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 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.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 9 and 10 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.
It seems that the substituents on the phenyl rings in formulae 2-11, 2-12, 2-21, 2-22 and 2-23 do not embrace the exemplified cations of claim 11 as they do not allow for the phenyl ring to be iodo or fluoro substituted.
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 1-8,12 and 14-20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Asano et al. 20140302438.
Asano et al. 20140302438 exemplifies the salts
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on page 14 These can be salts of onium compounds such as sulfonium salts [0108]. Salt B-4 has the structure
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as illustrated on page 23. In the resist of example 9, B-4 is combined with a resist polymer A-3 having acid labile repeating unit
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and repeating units
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, quencher c-4, polymer D and solvents (table 2, page 24). This was coated upon an AR coated wafer, dried, exposed using an ArF laser (193, DUV), post exposure baked and developed and the resist pattern evaluated [0184-0194]. Examples of radiation include far ultraviolet rays such as visible light, ultraviolet rays, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), X-rays, γ rays, etc., depending on the line width of the target pattern. Electromagnetic waves: Charged particle beams such as electron beams and α rays [0157]. Examples of the onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like [0108]. Examples of the sulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium 2-(1-adamantyl)-1,1-difluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium camphorsulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium camphorsulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-6-(1-adamantanecarbonyloxy)hexane-1-sulfonate, and the like. Examples of the tetrahydrothiophenium salts include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium nonafluoro-n-butanesufonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium perfluoro-n-octanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium camphorsulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium perfluoro-n-octanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophenium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1-(6-n-butoxynaphthalen2-yl)tetrahydrothiophenium camphorsulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium perfluoro-n-octanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium camphorsulfonate, and the like. Examples of the iodonium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nona fluoro-n-butanesufonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesufonate, bis(4-t-butylphenyl)iodonium perfluoro-n-octanesulfonate, bis(4-t-butylphenyl)iodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and the like [0080-0083]. Useful acid labile structures are disclosed at [0048-0060]. Useful sulfonium and iodonium cations are disclosed at [0093-
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In the formula (X-1), R.sup.a1, R.sup.a2, and R.sup.a3 are independently a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, --OSO.sub.2--R.sup.P, or --SO.sub.2--R.sup.Q, provided that two or more groups among R.sup.a1, R.sup.a2, and R.sup.a1 optionally bond to each other to form a cyclic structure, R.sup.P and R.sup.Q are independently a substituted or unsubstituted monovalent linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, and k1, k2, and k3 are independently an integer from 0 to 5, provided that a plurality of R.sup.a1 are either identical or different when a plurality of R.sup.a1 are present, a plurality of R.sup.a2 are either identical or different when a plurality of R.sup.a2 are present, a plurality of R.sup.a3 are either identical or different when a plurality of R.sup.a3 are present, a plurality of R.sup.P are either identical or different when a plurality of R.sup.P are present, and a plurality of R.sup.Q are either identical or different when a plurality of R.sup.Q are present. In the formula (X-2), R.sup.b1 is a substituted or unsubstituted monovalent linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, k4 is an integer from 0 to 7, provided that a plurality of R.sup.b1 are either identical or different, and optionally bond to each other to form a cyclic structure when a plurality of R.sup.b1 are present, R.sup.b2 is a substituted or unsubstituted monovalent linear or branched alkyl group having 1 to 7 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 or 7 carbon atoms, k5 is an integer from 0 to 6, provided that a plurality of R.sup.b2 are either identical or different, and optionally bond to each other to form a cyclic structure when a plurality of R.sup.b2 are present, and q is an integer from 0 to 3. In the formula (X-3), R.sup.a1 and R.sup.c2 are independently a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, --OSO.sub.2--R.sup.R, or --SO.sub.2--R.sup.S, provided that two or more groups among R.sup.c1 and R.sup.c2 optionally bond to each other to form a cyclic structure, R.sup.R and R.sup.S are independently a substituted or unsubstituted monovalent linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, and k6 to k7 are independently an integer from 0 to 5, provided that a plurality of R.sup.a1 are either identical or different when a plurality of R.sup.c1 are present, a plurality of R.sup.c2 are either identical or different when a plurality of R.sup.c2 are present, a plurality of R.sup.R are either identical or different when a plurality of R.sup.R are present, and a plurality of R.sup.S are either identical or different when a plurality of R.sup.S are present [0093-0106].
Claims 1-8,12 and 14-20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Shimizu et al. JP-WO2008133270.
Shimizu et al. JP-WO2008133270 (machine translation attached) exemplifies sulfonium salts B-1, B-2 and B-4.
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These are combined with polymers (A), basic compound (c) and solvents (D ) in examples 1-6,9-27 and comparative resists 1 and 2 (see table 1, page 24). The resist polymers include acid labile repeating units
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[0100]. The resists were coated upon an Ar coated substrate, dried, exposed using a photomask using a Nikon S306C post baked, develop[ed and the pattern evaluated [0093-0095]. They were also exposed using an ArF immersion exposure apparatus, processed and evaluated [0096-0097]. Examples of radiation used in this case include ultraviolet rays, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F .sub.2 excimer laser (wavelength 157 nm), EUV (extreme ultraviolet light, wavelength 13 nm, etc.), etc. Far ultraviolet rays, charged particle beams such as electron beams, and X-rays such as synchrotron radiation can be appropriately selected and used [0085].
Claims 1-8 and 12-20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Kamimura et al. 20110229832.
Kamimura et al. 20110299832 exemplifies compounds on page 51.
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(page 52)
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(page 53)
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(page 54)
PAG-14 has the structure
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illustrated on page 137. In resist Ar-84, it is combined with a resist polymer (3) having repeating units
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(the rightmost one is acid labile, page 117), another PAG, basic compounds (B-1 and B-3) a hydrophobic resin (W-1) and solvents (see table 6, page 141). This resist was coated, dried, exposed using an ArF laser, developed and evaluated (example 94) [0942-0951]. The exposure apparatus used for exposing the resist film is not limited in its light source wavelength, but, for example, a KrF excimer laser wavelength (248 nm), an ArF excimer laser wavelength (193 nm) and an F.sub.2 excimer laser wavelength (157 nm) can be applied. The exposure is performed through an appropriate mask [0119]. The compound capable of generating a sulfonic acid represented by formula (I), (I') or (II) upon irradiation with an actinic ray or radiation is preferably one member selected from sulfonium salt and iodonium salt compounds of the sulfonic acid. X.sup.- represents a sulfonate anion after removing a hydrogen atom from the sulfonic acid (--SO.sub.3H)
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[0632-643]. Useful acid labile groups are disclosed at [0025-0035, 0182-0249]. Useful photoacids are bounded by the formula
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In formula (I'), each of R'.sub.1 and R'.sub.2 independently represents a group selected from a hydrogen atom, a fluorine atom and an alkyl group, and when a plurality of R'.sub.1s and R'.sub.2s are present, these may be the same or different. L.sub.1 represents a divalent linking group and when a plurality of L.sub.1's are present, these may be the same or different (here, y represents a repetition number of L.sub.1). A represents a cyclic organic group. x represents an integer of 0 to 20. y represents an integer of 0 to 10. The alkyl group in R'.sub.1 and R'.sub.2 may have a substituent (preferably a fluorine atom) and is preferably an alkyl group having a carbon number of 1 to 4, more preferably a perfluoroalkyl group having a carbon number of 1 to 4. Specific examples thereof include CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7, C.sub.4F.sub.9, C.sub.5F.sub.11, C.sub.6F.sub.13, C.sub.7F.sub.15, C.sub.8F.sub.17, CH.sub.2CF.sub.3, CH.sub.2CH.sub.2CF.sub.3, CH.sub.2C.sub.2F.sub.5, CH.sub.2CH.sub.2C.sub.2F.sub.5, CH.sub.2C.sub.3F.sub.7, CH.sub.2CH.sub.2C.sub.3F.sub.7, CH.sub.2C.sub.4F.sub.9 and CH.sub.2CH.sub.2C.sub.4F.sub.9, with CF.sub.3 being preferred. Each of R'.sub.1 and R'.sub.2 is preferably a fluorine atom or CF.sub.3. L.sub.1 is not particularly limited and examples thereof include --COO--, --OCO--, --CO--, --O--, --S--, --SO--, --SO.sub.2--, an alkylene group, a cycloalkylene group and an alkenylene group. The number of atoms constituting L.sub.1 is preferably from 1 to 20, more preferably from 1 to 3. Among the groups above, --COO--, --OCO--, --CO-- and --O-- are preferred, and --COO-- and --OCO-- are more preferred. The cyclic organic group of A is not particularly limited, and examples thereof include an alicyclic group, an aryl group and a heterocyclic group (an aromatic heterocycle or a non-aromatic heterocycle, including, for example, tetrahydropyrane ring and lactone ring structures). The alicyclic group as A may be monocyclic or polycyclic and is preferably a monocyclic cycloalkyl group such as cyclopentyl group, cylohexyl group and cyclooctyl group, or a polycycloalkyl group such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Above all, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group, which are an alicyclic group having a bulky structure with a carbon number of 7 or more, are preferred from the standpoint that the diffusion in the film during the PEB (post-exposure heating) step can be suppressed and MEEF (mask error enhancement factor) can be improved. Examples of the aryl group as A include a benzene ring, a naphthalene ring, a phenanthrene ring and an anthracene ring. Among these, naphthalene having low absorbance is preferred in view of absorbance of light at 193 nm. Examples of the heterocyclic group as A include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring and a piperidine ring. Among these, a furan ring, a thiophene ring, a pyridine ring and a piperidine ring are preferred [0465-0522].
Claims 1-8,12 and 14-20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Nishimura et al. 20060234153.
Nishimura et al. 20060234153 teaches various fluorinated sulfonic acids, including 1-cyclobutyl-1,1-difluoromethanesulfonic acid, 1-cyclopentyl-1,1-difluoromethanesulfonic acid, 1-cyclohexyl-1,1-difluoromethanesulfonic acid, 1-phenyl-1,1-difluoromethanesulfonic acid, 1-(naphthalen-1-yl)-1,1-difluoromethanesulfonic acid, 1-(naphthalen-1-yl)-1,1-difluoromethanesulfonic acid, 1-(2-bicyclo[2.2.1]heptyl)-1,1-difluoromethanesulfonic acid, 1-adamantan-1-yl-1,1-difluoromethanesulfonic acid, 1-adamantan-2-yl-1,1-difluoromethanesulfonic acid [0109]. 2-cyclobutyl-1,1-difluoroethanesulfonic acid, 2-cyclopentyl-1,1-difluoroethanesulfonic acid, 2-cyclohexyl-1,1-difluoroethanesulfonic acid, 2-phenyl-1,1-difluoroethanesulfonic acid, 2-(naphthalen-1-yl)-1,1-difluoroethanesulfonic acid, 2-(naphthalen-2-yl)-1,1-difluoroethanesulfonic acid, 2-(2-bicyclo[2.2.1]heptyl)-1,1-difluoroethanesulfonic acid, 2-adamantan-1-yl-1,1-difluoroethanesulfonic acid, 2-adamantan-2-yl-1,1-difluoroethanesulfonic acid [0110]. diphenyliodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis(4-t-butylphenyl)iodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate [0137-0138]. As the radiation used in this instance, ultraviolet rays, deep ultraviolet rays such as KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F.sub.2 excimer laser (wavelength: 157 nm), and EUV (extreme ultraviolet rays, wavelength: 13 nm, etc.), charged particle rays such as electron beams, X-rays such as synchrotron radiation, and the like can be given [0171].
PAG B4 is 1-(4-n-butoxynaphthyl)tetrahydrothiophenium 2-bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate [0246] and is combined with resist resins including one having an acid labile repeating unit
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[0227] , other PAGs acid diffusion controller and solvent in resist 24 (table 5, [0258]. This is coated on a wafer, dried, exposed using a Nikon SD206C exposure apparatus, develop[ed and evaluated [0187-0192].
Claims 1-8,12 and 14-20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Takizawa et al. 20140193749.
Takizawa et al. 20140193749 exemplifies PAG z120 on page 81.
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In example 105 (table2, page 105), this is combined with resin A1-4, solvents, basic compound D-1 and a surfactant. In example 5 (page 102), PAG z120 is combined with resin A1-4, solvents, basic compound D-4, surfactant W-1
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(middle repeating unit is acid labile). The resist of example 5 is coated, exposed using an electron beam, post baked and developed [0596-0602]. The resist of example 105 is coated, dried, exposed using EUV, post baked and developed [0615-0623]. Useful acid labile containing repeating units include those bounded by formula V, In formula (V), each of R.sub.51, R.sub.52 and R.sub.53 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, and R.sub.52 may be bonded to L.sub.5 to form a ring, and R.sub.52 represents an alkylene group in that case. L.sub.5 represents a single bond or a divalent linking group, and when L.sub.5 forms a ring with R.sub.52, L.sub.5 represents a trivalent linking group. R.sub.54 represents an alkyl group; each of R.sub.55 and R.sub.56 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group or an aralkyl group, and R.sub.55 and R.sub.56 may be bonded to each other to form a ring, provided that R.sub.55 and R.sub.56 do not represent a hydrogen atom at the same time.
L.sub.5 preferably represents a single bond, a group represented by --COO-L.sub.1-, or a divalent aromatic ring group. L.sub.1 preferably represents an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group or a propylene group. As the divalent aromatic ring group, a 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, or a 1,4-naphthylene group is preferred, and a 1,4-phenylene group is more preferred. As the trivalent linking group represented by L.sub.5 in the case where L.sub.5 is bonded to R.sub.52 and forms a ring, a group obtained by removing one arbitrary hydrogen atom from any of the above-described specific examples of divalent linking groups represented by L.sub.5 can be preferably exemplified. As the alkyl group represented by each of R.sub.54 to R.sub.56, an alkyl group having 1 to 20 carbon atoms is preferred, more preferably an alkyl group having 1 to 10 carbon atoms, and especially preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. As the cycloalkyl group represented by each of R.sub.55 and R.sub.56, a cycloalkyl group having 3 to 20 carbon atoms is preferred. The cycloalkyl group may be a monocyclic group such as a cyclopentyl group or a cyclohexyl group, or may be a polycyclic group such as a norbonyl group, an adamantyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group.
Or formula VI.
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In formula (VI), each of R.sub.61, R.sub.62 and R.sub.63 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R.sub.62 may be bonded to Ar.sub.6 to form a ring, and R.sub.62 in such a case represents a single bond or an alkylene group. X.sub.6 represents a single bond, --COO-- or --CONR.sub.64--. R.sub.64 represents a hydrogen atom or an alkyl group. L.sub.6 represents a single bond or an alkylene group. Ar.sub.6 represents an (n+1)-valent aromatic ring group, and when Ar.sub.6 is bonded to R.sub.62 to form a ring, Ar.sub.6 represents an (n+2)-valent aromatic ring group. Each of Y.sub.2 independently represents a hydrogen atom or a group capable of leaving by the action of an acid in the case where n is equal to or larger than 2, provided that at least one of Y.sub.2 represents a group capable of leasing by the action of an acid. n represents an integer of 1 to 4 [0176-0330].
Useful anions for photoacid generators are disclosed with respect to formula AN1 and can be sulfonioum or iodonium salts.
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where In formula (AN 1), each of Xf independently represents a fluorine atom, or an alkyl group substituted with at least one fluorine atom. Each of R.sup.1 and R.sup.2 independently represents a hydrogen atom, a fluorine atom or an alkyl group, and each R.sup.1 and R.sup.2, when a plurality of R.sup.1 and R.sup.2 are present, may be the same with or different from every other R.sup.1 and R.sup.2. L represents a divalent linking group, and each L, when a plurality of L are present, may be the same with or different from every other L. A represents a cyclic organic group. x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10. The divalent linking group represented by L is not especially restricted, and --COO--, --OCO--, --CO--, --O--, --S--, --SO--, --SO.sub.2--, an alkylene group, a cycloalkylene group, an alkenylene group, and a linking group obtained by linking two or more of these groups are exemplified, and linking groups having total carbon atoms of 12 or less are preferred. Of these, --COO--, --OCO--, --CO-- and --O-- are preferred, and --COO-- and --OCO-- are more preferred. The cyclic organic group represented by A is not especially limited so long as it has a cyclic structure, and an alicyclic group, an aryl group, and a heterocyclic group (including not only those having an aromatic property but also those not having an aromatic property) are exemplified. The alicyclic group may be monocyclic or polycyclic, and monocyclic cycloalkyl groups, e.g., a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, and polycyclic cycloalkyl groups, e.g., a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferably exemplified. Of these groups, alicyclic groups having 7 or more carbon atoms and a bulky structure such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred for capable of controlling diffusibility in a film in the heating step after exposure and from the viewpoint of the improvement of MEEF. As the aryl group, a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring are exemplified. As the heterocyclic group, groups deriving from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, or a pyridine ring are exemplified, and groups deriving from a furan ring, a thiophene ring, or a pyridine ring are preferred of all. As the cyclic organic group, lactone structures can also be exemplified, and as the specific examples, the lactone structures represented by any of the above formulae (LC1-1) to (LC1-17) that resin (A) may have can be given [0439-0474]. Useful PAGs are bounded by
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In formula (ZI), each of R.sub.201, R.sub.202 and R.sub.203 independently represents an organic group. The number of carbon atoms of the organic groups of R.sub.201, R.sub.202 and R.sub.203 is generally 1 to 30, and preferably 1 to 20. Two of R.sub.201, R.sub.202 and R.sub.203 may be bonded to form a cyclic structure, and an oxygen atom, a sulfur atom, an ester bond, an amido bond, or a carbonyl group may be contained in the ring. As the group to be formed by bonding of two of R.sub.201, R.sub.202 and R.sub.203, an alkylene group (e.g., a butyrene group and a pentylene group) can be given. Z.sup.- represents a non-nucleophilic anion (an anion which is extremely low in capability of causing nucleophilic reaction). As the organic groups represented by R.sub.201, R.sub.202 and R.sub.203, an aryl group, an alkyl group and a cycloalkyl group are exemplified It is preferred that at least one of R.sub.201, R.sub.202 and R.sub.203 represents an aryl group, and more preferably all of three represent an aryl group. As the aryl group, besides a phenyl group and a naphthyl group, hetero aryl group such as an indole residue and a pyrrole residue are also included. As the alkyl group and cycloalkyl group represented by R.sub.201, R.sub.202 and R.sub.203, a straight chain or branched alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms are preferably exemplified. As the alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group can be exemplified. As the cycloalkyl group, more preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group can be exemplified. These groups may further have a substituent. As the substituents, a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms) are exemplified, but the substituents are not restricted thereto.
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When each of R.sup.1a to R.sup.13a does not represent a hydrogen atom, the specific examples include a halogen atom, a straight chain, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a carboxyl group, an alkoxy group, an acyloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyl-oxy group, an aryloxycarbonyloxy group, an amino group (including an anilino group), an ammonio group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo group, a heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a silyl group, a hydrazino group, a ureido group, a boronic acid group (--B(OH).sub.2), a phosphato group (--OPO(OH).sub.2), a sulfato group (--OSO.sub.3H), and other known substituents [0439-0442,0474-0489]
Claims 1-10 and 12-20 are rejected under 35 U.S.C. 103 as being unpatentable over Kamimura et al. 20110229832.
Kamimura et al. 20110229832 does not exemplify the full range of photoacid generators or resist polymers in resist compositions
It would have been obvious to one skilled in the art to modify the examples cited by replacing the PAG used with other disclosed or bounded by the teachings of formula
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where the cyclic groups A is an aryl, alicyclic, or heterocyclic groups and L1 is an alkyl or cycloalkylene as taught at [0465-0522], other resist polymers including acid labile groups disclosed at [0025-0035, 0182-0249] and/or other onium cations bounded by the teachings at [0632-643] are used with a reasonable expectation of forming a useful photoresist and resist pattern.
Claims 1-20 are rejected under 35 U.S.C. 103 as being unpatentable over Kamimura et al. 20110229832, in view of Kobayashi et al. JP 2019104713.
Kobayashi et al. JP 2019104713 (machine translation attached) teaches photoacid generators useful in photoresists. Useful cations are bounded formula
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In the above formula, each of R .sup.a1 to R .sup.a3 independently represents a linear hydrocarbon group which may have a substituent, a branched hydrocarbon group, a cyclic hydrocarbon group, an aryl group, a heteroaryl group, etc. Be The linear hydrocarbon group which may have a substituent of R .sup.a1 to R .sup.a3 , a branched hydrocarbon group, a cyclic hydrocarbon group, an aryl group and a heteroaryl group are the linear structures of R in the above formula (1) And the same hydrocarbon groups as branched hydrocarbon groups, branched hydrocarbon groups, cyclic hydrocarbon groups, aryl groups and heteroaryl groups. As the sulfonium ion, specifically, for example, trimethylsulfonium ion, tributylsulfonium ion, dimethyl (2-oxocyclohexyl) sulfonium ion, bis (2-oxocyclohexyl) methylsulfonium ion, (10-camphenoyl) methyl (2-oxocyclohexyl) ) Sulfonium ion, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium ion, triphenyl sulfonium ion, diphenyl tolyl sulfonium ion, diphenyl xylyl sulfonium ion, mesityl diphenyl sulfonium ion, (t-butylphenyl) diphenyl sulfonium ion , (Octylphenyl) diphenylsulfonium ion, (cyclohexylphenyl) diphenylsulfonium ion , Biphenyldiphenylsulfonium ion, (hydroxymethylphenyl) diphenylsulfonium ion, (methoxymethylphenyl) diphenylsulfonium ion, (acetylphenyl) diphenylsulfonium ion, (benzoylphenyl) diphenylsulfonium ion, (hydroxycarbonylphenyl) diphenylsulfonium ion, (Methoxycarbonylphenyl) diphenyl sulfonium ion, (trifluoromethyl phenyl) diphenyl sulfonium ion, (fluorophenyl) diphenyl sulfonium ion, (chlorophenyl) diphenyl sulfonium ion, (bromophenyl) diphenyl sulfonium ion, (iodophenyl) diphenyl sulfonium ion, Pentafluorophenyl diphe Sulfonium ion, (hydroxyphenyl) diphenyl sulfonium ion, (methoxyphenyl) diphenyl sulfonium ion, (butoxyphenyl) diphenyl sulfonium ion, (acetyloxyphenyl) diphenyl sulfonium ion, (benzoyloxyphenyl) diphenyl sulfonium ion, (dimethylcarbamoyl phenyl) ) Diphenyl sulfonium ion, (acetylamidophenyl) diphenyl sulfonium ion, phenyl ditolyl sulfonium ion, phenyl dixyl sulfonium ion, dimesityl phenyl sulfonium ion, bis (t-butyl phenyl) phenyl sulfonium ion, bis (octyl phenyl) phenyl Sulfonium ion, bis (cyclohexylphenyl) phenylsul Phonium ion, dibiphenylphenylsulfonium ion, bis (hydroxymethylphenyl) phenylsulfonium ion, bis (methoxymethylphenyl) phenylsulfonium ion, bis (acetylphenyl) phenylsulfonium ion, bis (benzoylphenyl) phenylsulfonium ion, bis (hydroxycarbonyl) Phenyl) phenylsulfonium ion, bis (methoxycarbonylphenyl) phenylsulfonium ion, bis (trifluoromethylphenyl) phenylsulfonium ion, bis (fluorophenyl) phenylsulfonium ion, bis (chlorophenyl) phenylsulfonium ion, bis (bromophenyl) phenyl Sulfonium ion, bis (iodophenyl) phenylsulfonium ion Dipentafluorophenylphenylsulfonium ion, bis (hydroxyphenyl) phenylsulfonium ion, bis (methoxyphenyl) phenylsulfonium ion, bis (butoxyphenyl) phenylsulfonium ion, bis (acetyloxyphenyl) phenylsulfonium ion, bis (benzoyloxy) Phenyl) phenylsulfonium ion, bis (dimethylcarbamoylphenyl) phenylsulfonium ion, bis (acetylamidophenyl) phenylsulfonium ion, tristrinylsulfonium ion, triskisilylsulfonium ion, trismesitylphenylsulfonium ion, tris (t-butylphenyl) ) Sulfonium ion, tris (octylphenyl) sulfonium ion, tris Lohexyl phenyl) sulfonium ion, tribiphenyl sulfonium ion, tris (hydroxymethyl phenyl) sulfonium ion, tris (methoxymethyl phenyl) sulfonium ion, tris (acetylphenyl) sulfonium ion, tris (benzoylphenyl) sulfonium ion, tris (hydroxy carbonyl) Phenyl) sulfonium ion, tris (methoxycarbonylphenyl) sulfonium ion, tris (trifluoromethylphenyl) sulfonium ion, tris (fluorophenyl) sulfonium ion, tris (chlorophenyl) sulfonium ion, tris (bromophenyl) sulfonium ion, tris (iodoPhenyl) sulfonium ion, dipentafluorophenyl sulfonium ion, Tris (hydroxyphenyl) sulfonium ion, tris (methoxyphenyl) sulfonium ion, tris (butoxyphenyl) sulfonium ion, tris (acetyloxyphenyl) sulfonium ion, tris (benzoyloxyphenyl) sulfonium ion, tris (dimethylcarbamoylphenyl) sulfonium ion Tris (acetylamidophenyl) sulfonium ion, methyl diphenyl sulfonium ion, ethyl diphenyl sulfonium ion, butyl diphenyl sulfonium ion, hexyl diphenyl sulfonium ion, octyl diphenyl sulfonium ion, cyclohexyl diphenyl sulfonium ion, 2-oxocyclohexyl diphenyl sulfonium ion, norbornyl Nyl diphenyl sulfo , Camphenoyl diphenyl sulfonium ion, pinanoyl diphenyl sulfonium ion, naphthyl diphenyl sulfonium ion, anthranil diphenyl sulfonium ion, benzyl diphenyl sulfonium ion, trifluoromethyl diphenyl sulfonium ion, methoxycarbonyl methyl diphenyl sulfonium ion, butoxycarbonyl methyl diphenyl sulfonium ion Benzoyl methyl diphenyl sulfonium ion, (methyl thio phenyl) diphenyl sulfonium ion, (phenyl thio phenyl) diphenyl sulfonium ion, (acetyl phenyl thio phenyl) diphenyl sulfonium ion, dimethyl phenyl sulfonium ion, diethyl phenyl sulfonium ion, dibutyl Phenyl sulfonium ion, dihexyl phenyl sulfonium ion, dioctyl phenyl sulfonium ion, dicyclohexyl phenyl sulfonium ion, bis (2-oxocyclohexyl) phenyl sulfonium ion, dinorbornyl phenyl sulfonium ion, dicamphenoyl phenyl sulfonium ion, dipinanoyl phenyl sulfonium Ion, dinaphthylphenylsulfonium ion, dibenzylphenylsulfonium ion, trifluoromethyldiphenylsulfonium ion, bis (methoxycarbonylmethyl) phenylsulfonium ion, bis (butoxycarbonylmethyl) phenylsulfonium ion, dibenzoylmethylphenylsulfonium ion, bis ( Methylthiophenyl) phenyl sulfone Ions, bis (phenylthiophenyl) phenylsulfonium ion, bis (acetylphenylthiophenyl) phenylsulfonium ion, dimethyl (2-oxocyclohexyl) sulfonium ion, bis (2-oxocyclohexyl) methylsulfonium ion, (10-camphenoyl) methyl (2-Oxocyclohexyl) sulfonium ion, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium ion, trimethylsulfonium ion, triethylsulfonium ion, tributylsulfonium ion, dihexylmethylsulfonium ion, trioctylsulfonium ion, dicyclohexylethylsulfonium ion , Methyltetrahydrothiophenium ion, methyltetrahydrothiophenium Ions, triphenyl oxosulfonium ions, bis [4- (diphenylsulfonio) phenyl] sulfide - Bisuion the like [0040-0042].
Kamimura et al. 20110229832 does not exemplify photoacid generators with iodophenyl, fluorophenyl or trifluoromethylphenyl containing sulfonium salts
It would have been obvious to modify exemplified PAG compounds, PAGs rendered obvious by Kamimura et al. 20110229832, resist compositions using these or processes using the resists containing them by replacing the cations used with sulfonium cations known in the art to be useful with PAGs such as those of Kobayashi et al. JP 2019104713 with a reasonable expectation of forming a useful photoacid generator, resist composition containing it or patterned resist based upon their disclosed equivalence.
Claims 1-10 and 12-20 are rejected under 35 U.S.C. 103 as being unpatentable over Takizawa et al. 20140193749.
Takizawa et al. 20140193749does not exemplify the full range of photoacid generators or resist polymers in resist compositions
It would have been obvious to one skilled in the art to modify the examples cited by replacing the PAG used with other disclosed or bounded by the teachings of formula
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where the cyclic groups A is an aryl, alicyclic, or heterocyclic groups and L1 is an alkyl or cycloalkylene as taught at [0439-0474], other resist polymers including acid labile groups disclosed at [0176-0330] and/or other onium cations bounded by the teachings at [0439-0442,0474-0489] are used with a reasonable expectation of forming a useful photoresist and resist pattern.
Claims 1-10 and 12-20 are rejected under 35 U.S.C. 103 as being unpatentable over Takizawa et al. 20140193749.
Takizawa et al. 20140193749 does not exemplify photoacid generators with iodophenyl, fluorophenyl or trifluoromethylphenyl containing sulfonium salts
It would have been obvious to modify exemplified PAG compounds, PAGs rendered obvious by Takizawa et al. 20140193749, resist compositions using these or processes using the resists containing them by replacing the cations used with sulfonium cations known in the art to be useful with PAGs such as those of Kobayashi et al. JP 2019104713 with a reasonable expectation of forming a useful photoacid generator, resist composition containing it or patterned resist based upon their disclosed equivalence.
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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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 August 25, 2026
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