 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 7 recites “and “n” represents an integer of 1 to 10”. However, n cannot be 1 since claim 7 also recites “0.70 ≤ a ≤ 0.99, and 0.01 ≤ b ≤ 0.30, where “a” represents a proportion of the structure represented by the formula (8) and “b” represents a proportion of the structure represented by the formula (9)”. Thus, n must be at least 2.
Claims 8-12 are rejected because they depend from rejected based claim 7.
Double Patenting
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the conflicting claims are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on nonstatutory double patenting provided the reference application or patent either is shown to be commonly owned with the examined application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. See MPEP § 717.02 for applications subject to examination under the first inventor to file provisions of the AIA as explained in MPEP § 2159. See MPEP § 2146 et seq. for applications not subject to examination under the first inventor to file provisions of the AIA . A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The filing of a terminal disclaimer by itself is not a complete reply to a nonstatutory double patenting (NSDP) rejection. A complete reply requires that the terminal disclaimer be accompanied by a reply requesting reconsideration of the prior Office action. Even where the NSDP rejection is provisional the reply must be complete. See MPEP § 804, subsection I.B.1. For a reply to a non-final Office action, see 37 CFR 1.111(a). For a reply to final Office action, see 37 CFR 1.113(c). A request for reconsideration while not provided for in 37 CFR 1.113(c) may be filed after final for consideration. See MPEP §§ 706.07(e) and 714.13.
The USPTO Internet website contains terminal disclaimer forms which may be used. Please visit www.uspto.gov/patent/patents-forms. The actual filing date of the application in which the form is filed determines what form (e.g., PTO/SB/25, PTO/SB/26, PTO/AIA /25, or PTO/AIA /26) should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to www.uspto.gov/patents/apply/applying-online/eterminal-disclaimer.
Claims 1-6, 13, 14, 16, and 17 rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-8 of U.S. Patent No. 7,358,025. Although the claims at issue are not identical, they are not patentably distinct from each other because both the instant claims and patented claims are directed to underlayer film material comprising a compound or resin having a phenolic hydroxy group, a base generator, a solvent, and a crosslinking agent. Formula (1) or resin of formula (2) of ‘025 when defined as: R1-R4 are hydrogen and Z is a divalent C13 hydrocarbon group containing a fused polycyclic hydrocarbon group encompass the instantly claimed compound or resin having a phenolic hydroxy group. The acid generator in claim 4 of ‘025 encompasses the instantly claimed base generator. Claims 5-8 of ‘025 encompass instant claims 16 and 17.
Claims 1-14, 16-20, and 22-25 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1, 2, and 5-14 of U.S. Patent No. 9,728,420. Although the claims at issue are not identical, they are not patentably distinct from each other because both the instant claims and patented claims are directed to underlayer film material comprising a compound or resin having a phenolic hydroxy group, a base generator, a solvent, a crosslinking agent, and a surfactant. Formula (4) of ‘420 when defined as: Q1 is a substituted phenyl group and/or naphthyl group,
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,
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encompass the instantly claimed compound having a phenolic hydroxy group, specifically formula (7) when formula (8) is any one of formula (10) to (12), formula (9) is formula (13) or (14), and W represents formula (15) where W1 represents
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, R15 is a hydrogen atom, and Y is a carbonyl group. The acid generator in claim 5 of ‘420 encompasses the instantly claimed base generator. Claims 6-14 of ‘420 encompass instant claims 16-20 and 22-25.
Claims 1-6, 13, 14, 16-20, 22, and 25 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-21 of U.S. Patent No. 10,416,563. Although the claims at issue are not identical, they are not patentably distinct from each other because both the instant claims and patented claims are directed to underlayer film material comprising a compound having a phenolic hydroxy group, a base generator, a solvent, a crosslinking agent, a surfactant, a plasticizer, and colorant. Formula (1) of ‘563 encompasses the instantly claimed compound having a phenolic hydroxy group. The acid generator in claim 7 of ‘563 encompasses the instantly claimed base generator. Claims 10-21 of ‘563 encompass instant claims 16-20, 22, and 25.
Claims 1-26 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-11 of U.S. Patent No. 12,147,160. Although the claims at issue are not identical, they are not patentably distinct from each other because both the instant claims and patented claims are directed to underlayer film material comprising a compound or resin having a phenolic hydroxy group, a base generator, a solvent, a crosslinking agent, a surfactant, a plasticizer, and colorant. Formula (1) of ‘160 encompasses the instantly claimed compound having a phenolic hydroxy group, specifically formula (7) when formula (8) is any one of formula (10) to (12), formula (9) is formula (13) or (14), and W represents formula (15). The acid generator in claim 3 of ‘160 encompasses the instantly claimed base generator. Claims 4-11 of ‘160 encompass instant claims 16-26.
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 § 102
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.
Claims 1, 3-6, and 13 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Takada et al. (WO2021153466). U.S. 2022/0382153 is being used as the English translation.
Takada et al. teaches a composition in Example Re-13 comprising resin A-5, ionic compounds B-11 and B-10, and solvents F-1, F-2, and F-5 [0626] wherein resin A-5 is the following:
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[0605] which is equivalent to a resin having a phenolic hydroxy group of instant claim 1; ionic compound B-11 is the following:
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[p 30] which is equivalent to a base generator of instant claims 1 and 3, specifically general formula (1) of instant claim 4 when R01-R03 are aryl groups having 6 carbon atoms and X- is general formula (4) of instant claim 5 when R10 is a linear hydrocarbon group having 3 carbon atoms substituted with halogen atoms in which the conjugate acid CF3(CF2)2COOH is known to have a boiling point of 120°C (claim 6); and solvent F-1 is propylene glycol monomethyl ether acetate (PGMEA), solvent F-2 is propylene glycol monomethyl ether (PGME), and solvent F-5 is γ-butyrolactone [0613-0617] in which PGMEA is known to have a boiling point of 145°C, PGME is known to having a boiling point of 120°C, and γ-butyrolactone is known to have a boiling point of 204°C (claims 1 and 13).
Claims 1, 3-6, and 13 recite “resist underlayer film material” which has not been given patentable weight because the recitation occurs in the preamble. A preamble is generally not accorded any patentable weight where it merely recites the purpose of a process or the intended use of a structure, and where the body of the claim does not depend on the preamble for completeness but, instead, the process steps or structural limitations are able to stand alone. See In re Hirao, 535 F.2d 67, 190 USPQ 15 (CCPA 1976) and Kropa v. Robie, 187 F.2d 150, 152, 88 USPQ 478, 481 (CCPA 1951).
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 1-26 are rejected under 35 U.S.C. 103 as being unpatentable over Kori et al. (U.S. 2022/0163890), incorporating Hatakeyama et al. (JP2007199653) by reference. Translation attached. ‘890 corresponds to U.S. Patent No. 12,147,160 above.
Kori et al. teaches a resist underlayer film material for use in a multilayer resist method, comprising: (A) one or more compounds shown by the following general formula (1); and (B) an organic solvent [0078-0080] (claim 1) wherein a specific example of general formula (1) includes the following compound 2:
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[0200] which has a weight-average molecular weight of 1120 [0200] (claim 2) which is equivalent to a compound having a phenolic hydroxy group of instant claim 1, specifically general formula (7) of instant claims 7 and 8 when n is 2 where a is 0.918 and b is 0.082, one Y is represented by formula (8), specifically formula (10) of instant claim 9, the other Y is represented by formula (9), specifically formula (13) of instant claim 10, and W is represented by general formula (15) of instant claim 11 when R15 is a hydrogen atom, Y is a carbonyl group, and W1 is
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of instant claim 12. Kori et al. also teaches the organic solvent is preferably a mixture of one or more organic solvents each having a boiling point of lower than 180°C and one or more organic solvents each having a boiling point of 180°C or higher [0115] (claim 13). Kori et al. further teaches in the inventive resist underlayer film material, (C) an acid generator can be added so as to further promote the curing reaction. The acid generator includes a material that generates an acid by thermal decomposition, and a material that generates an acid by light irradiation. Any acid generator can be added. Specifically, materials disclosed in paragraphs [0061] to [0085] of JP 2007-199653 A (Hatakeyama) can be added, but the present invention is not limited thereto [0120] (claims 1 and 3). Hatakeyama et al. teaches examples of the acid generators used in the present invention include onium salts of the following general formula (P1a-1), (P1a-2), (P1a-3) [0062]:
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[0063] wherein R101a, R101b, R101c represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and a part or all of hydrogen atoms of these groups may be substituted with an alkoxy group or the like, R101b and R101c may form a ring, and in a case where a ring is formed, R101b, R101c represents an alkylene group having 1 to 6 carbon atoms, and K- represents a non-nucleophilic counter ion [0063] in which examples of the non-nucleophilic counter ion represented by K- include halide ions such as a chloride ion and a bromide ion, arylsulfonates such as tosylate, benzenesulfonate and alkylsulfonates such as mesylate and butanesulfonate [0064], e.g. p-tolylsulfonyloxy tetramethylammonium salt, p-tolylsulfonyloxy diphenyliodonium, triphenylsulfonium butanesulfonate, p-tolylsulfonyloxy(p-tert-butoxyphenyl ester)diphenylsulfonium, p-tolylsulfonyloxy bis(p-tert-butoxyphenyl ester)phenylsulfonium, p-tolylsulfonyloxy trimethylsulfonium p-tolylsulfonyloxy tr is(p-tert-butoxyphenyl ester)sulfonium, p-tolylsulfonyloxy triphenylsulfonium, p-tolylsulfonyloxy dimethylphenylsulfonium, and p-tolylsulfonyloxy dicyclohexylphenyl sulfonium [0077] which is equivalent to a base generator of instant claim 1, specifically any one of formulae (1) to (3) of instant claims 4 and 5 when R01-R09 are linear or cyclic alkyl groups having 1-10 carbon atoms or aryl groups having 6 carbon atoms and X- is a chloride ion, a bromide ion, formula (5) when R11 is an aryl group having 6-7 carbon atoms, or formula (6) when R12 and R13 are hydrogen atoms and R4 is a hydrogen atom or a linear hydrocarbon group having 3 carbon atoms in which the conjugate acids hydrogen chloride, hydrogen bromide, toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, and butanesulfonic acid are known to have boiling points of -85°C, -66°C, 140°C, 190°C, 167C, and 134°C respectively (claim 6). Kori et al. also teaches the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited thereto [0194] and it should be noted that the present invention is not limited to the above-described embodiments. The embodiments are just examples, and any examples that have substantially the same feature and demonstrate the same functions and effects as those in the technical concept disclosed in claims of the present invention are included in the technical scope of the present invention [0229]. Kori et al. further teaches an object of the present invention is to provide: a resist underlayer film material in a fine patterning process by a multilayer resist method in a semiconductor device manufacturing process, where the resist underlayer film material makes it possible to form a resist underlayer film excellent in flatness and film-formability even on a substrate to be processed having portions that are particularly difficult to planarize such as a wide trench structure, and the material further has an appropriate etching property and optical characteristics; a patterning process in which the material is used; and a method for forming a resist underlayer film [0014].
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 specific teachings of Kori et al. to include an acid generator such as those in Hatakeyama which are incorporated by reference through routine experimentation of combining equally suitable components for the sought invention in order to achieve optimum flatness, and film-formability.
With regard to claims 14 and 15, Kori et al. teaches to the inventive resist underlayer film material, (D) a surfactant can be added so as to enhance the coating property in spin-coating [0122], (F) a plasticizer can be added so as to enhance the planarizing and filling properties further [0138], (G) a colorant can be added so as to enhance the resolution during patterning in multilayer lithography further [0139] and (E) a crosslinking agent can also be added so as to increase the curability and to further suppress intermixing with an upper layer film [0123] (claim 14) and specific examples of the crosslinking agents include compounds shown by the following general formula (10) [0133]:
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[0133] wherein Q represents a single bond or a hydrocarbon group with a valency of “q” having 1 to 20 carbon atoms. R2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. “q” represents an integer of 1 to 5 [0134] which is equivalent to a crosslinker (E) represented by general formula (16) of instant claim 15.
With regard to claims 16-26, Kori et al. teaches the present invention provides a patterning process for forming a pattern in a substrate to be processed, including the steps of: (I-1) applying the above-described resist underlayer film material on the substrate to be processed and then performing a heat treatment to form a resist underlayer film; (I-2) forming a resist upper layer film on the resist underlayer film by using a photoresist material; (I-3) subjecting the resist upper layer film to pattern exposure and then to development with a developer to form a pattern in the resist upper layer film; (I-4) transferring the pattern to the resist underlayer film by dry etching while using the resist upper layer film having the formed pattern as a mask; and (I-5) processing the substrate to be processed while using the resist underlayer film having the formed pattern as a mask to form the pattern in the substrate to be processed (2-layer resist process). Furthermore, the present invention provides a patterning process for forming a pattern in a substrate to be processed, including the steps of: (II-1) applying the above-described resist underlayer film material on the substrate to be processed and then performing a heat treatment to form a resist underlayer film; (II-2) forming a resist middle layer film on the resist underlayer film; (II-3) forming a resist upper layer film on the resist middle layer film by using a photoresist material; (II-4) subjecting the resist upper layer film to pattern exposure and then to development with a developer to form a pattern in the resist upper layer film; (II-5) transferring the pattern to the resist middle layer film by dry etching while using the resist upper layer film having the formed pattern as a mask; (II-6) transferring the pattern to the resist underlayer film by dry etching while using the resist middle layer film having the transferred pattern as a mask; and (II-7) processing the substrate to be processed while using the resist underlayer film having the formed pattern as a mask to form the pattern in the substrate to be processed (3-layer resist process). Additionally the present invention provides a patterning process for forming a pattern in a substrate to be processed, including the steps of: (III-1) applying the above-described resist underlayer film material on the substrate to be processed and then performing a heat treatment to form a resist underlayer film; (III-2) forming an inorganic hard mask middle layer film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) forming an organic thin film on the inorganic hard mask middle layer film; (III-4) forming a resist upper layer film on the organic thin film by using a photoresist material; (III-5) subjecting the resist upper layer film to pattern exposure and then to development with a developer to form a pattern in the resist upper layer film; (III-6) transferring the pattern to the organic thin film and the inorganic hard mask middle layer film by dry etching while using the resist upper layer film having the formed pattern as a mask; (III-7) transferring the pattern to the resist underlayer film by dry etching while using the inorganic hard mask middle layer film having the transferred pattern as a mask; and (III-8) processing the substrate to be processed while using the resist underlayer film having the formed pattern as a mask to form the pattern in the substrate to be processed (4-layer resist process) [0140-0162]. Kori et al. also teaches when an inorganic hard mask middle layer film is formed on the resist underlayer film as described above, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) is formed by a CVD method, an ALD method, or the like [0168]. Kori et al. further teaches the inventive patterning processes are also suitable for processing a stepped substrate having a structure or a step with a height of 30 nm or more [0176]. Kori et al. also teaches the present invention provides a method for forming a resist underlayer film that functions as an organic flat film employed in a semiconductor device manufacturing process, the method including: spin-coating a substrate to be processed with the above-described resist underlayer film material; and heating the substrate coated with the resist underlayer film material at a temperature of 100°C or higher to 600°C or lower for 10 to 600 seconds to form a cured film. In addition, the present invention provides a method for forming a resist underlayer film that functions as an organic flat film employed in a semiconductor device manufacturing process, the method including: spin-coating a substrate to be processed with the above-described resist underlayer film material; and heating the substrate coated with the resist underlayer film material in an atmosphere having an oxygen concentration of 1% or more to 21% or less to form a cured film. Alternatively, the present invention provides a method for forming a resist underlayer film that functions as an organic flat film employed in a semiconductor device manufacturing process, the method including: spin-coating a substrate to be processed with the above-described resist underlayer film material; and heating the substrate coated with the resist underlayer film material in an atmosphere having an oxygen concentration of less than 1% to form a cured film [0182-0190]. Kori et al. further teaches each of the resist underlayer film materials (UDL-1 to -18, comparative UDL-1 to -5) prepared above were applied onto each of a Bare-Si substrate, a substrate treated with hexamethyldisilazane (HMDS), and a substrate treated with SiON, which are shown in Table 10, and baked at 250°C for 60 seconds to form a resist underlayer film with a film thickness of 100 nm [0206] in which a hexamethyldisilazane (HDMS)-treated substrate has a static contact angle with respect to water of 50° or more based on page 90 of instant specification.
Claims 1-14 and 16-26 are rejected under 35 U.S.C. 103 as being unpatentable over Kori et al. (U.S. 9,728,420), incorporating Hatakeyama et al. (JP2007199653) by reference.
Kori et al. teaches an organic film composition comprising a compound represented by the following general formula (1) [col 10 lines 40-42]:
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[col 10 line 45] wherein n1 and n2 can be 1, m1 and m2 can be 1, W can be
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[col 10 lines 52-60],
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[col 11 line 20], and Q1 can be a substituted phenyl group and/or naphthyl group [col 11 lines 36-39], and illustrative examples of the substituent include a hydrocarbon group and a hydroxyl group [col 20 lines 21-22] moreover, the compound represented by the general formula (1) preferably has two or more Q1 in the molecule [col 20 lines 27-28] one or both can be of the following general formula (7):
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[col 20 line 40] wherein n5 can be 0 or 1, n3 can be 1 or 2 where Rj can be a hydrogen atom or a linear hydrocarbon group having 3 carbon atoms, and n4 can be 0 [col 20 lines 49-59], e.g.
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seen in synthesis example 4 [col 43-44] and
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seen in synthesis example 8 [col 45-46]. Kori et al. also teaches in synthesis example 15 a compound comprising a 50:50 ratio of two aromatic rings representative of Kori’s formula (7) [col 51-52]. Thus, when formula (1) of Kori et al. has two Q1 represented by formula (7) as defined above it is equivalent to a compound having a phenolic hydroxy group of instant claim 1, specifically general formula (7) of instant claims 7 and 8 when formula (8) is represented by general formula (10) of instant claim 9, general formula (9) is represented by general formula (13) of instant claim 10, and W represents general formula (15) of instant claim 11 where W1 represents
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of instant claim 12, R15 is a hydrogen atom, Y is a carbonyl group, and 0.70 ≤ a ≤ 0.99 and 0.01 ≤ b ≤ 0.30. Kori et al. also teaches all of the compounds synthesized in the examples have a molecular weight ranging from 760-1890 [col 41-col 54]. Thus, one of ordinary skill in the art would expect the compound described above to have a molecular weight of 3,000 or less, absent any evidence to the contrary (claim 2). Kori et al. further teaches into the organic film composition of the present invention, (A) an acid generator and (B) a cross-linking agent can be added to further accelerate a thermal cross-linking reaction. As (A) the acid generators, it is possible to add any of the one which generates an acid by thermal decomposition and the one which generates an acid by light irradiation. Specifically, compositions described in paragraphs (0061) to (0085) of JP 2007-199653A (Hatakeyama) can be added. As (B) the cross-linking agent usable for the organic film composition of the present invention, materials described in paragraphs (0055) to (0060) of JP 2007-199653A (Hatakeyama) can be added [col 30 lines 25-36] (claims 1, 3, and 14). Hatakeyama et al. teaches examples of the acid generators used in the present invention include onium salts of the following general formula (P1a-1), (P1a-2), (P1a-3) [0062]:
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[0063] wherein R101a, R101b, R101c represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and a part or all of hydrogen atoms of these groups may be substituted with an alkoxy group or the like, R101b and R101c may form a ring, and in a case where a ring is formed, R101b, R101c represents an alkylene group having 1 to 6 carbon atoms, and K- represents a non-nucleophilic counter ion [0063] in which examples of the non-nucleophilic counter ion represented by K- include halide ions such as a chloride ion and a bromide ion, arylsulfonates such as tosylate, benzenesulfonate and alkylsulfonates such as mesylate and butanesulfonate [0064], e.g. p-tolylsulfonyloxy tetramethylammonium salt, p-tolylsulfonyloxy diphenyliodonium, triphenylsulfonium butanesulfonate, p-tolylsulfonyloxy(p-tert-butoxyphenyl ester)diphenylsulfonium, p-tolylsulfonyloxy bis(p-tert-butoxyphenyl ester)phenylsulfonium, p-tolylsulfonyloxy trimethylsulfonium p-tolylsulfonyloxy tris(p-tert-butoxyphenyl ester)sulfonium, p-tolylsulfonyloxy triphenylsulfonium, p-tolylsulfonyloxy dimethylphenylsulfonium, and p-tolylsulfonyloxy dicyclohexylphenyl sulfonium [0077] which is equivalent to a base generator of instant claim 1, specifically any one of formulae (1) to (3) of instant claims 4 and 5 when R01-R09 are linear or cyclic alkyl groups having 1-10 carbon atoms or aryl groups having 6 carbon atoms and X- is a chloride ion, a bromide ion, formula (5) when R11 is an aryl group having 6-7 carbon atoms, or formula (6) when R12 and R13 are hydrogen atoms and R4 is a hydrogen atom or a linear hydrocarbon group having 3 carbon atoms in which the conjugate acids hydrogen chloride, hydrogen bromide, toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, and butanesulfonic acid are known to have boiling points of -85°C, -66°C, 140°C, 190°C, 167C, and 134°C respectively (claim 6). Kori et al. also teaches the present invention is explained in more detail by referring to Synthesis Examples, Comparative Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited thereto [col 36 lines 22-25] and it should be noted that the present invention is not limited to the foregoing embodiments. The embodiment is just an exemplification, and any examples that have substantially the same feature and demonstrate the same functions and effects as those in the technical concept described in claims of the present invention are included in the technical scope of the present invention [col 64 line 58-col 65 line 3]. Kori et al. further teaches By using the inventive organic film composition to form a multilayer resist film which is applied to a fine processing in the manufacturing step of a semiconductor apparatus and so on, it is possible to provide a resist under layer film composition for forming a resist under layer film having both of high dry etching resistance and high filling/planarizing characteristics. It is also possible to provide a planarizing composition for manufacturing a semiconductor apparatus with excellent filling/planarizing characteristics applicable to planarization in the manufacturing step of a semiconductor apparatus other than multilayer resist processes [col 6 lines 5-15].
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 specific teachings of Kori et al. to include an acid generator such as those in Hatakeyama which are incorporated by reference through routine experimentation of combining equally suitable components for the sought invention in order to achieve optimum dry etching resistance and filling/planarizing characteristics.
With regard to claims 13 and 14, Kori et al. teaches as (D) the organic solvent usable in the organic film composition of the present invention, those which can dissolve (A) an acid generator, (B) a cross-linking agent, and (C) a surfactant are preferred. Specifically, the solvents described in paragraphs (0091) to (0092) of JP 2007-199653A can be added. Of these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, γ-butyrolactone, and a mixture of two or more kinds of these solvents are preferably used [col 30 lines 42-51] in which PGMEA is known to have a boiling point of 145°C, PGME is known to having a boiling point of 120°C, and γ-butyrolactone is known to have a boiling point of 204°C. Kori et al. also teaches further, into the organic film composition of the present invention, (C) a surfactant can be added to improve coating property in spin coating [col 30 lines 37-39].
With regard to claims 16-20 and 21-25, Kori et al. teaches the present invention also provides a process for forming an organic film which is used as a resist under layer film of a multilayer resist film used in lithography or a planarizing film for manufacturing a semiconductor apparatus, comprising: coating a substrate to be processed with the foregoing organic film composition, and subjecting the organic film composition to heat treatment at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to form a cured film. The present invention also provides a process for forming an organic film which is used as a resist under layer film of a multilayer resist film used in lithography or a planarizing film for manufacturing a semiconductor apparatus, comprising: coating a substrate to be processed with the foregoing organic film composition, and baking the organic film composition under an atmosphere with an oxygen concentration of 0.1% or more and 21% or less to form a cured film. The inventive organic film composition is excellent in filling/planarizing characteristics, so that it is particularly useful for forming a planarizing organic film on the substrate having a structure or step(s) each with a height of 30 nm or more. The present invention also provides a patterning process which is a process for forming a pattern on a substrate to be processed, comprising at least the steps of: forming a resist under layer film on the substrate to be processed by using the foregoing organic film composition; forming a resist middle layer film on the resist under layer film by using a resist middle layer film composition containing a silicon atom; forming a resist upper layer film on the resist middle layer film by using a resist upper layer film composition comprising a photoresist composition, to form a multilayer resist film; forming a resist pattern on the resist upper layer film by exposing a pattern circuit region of the resist upper layer film and then developing the same with a developer; forming a resist middle layer film pattern by etching the resist middle layer film using the obtained resist pattern as an etching mask; forming a resist under layer film pattern by etching the resist under layer film using the obtained resist middle layer film pattern as an etching mask; and further forming a pattern on the substrate to be processed by etching the substrate to be processed using the obtained resist under layer film pattern as an etching mask. In such a multilayer resist process, the patterning process using the inventive organic film composition can form a fine pattern on the substrate to be processed with high precision. In this case, the step of etching the resist under layer film using the obtained resist middle layer film as an etching mask is preferably performed by using an etching gas mainly comprising an oxygen gas or a hydrogen gas. The present invention also provides a patterning process which is a process for forming a pattern on a substrate to be processed, comprising at least the steps of: forming a resist under layer film on the substrate to be processed by using the foregoing organic film composition; forming an inorganic hard mask middle layer film selected from any one of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist under layer film; forming a resist upper layer film on the inorganic hard mask middle layer film by using a resist upper layer film composition comprising a photoresist composition, to form a multilayer resist film; forming a resist pattern on the resist upper layer film by exposing a pattern circuit region of the resist upper layer film and then developing the same with a developer; forming an inorganic hard mask middle layer film pattern by etching the inorganic hard mask middle layer film using the obtained resist pattern as an etching mask; forming a resist under layer film pattern by etching the resist under layer film using the obtained inorganic hard mask middle layer film pattern as an etching mask; and further forming a pattern on the substrate to be processed by etching the substrate to be processed using the obtained resist under layer film pattern as an etching mask. Further, the present invention provides a patterning process which is a process for forming a pattern on a substrate to be processed, comprising at least the steps of: forming a resist under layer film on the substrate to be processed by using the foregoing organic film composition; forming an inorganic hard mask middle layer film selected from any one of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist under layer film; forming an organic antireflection film on the inorganic hard mask middle layer film; forming a resist upper layer film on the organic antireflection film by using a resist upper layer film composition comprising a photoresist composition, to form a multilayer resist film; forming a resist pattern on the resist upper layer film by exposing a pattern circuit region of the resist upper layer film and then developing the same with a developer; forming an inorganic hard mask middle layer film pattern by etching the organic antireflection film and the inorganic hard mask middle layer film using the obtained resist pattern as an etching mask; forming a resist under layer film pattern by etching the resist under layer film using the obtained inorganic hard mask middle layer film pattern as an etching mask; and further forming a pattern on the substrate to be processed by etching the substrate to be processed using the obtained resist under layer film pattern as an etching mask [col 6 line 16-col 8 line 12]. Kori et al. also teaches in the patterning process of the present invention, the inorganic hard mask middle layer film can be formed by a CVD method or an ALD method [col 8 lines 33-35].
Claim 15 is rejected under 35 U.S.C. 103 as being unpatentable over Kori et al. (U.S. 9,728,420) as applied to claim 1 above, and further in view of Minegishi et al. (U.S. 2012/0181251).
With regard to claim 15, Kori et al. teaches into the organic film composition of the present invention, (A) an acid generator and (B) a cross-linking agent can be added to further accelerate a thermal cross-linking reaction. As (B) the cross-linking agent usable for the organic film composition of the present invention, materials described in paragraphs (0055) to (0060) of JP 2007-199653A (Hatakeyama) can be added [col 30 lines 25-36]. Hatakeyama et al. teaches specific examples of the crosslinking agent that can be used in the present invention include melamine compounds, guanamine compounds, glycoluril compounds, or urea compounds substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and compounds containing a double bond such as an alkenyl ether group [0056].
Kori et al. (or Hatakeyama) do not teach a crosslinking agent represented by general formula (16).
However, Minegishi et al. teaches a resist underlayer film-forming composition includes a base component and a crosslinking agent. The crosslinking agent includes a partial structure represented by a general formula (i) [0010] such as the following compound (B-1):
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[0196] which is equivalent to general formula (16) of instant claim 15 when q is 2, Q is a single bond, and R16 is a hydrogen atom. Minegishi et al. also teaches according to the pattern-forming method of the embodiment of the present invention in which a specific resist underlayer film-forming composition is used, a resist underlayer film can easily be formed on a substrate, which leads to excellent etching resistance, and suppresses a situation in which the underlayer film pattern is bent when transferring a fine pattern by etching. Moreover, the resist pattern can be transferred to the substrate with excellent reproducibility. Since the underlayer film pattern is not bent when etching the substrate, an increase in yield is expected to be achieved in microfabrication employed in a lithographic process, and particularly the production of integrated circuit devices [0015].
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 Kori et al. to include other known crosslinking agents such as those taught by Minegishi et al. through routine experimentation of substituting equally suitable components for the sought invention in order to achieve optimum etching resistance.
Claims 21 and 26 are rejected under 35 U.S.C. 103 as being unpatentable over Kori et al. (U.S. 9,728,420) as applied to claims 16 and 22 above, and further in view of Hakamata et al. (U.S. 2022/0009152).
With regard to claims 21 and 26, Kori et al. teaches it is noted that the substrate to be processed is not particularly limited, and a substrate made of Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN or Al, or a substrate in which a layer to be processed is formed thereon may be used. Examples of the layer to be processed include various Low-k films made of Si, SiO2, SiON, SiN, p-Si, α-Si, W, W—Si, Al, Cu or Al—Si, and stopper films thereof, which can each typically form into a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. When the layer to be processed is formed, different material is used for each of the substrate and the layer to be processed [col 35 lines 5-15].
Kori et al. does not specify the static contact angle with respect to water of 50° or more.
However, Hakamata et al. teaches a composition for forming an underlayer film in an imprinting method [abstract] in which the underlayer film is preferably formed by applying the composition for forming an underlayer film in a layer form onto the substrate. The substrate 1 may have an undercoat layer or a closely adhesive layer in addition to a case where the substrate 1 consists of a single layer [0237] and a material for the substrate is not particularly specified, and reference can be made to the description in paragraph 0103 of JP2010-109092A, the contents of which are incorporated in the present specification. In the present invention, a silicon substrate, a glass substrate, a quartz substrate, a sapphire substrate, a silicon carbide substrate, a gallium nitride substrate, an aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, and a substrate made of spin-on carbon (SOC), spin-on glass (SOG), silicon nitride, silicon oxynitride, GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP, or ZnO can be mentioned. Furthermore, specific examples of a material for the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate and a substrate coated with spin-on carbon (SOC) are preferable.
As the silicon substrate, a surface-modified silicon substrate can be appropriately used [0241-0242] and a contact angle of the surface of the substrate to water is preferably 20° or larger, more preferably 40° or larger, and still more preferably 60° or larger. The upper limit thereof is practically 90° or smaller [0246]. 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, both Kori et al. and Hakamata et al. teach known methods of forming underlayers using known substrates. Hakamata et al. also teaches the contact angle can be adjusted.
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 Kori et al. to include substrates having various contact angles with respect to water as taught by Hakamata et al. and arrive at the instant claims with a reasonable expectation of success.
Claims 1-6, 13, 14, 16, and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama (U.S. 7,358,025).
Hatakeyama teaches the patterning process of the invention involves the steps of applying a photoresist undercoat-forming material comprising a specific bisphenol compound with a group of many carbon atoms as represented by the general formula (1) or a resin comprising recurring units derived by novolac formation of a bisphenol compound as represented by the general formula (2) as a base resin onto a substrate to form an undercoat layer, applying a layer of a photoresist composition over the undercoat layer, optionally with an intermediate layer interposed therebetween, exposing the photoresist layer in a predetermined region to radiation, developing the photoresist layer with a liquid developer to form a resist pattern, and processing the undercoat layer and the substrate through the patterned photoresist layer as a mask, by means of a dry etching apparatus. The undercoat-forming material used herein comprises essentially (A) a specific bisphenol compound with a group of many carbon atoms as represented by the general formula (1) and/or a resin comprising recurring units derived by novolac formation of a bisphenol compound as represented by the general formula (2), and optionally and preferably (B) an organic solvent. For improving the spin coating characteristics, burying of stepped substrates and film's rigidity and solvent resistance, the undercoat-forming material may further comprise (C) a blending polymer, (D) a crosslinker, and (E) an acid generator [col 6 line 46-col 7 line 4] (claims 1, 14, 16, and 17) and a specific example of general formula (1) includes the following Compound 1:
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[col 34 line 35] which is equivalent to a resin having a phenolic hydroxy group of instant claim 1 having a molecular weight of 376.45 (claim 2). Hatakeyama also teaches an acid generator may be added to accelerate the thermally induced crosslinking reaction. Acid generators include those which generate an acid through pyrolysis and those which generate an acid upon exposure to light, and both are useful. The acid generators used herein include (i) onium salts of the formula (P1a-1), (P1a-2), (P1a-3) or (P1b), (ii) diazomethane derivatives of the formula (P2), (iii) glyoxime derivatives of the formula (P3), (iv) bissulfone derivatives of the formula (P4), (v) sulfonic acid esters of N-hydroxyimide compounds of the formula (P5), (vi) .beta.-ketosulfonic acid derivatives, (vii) disulfone derivatives, (viii) nitrobenzylsulfonate derivatives, and (ix) sulfonate derivatives [col 21 line 56-col 22 line 6]. Hatakeyama also teaches the salts of (P1a-1) and (P1a-2) have both the functions of a photoacid generator and a thermal acid generator while the salts of (P1a-3) function as a thermal acid generator [col 23 lines 40-42] in which (P1a-1), (P1-a-2), and (P1a-3) are the following:
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[col 22 line 10] herein, R101a, R101b, and R101c independently represent straight, branched or cyclic alkyl, alkenyl, oxoalkyl or oxoalkenyl groups of 1 to 12 carbon atoms, aryl groups of 6 to 20 carbon atoms, or aralkyl or aryloxoalkyl groups of 7 to 12 carbon atoms, wherein some or all of the hydrogen atoms may be replaced by alkoxy or other groups. Also, R101b and R101c, taken together, may form a ring. R101b and R101c each are alkylene groups of 1 to 6 carbon atoms when they form a ring. K- is a non-nucleophilic counter ion [col 22 lines 24-34] wherein examples of the non-nucleophilic counter ion represented by K- include halide ions such as chloride and bromide ions, fluoroalkylsulfonate ions such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate, arylsulfonate ions such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonate ions such as mesylate and butanesulfonate [col 23 lines 1-6] and illustrative examples of the acid generator include onium salts such as tetramethylammonium p-toluenesulfonate [col 25 line 66], diphenyliodonium p-toluenesulfonate [col 26 line 3], (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate [col 26 line 4], triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate [col 26 lines 12-17], triphenylsulfonium butanesulfonate [col 26 line 19], trimethylsulfonium p-toluenesulfonate [col 26 line 21], cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate [col 26 lines 24-25], dimethylphenylsulfonium p-toluenesulfonate [col 26 line 27], and dicyclohexylphenylsulfonium p-toluenesulfonate [col 26 line 29] which is equivalent to a base generator of instant claims 1 and 3, specifically any one of formulae (1) to (3) of instant claims 4 and 5 when R01-R09 are linear or cyclic alkyl groups having 1-10 carbon atoms or aryl groups having 6 carbon atoms and X- is a chloride ion, a bromide ion, formula (5) when R11 is an aryl group having 7 carbon atoms, or formula (6) when R12 and R13 are hydrogen atoms and R4 is a linear hydrocarbon group having 3 carbon atoms in which the conjugate acids hydrogen chloride, hydrogen bromide, toluenesulfonic acid, and butanesulfonic acid are known to have boiling points of -85°C, -66°C, 140°C, and 134°C respectively (claim 6). Hatakeyama further teaches the organic solvent used in the undercoat-forming material of the invention may be any organic solvent in which the base polymer, acid generator, crosslinker and other components are soluble. Illustrative, non-limiting, examples of the organic solvent include 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 (PGMEA), 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. These solvents may be used alone or in combinations of two or more thereof. Of the above organic solvents, preferred are diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, ethyl lactate, propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether, and mixtures thereof [col 30 lines 33-54] in which PGMEA is known to have a boiling point of 145°C and γ-butyrolactone is known to have a boiling point of 204°C (claim 13). It is prima facie obvious to combine two compositions each of which is taught by the prior art to be useful for the same purpose, in order to form a third composition to be used for the very same purpose…[T]he idea of combining them flows logically from their having been individually taught in the prior art. In re Kerkhoven, 205 USPQ 1069 1072. In the instant case, it would have been obvious to one of ordinary skill in the art to obtain a composition comprising two solvents through routine experimentation. Hatakeyama also teaches Synthesis Examples and Examples are given below together with Comparative Examples for further illustrating the invention although the invention is not limited thereby [col 33 lines 14-16] and 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 [col 43 lines 28-33]. Hatakeyama further teaches an object of the present invention is to provide an undercoat-forming material comprising a specific bisphenol compound with a group of many carbon atoms which material is useful as an undercoat layer in the bi- or tri-layer resist technology and has greater etching resistance than polyhydroxystyrene and cresol novolac resins, and a pattern-forming process using the same [col 4 lines 28-34].
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 specific teachings of Hatakeyama to include additional compositions comprising the above detailed acid generators and arrive at the instant claims through routine experimentation of substituting equally suitable components for the sought invention in order to achieve optimum etching resistance.
Claim 15 is rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama (U.S. 7,358,025) as applied to claim 1 above, and further in view of Minegishi et al. (U.S. 2012/0181251).
With regard to claim 15, Hatakeyama teaches examples of the crosslinker which can be used herein include melamine compounds, guanamine compounds, glycoluril compounds and urea compounds having substituted thereon at least one group selected from among methylol, alkoxymethyl and acyloxymethyl groups, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and compounds having a double bond such as an alkenyl ether group. These compounds may be used as an additive or introduced as pendant groups on polymer side chains. Compounds having a hydroxy group are also useful as the crosslinker [col 20 lines 13-23].
Hatakeyama does not teach a crosslinking agent represented by general formula (16).
However, Minegishi et al. teaches a resist underlayer film-forming composition includes a base component and a crosslinking agent. The crosslinking agent includes a partial structure represented by a general formula (i) [0010] such as the following compound (B-1):
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[0196] which is equivalent to general formula (16) of instant claim 15 when q is 2, Q is a single bond, and R16 is a hydrogen atom. Minegishi et al. also teaches according to the pattern-forming method of the embodiment of the present invention in which a specific resist underlayer film-forming composition is used, a resist underlayer film can easily be formed on a substrate, which leads to excellent etching resistance, and suppresses a situation in which the underlayer film pattern is bent when transferring a fine pattern by etching. Moreover, the resist pattern can be transferred to the substrate with excellent reproducibility. Since the underlayer film pattern is not bent when etching the substrate, an increase in yield is expected to be achieved in microfabrication employed in a lithographic process, and particularly the production of integrated circuit devices [0015].
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 to include other known crosslinking agents such as those taught by Minegishi et al. through routine experimentation of substituting equally suitable components for the sought invention in order to achieve optimum etching resistance.
Claim 21 is rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama (U.S. 7,358,025) as applied to claim 16 above, and further in view of Hakamata et al. (U.S. 2022/0009152).
With regard to claim 21, Hatakeyama teaches like photoresists, the undercoat-forming material of the invention can be applied onto a processable substrate by any desired technique such as spin coating, to form an undercoat layer thereon [col 30 lines 59-62] and the processable substrate is formed on a support substrate. The support substrate includes those of Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al and the like, and a suitable material different from the processable film (or processable substrate) is selected among them. The processable film is selected from low-k films of Si, SiO2, SiON, SiN, p-Si, α-Si, W, W--Si, Al, Cu, Al--Si and the like and stop films thereof [col 32 lines 22-29].
However, Hakamata et al. teaches a composition for forming an underlayer film in an imprinting method [abstract] in which the underlayer film is preferably formed by applying the composition for forming an underlayer film in a layer form onto the substrate. The substrate 1 may have an undercoat layer or a closely adhesive layer in addition to a case where the substrate 1 consists of a single layer [0237] and a material for the substrate is not particularly specified, and reference can be made to the description in paragraph 0103 of JP2010-109092A, the contents of which are incorporated in the present specification. In the present invention, a silicon substrate, a glass substrate, a quartz substrate, a sapphire substrate, a silicon carbide substrate, a gallium nitride substrate, an aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, and a substrate made of spin-on carbon (SOC), spin-on glass (SOG), silicon nitride, silicon oxynitride, GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP, or ZnO can be mentioned. Furthermore, specific examples of a material for the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate and a substrate coated with spin-on carbon (SOC) are preferable.
As the silicon substrate, a surface-modified silicon substrate can be appropriately used [0241-0242] and a contact angle of the surface of the substrate to water is preferably 20° or larger, more preferably 40° or larger, and still more preferably 60° or larger. The upper limit thereof is practically 90° or smaller [0246]. 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, both Hatakeyama and Hakamata et al. teach known methods of forming underlayers using known substrates. Hakamata et al. also teaches the contact angle can be adjusted.
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 to include substrates having various contact angles with respect to water as taught by Hakamata et al. and arrive at the instant claims with a reasonable expectation of success.
Claims 1-6, 13, 14, 16-20, 22, and 25 are rejected under 35 U.S.C. 103 as being unpatentable over Satoh et al. (U.S. 10,416,563).
Satoh et al. teaches a resist underlayer film composition to be used for a multilayer resist method, the composition comprising: (A1) one, or two or more, of a compound represented by general formula (X); and (B) an organic solvent ]col 11 lines 11-15] in which a specific example of general formula (X) includes the following compound (X-1):
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[col 95 line 3] which has a molecular weight of 780 [col 95 lines 32-33] (claim 2) which is equivalent to a compound having a phenolic hydroxy group of instant claim 1. Satoh et al. also teaches the (B) component in the resist underlayer film composition of the present invention is an organic solvent. The organic solvent (B) usable in the resist underlayer film composition of the present invention is not particularly restricted so far as it can dissolve the compound of the (A1) component; and in addition, it is preferable that the solvent can also dissolve the polymer (1A) of the (A2) component, (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, (F) a plasticizer, and (G) a pigment (claim 14), wherein the (C) to (G) additives will be discussed later. Specifically, the solvents described in the paragraphs [0091] to [0092] of Japanese Patent Laid-Open Publication No. 2007-199653 may be added. Among them, preferable solvents are as follows: propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, y-butyrolactone, as well as mixtures of two or more of the above-mentioned solvents [col 77 line 40-col 78 line 20] in which propylene glycol monomethyl ether acetate is known to have a boiling point of 145°C and γ-butyrolactone is known to have a boiling point of 204°C (claim 13). It is prima facie obvious to combine two compositions each of which is taught by the prior art to be useful for the same purpose, in order to form a third composition to be used for the very same purpose…[T]he idea of combining them flows logically from their having been individually taught in the prior art. In re Kerkhoven, 205 USPQ 1069 1072. In the instant case, it would have been obvious to one of ordinary skill in the art to obtain a composition comprising two solvents through routine experimentation. Satoh et al. further teaches the resist underlayer film composition of the present invention may be blended with (C) an acid generator in order to further facilitate a crosslinking reaction by heat or the like. There are acid generators generating an acid by thermal decomposition or by photo irradiation, wherein any of them may be blended. Illustrative example of the acid generator (C) which can be used in the resist underlayer film composition of the present invention includes following compounds: i onium salts represented by the following general formulae (P1a-1), (P1a-2), (P1a-3), or (P1b), ii diazomethane derivatives represented by the following general formula (P2), iii glyoxime derivatives represented by the following general formula (P3), iv bissulfone derivatives represented by the following general formula (P4), v sulfonate esters of N-hydroxyimide compounds represented by the following general formula (P5), vi β-ketosulfonic acid derivatives, vii disulfone derivatives, viii nitrobenzylsulfonate derivatives, and ix sulfonate ester derivative [col 78 lines 27-49] in which (P1a-1), (P1-a-2), and (P1a-3) are the following:
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[col 78 line 50] wherein, R101a, R101b, and R101c represents a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group each having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl or aryl oxoalkyl group having 7 to 12 carbon atoms, and part or all of the hydrogen atoms in these groups may be optionally substituted by an alkoxy group or the like; R101b and R101c may form a ring, and when they form the ring, R101b and R101c each represent an alkylene group having 1 to 6 carbon atoms. K- represents a non-nucleophilic counter ion [col 78 line 65-col 79 line 8] wherein illustrative example of the non-nucleophilic counter ion K- includes halide ions such as a chloride ion and a bromide ion; fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutane sulfonate; arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkylsulfonates such as mesylate and butane sulfonate; imidic acids such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and bis(perfluorobutylsulfonyl)imide; methidic acids such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide; and sulfonates such as the sulfonate whose α-position is substituted by fluorine as illustrated in the following general formula (K-1) and the sulfonate whose α-position and β-position are substituted by fluorine as illustrated in the following general formula (K-2) [col 79 lines 53-67] and illustrative example of the onium salt includes tetramethyl ammonium p-toluene sulfonate, diphenyl iodonium p-toluene sulfonate, (p-tert-butoxyphenyl)phenyl iodonium p-toluene sulfonate, triphenyl sulfonium p-toluene sulfonate, (p-tert-butoxyphenyl) diphenyl sulfonium p-toluene sulfonate, bis(p-tert-butoxyphenyl) phenyl sulfonium p-toluene sulfonate, tris(p-tert-butoxyphenyl) sulfonium p-toluene sulfonate, triphenyl sulfonium butanesulfonate, trimethyl sulfonium p-toluene sulfonate, cyclohexylmethyl(2-oxocyclohexyl) sulfonium p-toluene sulfonate, dimethylphenyl sulfonium p-toluene sulfonate, and dicyclohexylphenyl sulfonium p-toluene sulfonate [col 83 lines 11-46] which is equivalent to a base generator of instant claims 1 and 3, specifically any one of formulae (1) to (3) of instant claims 4 and 5 when R01-R09 are linear or cyclic alkyl groups having 1-10 carbon atoms or aryl groups having 6 carbon atoms and X- is a chloride ion, a bromide ion, formula (5) when R11 is an aryl group having 7 carbon atoms, or formula (6) when R12 and R13 are hydrogen atoms and R4 is a linear hydrocarbon group having 3 carbon atoms in which the conjugate acids hydrogen chloride, hydrogen bromide, toluenesulfonic acid, and butanesulfonic acid are known to have boiling points of -85°C, -66°C, 140°C, and 134°C respectively (claim 6). Satoh et al. also teaches the present invention will be specifically explained by showing Synthesis Examples, Examples, and Comparative Examples; however, the present invention is not restricted by these descriptions [col 93 lines 40-43] and it must be noted here that the present invention is not limited to the embodiments as described above. The foregoing embodiments are mere examples; any form having substantially the same composition as the technical idea described in claims of the present invention and showing similar effects is included in the technical scope of the present invention [col 115 lines 18-24]. Satoh et al. further teaches an object to provide: a resist underlayer film composition which is excellent in a resistance to a basic hydrogen peroxide aqueous solution as well as in gap-filling and planarization characteristics while having a dry etching characteristic; a patterning process using this composition; and a method for forming a resist underlayer film [col 4 lines 56-62].
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 specific teachings of Satoh et al. to include additional compositions comprising the above detailed acid generators and arrive at the instant claims through routine experimentation of substituting equally suitable components for the sought invention in order to achieve optimum etching resistance and planarization characteristics.
With regard to claims 16-20, 22, and 25, Satoh et al. teaches the present invention provides a patterning process, wherein the patterning process is to form a pattern on a substrate to be processed and comprises steps of: (I-1) forming a resist underlayer film on the substrate to be processed by using the resist underlayer film composition, (I-2) forming a resist upper layer film on the resist underlayer film by using a photoresist composition, (I-3) forming a pattern on the resist upper layer film by developing the resist upper layer film by using a developer after the resist upper layer film is pattern-exposed, and (I-4) transcribing the pattern to the resist underlayer film by dry etching using as a mask the resist upper layer film formed with the pattern. In addition, the present invention provides a patterning process, wherein the patterning process is to form a pattern on a substrate to be processed and comprises steps of: (II-1) forming a resist underlayer film on the substrate to be processed by using the resist underlayer film composition, (II-2) forming a resist intermediate film on the resist underlayer film, (II-3) forming a resist upper layer film on the resist intermediate film by using a photoresist composition, (II-4) forming a pattern on the resist upper layer film by developing the resist upper layer film by using a developer after the resist upper layer film is pattern-exposed, (II-5) transcribing the pattern to the resist intermediate film by dry etching using as a mask the resist upper layer film formed with the pattern, and (II-6) transcribing the pattern to the resist underlayer film by dry etching using as a mask the resist intermediate film transcribed with the pattern. In addition, the present invention provides a patterning process, wherein the patterning process is to form a pattern on a substrate to be processed and comprises steps of: (III-1) forming a resist underlayer film on the substrate to be processed by using the resist underlayer film composition, (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the resist underlayer film, (III-3) forming an organic antireflective film on the inorganic hard mask intermediate film, (III-4) forming a resist upper layer film on the organic antireflective film by using a photoresist composition, (III-5) forming a pattern on the resist upper layer film by developing the resist upper layer film by using a developer after the resist upper layer film is pattern-exposed, (III-6) transcribing the pattern to the organic antireflective film and the inorganic hard mask intermediate film by dry etching using as a mask the resist upper layer film formed with the pattern, and (III-7) transcribing the pattern to the resist underlayer film by dry etching using as a mask the inorganic hard mask intermediate film transcribed with the pattern [col 7 line 42-col 8 line 29] wherein it is preferable to use, as the substrate to be processed, a substrate having a structural body with a height of 30 nm or more, or having a step [col 9 lines 44-46] and the present invention provides a method for forming a resist underlayer film wherein the resist underlayer film composition mentioned above is applied onto a substrate to be processed, and then, the resist underlayer film composition is subjected to heat-treatment in a temperature range of 100°C or more and 500°C or less, and for a period of in a range of 10 to 600 seconds to form a cured film [col 9 lines 54-60]. Satoh et al. also teaches in the case that the inorganic hard mask intermediate film is formed on the resist underlayer film as mentioned above, a silicon oxide film, a silicon nitride film, or a silicon oxide nitride film (SiON film) is formed by a CVD method, an ALD method, or the like [col 92 lines 29-33].
Claim 15 is rejected under 35 U.S.C. 103 as being unpatentable over Satoh et al. (U.S. 10,416,563) as applied to claim 1 above, and further in view of Minegishi et al. (U.S. 2012/0181251).
With regard to claim 15, Satoh et al. teaches The resist underlayer film composition of the present invention may also be blended with (E) crosslinking agent in order to enhance the curability and further suppress the intermixing with the upper layer films. There is no particular restriction in the crosslinking agent, so that heretofore known crosslinking agents with various types may be widely used. Illustrative example thereof includes a melamine-type crosslinking agent, a glycoluril-type crosslinking agent, a benzoguanamine-type crosslinking agent, a urea-type crosslinking agent, a β-hydroxyalkylamide-type crosslinking agent, an isocyanurate-type crosslinking agent, an aziridine-type crosslinking agent, an oxazoline-type crosslinking agent, and an epoxy-type crosslinking agent [col 85 lines 39-50].
Satoh et al. does not teach a crosslinking agent represented by general formula (16).
However, Minegishi et al. teaches a resist underlayer film-forming composition includes a base component and a crosslinking agent. The crosslinking agent includes a partial structure represented by a general formula (i) [0010] such as the following compound (B-1):
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[0196] which is equivalent to general formula (16) of instant claim 15 when q is 2, Q is a single bond, and R16 is a hydrogen atom. Minegishi et al. also teaches according to the pattern-forming method of the embodiment of the present invention in which a specific resist underlayer film-forming composition is used, a resist underlayer film can easily be formed on a substrate, which leads to excellent etching resistance, and suppresses a situation in which the underlayer film pattern is bent when transferring a fine pattern by etching. Moreover, the resist pattern can be transferred to the substrate with excellent reproducibility. Since the underlayer film pattern is not bent when etching the substrate, an increase in yield is expected to be achieved in microfabrication employed in a lithographic process, and particularly the production of integrated circuit devices [0015].
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 Satoh et al. to include other known crosslinking agents such as those taught by Minegishi et al. through routine experimentation of substituting equally suitable components for the sought invention in order to achieve optimum etching resistance.
Claims 21 and 26 are rejected under 35 U.S.C. 103 as being unpatentable over Satoh et al. (U.S. 10,416,563) as applied to claims 16 and 22 above, and further in view of Hakamata et al. (U.S. 2022/0009152).
With regard to claims 21 and 26, Satoh et al. teaches with regard to the substrate to be processed, a layer to be processed is formed on the substrate. There is no particular restriction in the substrate, wherein a material different from the layer to be processed, such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, may be used. With regard to the layer to be processed, various low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, TiN, W—Si, Al, Cu, and Al—Si, as well as stopper films of them, and the like, may be used [col 90 line 61-col 91 line 2].
However, Hakamata et al. teaches a composition for forming an underlayer film in an imprinting method [abstract] in which the underlayer film is preferably formed by applying the composition for forming an underlayer film in a layer form onto the substrate. The substrate 1 may have an undercoat layer or a closely adhesive layer in addition to a case where the substrate 1 consists of a single layer [0237] and a material for the substrate is not particularly specified, and reference can be made to the description in paragraph 0103 of JP2010-109092A, the contents of which are incorporated in the present specification. In the present invention, a silicon substrate, a glass substrate, a quartz substrate, a sapphire substrate, a silicon carbide substrate, a gallium nitride substrate, an aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, and a substrate made of spin-on carbon (SOC), spin-on glass (SOG), silicon nitride, silicon oxynitride, GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP, or ZnO can be mentioned. Furthermore, specific examples of a material for the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate and a substrate coated with spin-on carbon (SOC) are preferable.
As the silicon substrate, a surface-modified silicon substrate can be appropriately used [0241-0242] and a contact angle of the surface of the substrate to water is preferably 20° or larger, more preferably 40° or larger, and still more preferably 60° or larger. The upper limit thereof is practically 90° or smaller [0246]. 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, both Satoh et al. and Hakamata et al. teach known methods of forming underlayers using known substrates. Hakamata et al. also teaches the contact angle can be adjusted.
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 Satoh et al. to include substrates having various contact angles with respect to water as taught by Hakamata et al. and arrive at the instant claims with a reasonable expectation of success.
Claim 23 is rejected under 35 U.S.C. 103 as being unpatentable over Satoh et al. (U.S. 10,416,563) as applied to claim 1 above, and further in view of Kori et al. (U.S. 9,728,420).
With regard to claim 23, Satoh et al. teaches the present invention provides a method for forming a resist underlayer film wherein the resist underlayer film composition mentioned above is applied onto a substrate to be processed, and then, the resist underlayer film composition is subjected to heat-treatment in a temperature range of 100°C or more and 500°C or less, and for a period of in a range of 10 to 600 seconds to form a cured film [col 9 lines 54-60].
Satoh et al. does not specify the oxygen concentration in the atmosphere, specifically 1 vol% or more and 21 vol% or less, for the method.
However, Kori et al. teaches a process for forming an organic film which is used as a resist under layer film of a multilayer resist film used in lithography or a planarizing film for manufacturing a semiconductor apparatus, comprising: coating a substrate to be processed with the foregoing organic film composition, and baking the organic film composition under an atmosphere with an oxygen concentration of 0.1% or more and 21% or less to form a cured film. By baking the inventive organic film composition under such an oxygen atmosphere, a sufficiently cured organic film can be obtained [col 6 lines 32-44]. 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, both Satoh et al. and Kori et al. teach known methods of forming films using underlayer compositions.
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 Satoh et al. to include the conditions taught by Kori et al. and arrive at the instant claims through routine experimentation with a reasonable expectation of success.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. WO2021157551 (U.S. 2023/0096137), WO2021153466 (U.S. 2022/0382153), U.S. 2021/0026246, and U.S. 2018/0011405.
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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/Anna Malloy/Examiner, Art Unit 1737
/MARK F. HUFF/Supervisory Patent Examiner, Art Unit 1737