Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
The response of the applicant has been read and given careful consideration. Rejection of the previous action not repeated below are withdrawn in view of the arguments and amendments of the applicant. Responses to the arguments and amendment of the applicant are presented after the first rejection they are directed to.
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.
Claim 9 is 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 9 is dependent upon cancelled claim 8.
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 1-5,10 and 22 are rejected under 35 U.S.C. 102(a)(1) or 102(a)(2) as being fully anticipated by Kuroko et al. WO 2021220920.
Kuroko et al. WO 2021220920 (cited by applicant is machine translation) in example 1 combines 10 parts a 50% by weight of a dispersion of zirconium dioxide in solvent and 0.5 parts of a coating agent having the structure:
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(which yields a ratio of 5/0.5 or ~ 9.1% or A) [0870]
Example 3 is similar but increases the amount of the coating agent to 1 part by mass, which yields a ratio of 5/1 or 16.7% of A) [0872]. Example 7 is similar but the amount of zirconium oxide syrup including the zirconium oxide, PGMEA, 2-acryloyloxyethyle phthalic acid and N,N,N’,N’-tetramethylurea was 5.5 parts and of the coating agent used in example 1 was changed to 0.55 part by mass, which yields a ratio of 5.5/0.55 or ~10% of A) [0879]. Example 8 is similar but the amount of zirconium oxide syrup was 5.5 parts and of the coating agent used in example 1 was changed to 2.2 part by mass, which yields a ratio of 5.5/2.2 or ~28.6% of A) [0880]. Example 11 combined 5.5 parts of a dispersion of 29.7 nm zirconium dioxide in solvent and 2.2 parts of a coating agent (A) having the structure:
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(which yields 5.5/0/2.2, which yields ~28.6% of A). This is coated upon a glass substrate, dried at 90 degrees C for 120 seconds, exposed using UV light and developed in tetramethylammonium hydroxide (TMAH) and then post baked at 230 degrees C for 20 miniutes as in texample 7 [0079-0080]. The curable composition as the energy-sensitive composition of the fourth aspect includes, if necessary, a surfactant, a thermoplastic inhibitor, an antifoaming agent, a silane coupling agent, a colorant (pigment, dye), and the like. Additives such as resins (thermoplastic resins, alkali-soluble resins, etc.), inorganic fillers other than metal oxide fine particles, and organic fillers can be contained [0658]. Energy Sensitive Composition of the Second Aspect The energy sensitive composition of the third aspect is a negative photosensitive composition. Such a negative photosensitive composition includes metal oxide fine particles containing surface-modified metal oxide fine particles, an alkali-soluble resin having a phenolic hydroxyl group as a base material component (D), an acid crosslinkable substance, a photoacid generator, and the like [0453]. Useful solvents incluyding ethylene glycol (197.3 C) are disclosed [0813-0823]. The metal oxides can be used singly or combinations of two or more, The metal contained in the metal oxide constituting the metal oxide fine particles (B) is selected from the group consisting of, for example, Ag, Cu, In, Sn, Ti, Hf, Al, Zr, Zn, Sn, Ru and Ce. At least one type is preferable. From the viewpoint of providing a metal oxide having a high refractive index, at least one selected from the group consisting of Ti, Al, Zr, Zn, Sn and Ce is preferable among the above metal elements, and Zr is particularly preferable. Preferable examples of the metal oxide constituting the metal oxide fine particles (B) include aluminum oxide (Al .sub.2 O .sub.3 ), titanium oxide (TiO .sub.2 ), hafnium oxide (HfO .sub.2 ), zirconium oxide (ZrO .sub.2 ), and the like. Indium oxide (In .sub.2 O .sub.3 ), zinc oxide (ZnO), tin oxide (SnO .sub.2 ), lanthanum oxide (La .sub.2 O .sub.3 ), yttrium oxide (Y .sub.2 O .sub.3 ), cerium oxide (CeO .sub.2 ), ruthenium oxide (CeO 2) Single metal oxides such as RuO .sub.2 ) and magnesium oxide (MgO); solid solutions of metal oxides such as ITO and ATO; barium titanate (BaTIO .sub.3 ), titanium ash (CaTIO .sub.3 ), and spinels (MgAl .sub.2). Examples thereof include composite metal oxides such as .sub.O 4) [0069-0070]. The amount of the coating agent (A) used is, for example, 0.1 part by mass or more and 500 parts by mass or less, preferably 0.5 parts by mass or more and 300 parts by mass or less, with respect to 100 parts by mass of the metal oxide fine particles (B). More preferably, it is 1 part by mass or more and 100 parts by mass or less [0066]
Example 11 meets the claims rejected under this heading. The heating at 230 degrees C is considered to meet the limitation of claim 22 as air is approximately 20.9% oxygen.
Claims 1-5,10,13-15 and 22 are rejected under 35 U.S.C. 103 as being unpatentable over Kuroko et al. WO 2021220920.
Kuroko et al. WO 2021220920 does not exemplify composition including the full range of metal oxides disclosed, the additives recited in claim or the use of a mixture of solvents including a solvent with a boiling point above 180 degrees C.
With respect to claims 1-5,10,13-15 and 22, it would have been obvious to add surfactants, an acid crosslinkable substance, a photoacid generator or a high boiling solvent such as ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol, to the composition of example 11 based upon the disclosure at [0468,0453 or 0813-0823], noting the use of PGMEA (BP 146 degrees C, which is removed by the heating used to form the syrup) and N,N,N’,N’-tetramethylurea (BP 176.5 degrees C, which is not removed by the heating used to form the syrup) With respect to claims 15, the claim does not require a blend polymer, but merely requires that when the composition does it meets the limitations of claim 15. The limitations of claim 15 are met by the addition of a surfactant, crosslinking agent or acid generator.
With respect to claims 1-5,10 and 22, it would have been obvious to modify example 11 by replacing at least a portion of the zirconia with other metal oxides of hafnium, aluminum, titanium, copper, tin, indium, zinc, cerium, yttrium or lanthanum based upon the disclosure of these as equivalents and the use of them in combinations of two or more at [0069-0070].
With respect to claims 1-5,10 and 22, it would have been obvious to modify example 11 by using 10-50 mass% of additive A based upon the disclosure that 0.1 to 500 parts based upon 100 parts of the metal oxide is useful at [0066]
With respect to claims 1-5,10,13-15 and 22, it would have been obvious to modify embodiments rendered obvious above by replacing at least a portion of the zirconia with other metal oxides of hafnium, aluminum, titanium, copper, tin, indium, zinc, cerium, yttrium or lanthanum based upon the disclosure of these as equivalents and the use of them in combinations of two or more at [0069-0070].
With respect to claims 1-5,10,13-15 and 22, it would have been obvious to modify the embodiments rendered obvious above by using 10-50 mass% of additive A based upon the disclosure that 0.1 to 500 parts based upon 100 parts of the metal oxide is useful at [0066]
Claims 1-5,10,13,14 and 21-22, are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki et al. WO 2014199967
Suzuki et al. WO 2014199967 (machine translation attached) exemplifies B-2 and B-3 in page 136.
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30 or 50 nm Titanium oxide dispersions (I-IV) including a polymer are disclosed at [0320-0326].
Examples all use 41 parts of the titanium dispersion. Example 7 uses 5 parts B-2 (~10.9%), 12 parts D-2, 0.7 parts E-1 (photoacid generator)), 0.5 parts H-1 (silane coupling agent), 3 parts J-1 (amine, CMTU), 1.5 parts K-1 (polymeric dispersant, surfactant), 0.3 parts L-2
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[0327-0334] and tables 3-7 . Example 10 is similar, but uses 5 parts B-3 (~10.9%. Examples 62,77,79,90,94,96 are similar but uses 6 parts B-3 (~12.8%). The composition are coated on a substrate, dried at 80 degrees C, exposed to 200mJ/cm2 of UV light and post baked as 230 for 60 minutes [0341—344]. These are bounded by formula (I),
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(In the formula (I), Ar .sup.1 and Ar .sup.2 each independently represent an arylene group, and R .sup.1 and R .sup.2 each independently represent a hydroxy group, a carboxy group, an alkoxy group, or a hydroxy group, a carboxy group, an epoxy. A monovalent organic group having at least one group selected from the group consisting of a group and an oxetanyl group, wherein at least one of R .sup.1 and R .sup.2 is a hydroxy group, a carboxy group, or a hydroxy group, a carboxy group, It is a monovalent organic group having at least one group selected from the group consisting of an epoxy group and an oxetanyl group, R .sup.3 and R .sup.4 each independently represent a monovalent substituent, and p and q are each independently Represents an integer of 0 to 4, and different R .sup.3 groups and different R .sup.4 groups may combine to form an alicyclic ring or aromatic ring. Ar .sup.1 and Ar .sup.2 are each independently preferably a divalent aromatic hydrocarbon group, more preferably a phenylene group or a naphthylene group, from the viewpoints of synthesis and relative dielectric constant, more preferably 1,4-phenylene. Group or a 2,6-naphthylene group is more preferable, and a 1,4-phenylene group is particularly preferable. Ar .sup.1 and Ar .sup.2 are each independently preferably a naphthylene group, more preferably a 2,6-naphthylene group from the viewpoint of refractive index [0026-0032]. The content of the compound represented by formula (I) in the photosensitive resin composition of the present invention is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the total content of Component D, and 5 to 150 parts by mass. More preferred is 10 to 150 parts by mass, still more preferred is 50 to 120 parts by mass. When it is the said aspect, the refractive index of the hardened | cured material obtained is higher, a relative dielectric constant is lower, and it is excellent by transparency [0049].
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(page 15). Useful metal oxide particles are disclosed and include oxides of Note that the metal of the metal oxide particles in the present invention includes semimetals such as B, Si, Ge, As, Sb, and Te. The light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium oxide is most preferable. Titanium oxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability. From the viewpoint of the transparency of the resin composition, the average primary particle size of Component A is preferably 1 to 200 nm, more preferably 3 to 80 nm, and particularly preferably 5 to 50 nm. Here, the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter. Moreover, the component A may be used individually by 1 type, and can also use 2 or more types together.The content of the metal oxide particles in the resin composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, etc. The total solid content of the resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 60% by mass, and further preferably 20 to 50% by mass. It is especially preferable to set it as the mass%.
[0020-0023]. Component C is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof. Useful solvents are disclosed including Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) [0051-0054]. In the heat treatment step (post-bake) of (5), the obtained positive image is heated to thermally decompose the acid-decomposable group to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group, and a crosslinkable group, A cured film can be formed by crosslinking with a crosslinking agent or the like. This heating is performed using a heating device such as a hot plate or oven at a predetermined temperature, for example, 180 ° C. to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. By proceeding with a crosslinking reaction that is preferably treated, a protective film and an interlayer insulating film having excellent heat resistance, hardness, and the like can be formed. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere. When a plastic substrate is used, heat treatment is preferably performed at 80 to 140 ° C. for 5 to 120 minutes. Prior to the heat treatment step (post-bake), the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step). When middle baking is performed, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater [0296].
With respect to claims 1-5,10,14 and 22, it would have been obvious to modify example 7 by replacing the B-2 with bis(hydroxynaphthyl)fluorene based upon the disclosed equivalence of the hydroxy and glycidylethxoy moieties at [0026-0032] with a reasonable expectation of forming a useful curable composition. The heating at 230 degrees C is considered to meet the limitation of claim 22 as air is approximately 20.9% oxygen.
Alternatively, with respect to claims 1-5,10,14 and 22, it would have been obvious to modify example 10,62,77,79,90,94 or 96 by replacing (bis(hydroxyphenyl)fluorene (B-3) with bis(hydroxynaphthyl)fluorene based upon the disclosed equivalence of the phenyl and naphthyl moieties at [0026-0032] with a reasonable expectation of forming a useful curable composition. The heating at 230 degrees C is considered to meet the limitation of claim 22 as air is approximately 20.9% oxygen.
With respect to claims 1-5,10,14 and 21-22, in addition to the basis above, it would have been obvious to modify the embodiments rendered obvious above by heating for 5-10 minutes on a hot plate, rather than in the over based upon the disclosed equivalence at [0296] with a reasonable expectation of forming a useful cured pattern.
With respect to claims 1-5,10,13,14 and 21-22, in addition to the basis above, it would have been obvious to modify the embodiments rendered obvious above by using a combination of solvents including dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), or 1,3-butylene glycol diacetate (boiling point 232 ° C) based upon the disclosure at [0051-0054] with a reasonable expectation of forming a useful curable composition.
In addition to the basis above, it would have been obvious to modify the embodiments rendered obvious above by replacing at least a portion of the titanium dioxide with oxides of Ge, Sb, Y, La, Ce, Zr, Hf, W, Zn, Al, or Sn in amounts of 10-70 wt% based upon the disclosured equivalence at [0020-0023].
In addition to the basis above, it would have been obvious to modify the embodiments rendered obvious above by increasing the amount of bis(hydroxynaphthyl)fluorene to 1 to 200 parts by mass based upon the disclosured equivalence at [0049].
Claims 1-5, 7,10 and 21-22 are rejected under 35 U.S.C. 102(a)(2) as being fully anticipated by Noda et al. 20230049429.
Noda et al. 20230049429 exemplifies 3-A (BNF)
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on page 8. In comparative example 4 0.7 parts is combined with 3.3 parts of 2.5 nm ZrO2 particles in PGMEA, coated upon a silicon wafer, heated at 100 degrees for 120 seconds, followed by 450 degrees C for 90 seconds to yield a 30 nm oxide film. It exhibnited gracking, but had a good etch rate and coating quality [0078-0082].
Claims 1-5,7,9,10,13,14 and 21-22 are rejected under 35 U.S.C. 103 as being unpatentable over Urakawa et al. 20230099775, in view of Shiota et al. 20160046551 and Ogihara et al. 20140193757.
Urakawa et al. 20230099775 in example 5 teaches 19 parts of monomer A-2, 80 parts TiO2, thermal initiator and solvent. Example 6 teaches 29 parts monomer A-2 , 70 parts TiO2, thermal initiator and solvent as evidenced in table 1. These are coated upon a substrate, heated at 120 degrees C for 2 minutes to form a cured film [0207]
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(see page)
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These monomers are bounded by formulae a1 and a2
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wherein, in the formula (a1), W.sup.1 and W.sup.2 each independently represent a group represented by the following formula (a2): wherein, in the formula (a2), a ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by —S—, R.sup.1 represents a single bond, an alkylene group having 1 or more and 4 or less carbon atoms, or an alkyleneoxy group having 1 or more and 4 or less carbon atoms, and when R.sup.1 is an alkyleneoxy group, the oxygen atom in the alkyleneoxy group is bonded with a ring Z, R.sup.2 represents a monovalent hydrocarbon group, a hydroxy group, a group represented by —OR.sup.4a, a group represented by —SR.sup.4b, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxy group, an amino group, a carbamoyl group, a group represented by —NHR.sup.4c, a group represented by —N(R.sup.4d).sub.2, a sulfo group, or a group in which at least a part of hydrogen atoms bonded to the carbon atom included in a monovalent hydrocarbon group, a group represented by —OR.sup.4a, a group represented by —SR.sup.4b, an acyl group, an alkoxycarbonyl group, a group represented by —NHR.sup.4c, or a group represented by —N(R.sup.4d).sub.2 is/are substituted with a monovalent hydrocarbon group, a hydroxy group, a group represented by —OR.sup.4a, a group represented by —SR.sup.4b, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by —NHR.sup.4c, a group represented by —N(R.sup.4d).sub.2, a mesyloxy group, or a sulfo group, R.sup.4a to R.sup.4d independently represent a monovalent hydrocarbon group, m represents an integer of 0 or more, R.sup.3 represents a hydrogen atom, a vinyl group, a thiiran-2-ylmethyl group, a glycidyl group, or a (meth)acryloyl group, both W.sup.1 and W.sup.2 do not have a hydrogen atom as R.sup.3, a ring Y.sup.1 and a ring Y.sup.2 represent the same or different aromatic hydrocarbon ring, R represents a single bond, an optionally substituted methylene group, an ethylene group which is optionally substituent and includes a heteroatom between two carbon atoms, a group represented by —O—, a group represented by —NH—, or a group represented by —S—, R.sup.3a and R.sup.3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 or more and 4 or less [0021]. The polymerizable compounds can be sued in amounts of 3-95 wt%, most preferably 5-29 wt% [0096] Useful metal oxide particles including titania, zirconia, barium titanate and ceria with sizes in the 20-100 nm range in amounts of 50-90% by mass [0097-0108]. Initiators including photoacid generating diphenyliodonioum and triphenylsulfonium salts are disclosed [0109-0181]. Useful solvents are disclosed and can be used in mixture of two or more [0188-0190]. The curable composition can optionally contain additives such as surfactants, thermal polymerization inhibitors, defoamers, silane coupling agents, resins (thermoplastic resins, alkali-soluble resins, etc.), inorganic fillers other than the metal oxide microparticles (B), organic fillers, and the like. It is possible to use, as any additives, conventionally known additives. Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, and the like, and examples of the defoamer include silicone-based compounds, fluorine-based compounds, and the like [0187].
Shiota et al 20160046551 teaches vinyl group containing fluorene compounds bounded by formulae 1, 2 and 4.
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wherein W.sup.1 and W.sup.2 each independently represent a group represented by the following general formula (2), a group represented by the following general formula (4), a hydroxyl group, or a (meth)acryloyloxy group, provided that W.sup.1 and W.sup.2 do not simultaneously represent a hydroxyl group or the group represented by the following general formula (4); R.sup.3a and R.sup.3b each independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group; and n1 and n2 each independently represent an integer of 0 to 4,
wherein a ring Z represents an aromatic hydrocarbon ring; X represents a single bond or a group represented by —S—; R.sup.1 represents a single bond or an alkylene group having 1 to 4 carbon atoms; R.sup.2 represents a monovalent hydrocarbon group, a hydroxyl group, a group represented by —OR.sup.4a, a group represented by —SR.sup.4b, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by —NHR.sup.4c, a group represented by —N(R.sup.4d).sub.2, a (meth)acryloyloxy group, a sulfo group, or a group formed by substituting at least a part of hydrogen atoms bonded to carbon atoms contained in a monovalent hydrocarbon group, a group represented by —OR.sup.4a, a group represented by —SR.sup.4b, an acyl group, an alkoxycarbonyl group, a group represented by —NHR.sup.4c, or a group represented by —N(R.sup.4d).sub.2 with a monovalent hydrocarbon group, a hydroxyl group, a group represented by —OR.sup.4a, a group represented by —SR.sup.4b, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by —NHR.sup.4c, a group represented by —N(R.sup.4d).sub.2, a (meth)acryloyloxy group, a mesyloxy group, or a sulfo group; R.sup.4a to R.sup.4d each independently represent a monovalent hydrocarbon group; and m is an integer of 0 or more
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[0006].
Exemplified compounds include
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[0030,0106].
The negative-type photosensitive resin composition may contain various additives as required. Examples of the additives include a sensitizer, a curing accelerator, a filler, an adhesion accelerator, an antioxidant, an ultraviolet ray absorber, a flocculation inhibitor, thermal polymerization inhibitor, an anti-foaming agent, a surfactant, and the like [0102].
Ogihara et al. 20140193757 teaches phenol (B-III)
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[0159-0160]. Synthetic examples teach zirconium, titanium, hafnium and/or aluminum oxide dispersions [0148-0154]. Underlayer sol 15 includes oxide dispersion 4 parts A-1, 0.4 parts B-III and PGMEA. Underlayer sol 19 includes oxide dispersion 4 parts A-1, 0.4 parts B-III, a silicon polymer C-III, thermal acid generator (triphenyl sulfonium maleate and PGMEA (table 2). These were spin coated on a wafer, heated to 350 degrees C for 1 minute to form thin films. [0166-0167]. A wafer coated with a carbon film was spin coated with the underlayer compositions, a carbon thin film was then coated followed by a silicon film and resist, which was dried, a top coat applied,, exposed using an ArF immersion exposure apparatus, post baked as 100 degrees C for 60 seconds and developed in TMAH [0168-0170]. The etch characteristics were then evaluated [0171-0182]. Negative development of a wafer/carbon layer/ underlayer/resist laminate was evaluated as well as the etch characteristics of the resulting pattern [0183-0190]. Useful compounds include (page 14)
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Component A can be oxides of aluminum, gallium, yttrium, titanium, zirconium, hafnium, bismuth, tin, vanadium, and tantalum [0070-0092]. The composition for forming a metal oxide-containing film of the present invention may further contain a photoacid generator. As the photoacid generator, the materials specifically described at the paragraphs [0160] to [0179] of Japanese Patent Laid-Open Publication No. 2009-126940 can be used. The composition for forming a metal oxide-containing film of the present invention may further contain a thermal acid generator. As the thermal acid generator, the materials specifically described at the paragraphs [0061] to [0085] of Japanese Patent Laid-Open Publication No. 2007-199653 can be used. As mentioned above, when the photoacid generator or the thermal acid generator is added to the composition for forming a metal oxide-containing film of the present invention, in addition to the above-mentioned characteristics, resolution of the pattern can be further improved. The composition for forming a metal oxide-containing film of the present invention may further contain a crosslinking accelerator, if necessary. Such a crosslinking accelerator may be exemplified by the compound shown by the following general formula (1) or (2)
K.sub.aH.sub.bX (1)
wherein K represents lithium, sodium, potassium, rubidium or cesium, X represents a hydroxyl group, or a monovalent or divalent or more of an organic acid group having 1 to 30 carbon atoms, "a" is an integer of 1 or more, "b" is 0 or an integer of 1 or more, and "a+b" is a valence number of the hydroxyl group or the organic acid group.
SY (2)
wherein S represents a sulfonium, an iodonium or an ammonium, and Y represents a non-nucleophilic counter-ion. Incidentally, the above crosslinking accelerator may be used a single kind alone or two or more kinds in combination. To the composition for forming a metal oxide-containing film of the present invention may be further added a surfactant, if necessary. As such a surfactant, the materials specifically described at the paragraph [0129] of Japanese Patent Laid-Open Publication No. 2009-126940 can be used [0124- 0132]. The resist upper layer film is not particularly limited, and may be exemplified by, for example, a chemical amplification type photoresist film. Also, in the patterning process of the present invention, a middle layer film may be formed between the resist upper layer film and the metal oxide-containing film, if necessary[0139].
With respect to claims 1-5,7,10,13,14 and 21-22 , it would have been obvious to one skilled in the art to modify examples 5 or 6 of Urakawa et al. 20230099775 by replacing the bis(vinyloxynaphthyl)fluorene with bis(allyloxynaphthyl)fluorene [aka bis(vinylmethyloxynaphthyl)fluorene] based upon the disclosed equivalence in Shiota et al 20160046551 with a reasonable expectation of forming a useful metal oxide particle containing composition based upon the teachings in Ogihara et al. 20140193757 that bis(allyloxynaphthyl)fluorene is a useful monomer on page 14. Further it would have been obvious to use the resulting composition as in the examples with a reasonable expectation forming a cured film.
With respect to claims 1-5,7,9,10,13,14 and 21-22 , it would have been obvious to one skilled in the art to modify examples 5 or 6 of Urakawa et al. 20230099775 by replacing the bis(vinyloxynaphthyl)fluorene with 9-hydroxynaphthyl-9-allyloxynaphthyl)fluorene [aka 9-hydroxynaphthyl-9-vinylmethyloxynaphthyl)fluorene] based upon the disclosure of the monomer
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in Urakawa et al. 20230099775 and Shiota et al 20160046551 and the disclosed equivalence or vinyl and allyl (vinylmethyl) in Shiota et al 20160046551 with a reasonable expectation of forming a useful metal oxide particle containing composition based upon the teachings in Ogihara et al. 20140193757 that bis(allyloxynaphthyl)fluorene is a useful monomer on page 14. Further it would have been obvious to use the resulting composition as in the examples with a reasonable expectation forming a cured film. (the proportion of hydrogen would be 0.5 in claim 9)
In addition to the basis above, it would have been obvious to modify the compositions rendered obvious above by adding a surfactant or resin (blend polymer) or a solvent mixture including high and low boiling solvents based upon the disclosure in Urakawa et al. 20230099775 at [0187],0188-0190].
In addition to the basis above, it would have been obvious to modify the compositions rendered obvious above by replacing a portion of the titania with zirconia or ceria based and/or changing the amounts of the oxide particles within the disclosed range upon the disclosure at [0097-0108] with a reasonable expectation of forming a useful curable composition and cured film
Claims 1-5,7 and 10 are rejected under 35 U.S.C. 103 as being unpatentable over Kawasaki et al. JP 2013199388.
Kawasaki et al. JP 2013199388 exemplifies the combination of 3.76 g of zirconia tetraisopropoxide and 1g of 9,9-[4-(2-hydroxyethoxy)phenyl]fluorene in ethanol, heating to form particles which are dispersible/surface modified. (example 1) [0076]. In the present invention, the metal oxide nanoparticles are not particularly limited. Examples of the metal contained in the metal oxide nanoparticles include titanium, zirconium, barium, zinc, strontium, cerium, cobalt, and indium. , Tin, silicon, aluminum, hafnium, yttrium, lithium and the like. The metal oxide in the metal oxide nanoparticles may contain only one kind of these metals or may be a composite oxide containing two or more kinds in any combination and ratio. Specific examples of the metal oxide include zirconia, titanium oxide, barium titanate, zinc oxide, iron oxide, silica, alumina, lithium cobaltate, and lithium manganese phosphate. Among them, for the purpose of imparting optical, electromagnetic, and mechanical properties by dispersing metal oxide nanoparticles in organic materials such as polymers, zirconia, titanium oxide, barium titanate, zinc oxide, iron oxide Silica and alumina are preferred, and lithium cobaltate and lithium manganese phosphate are preferred for application to batteries and the like. The metal particles will have a size of 1-50 nm [0024-0027]. The fluorene compound is bounded by formula (1)
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Wherein, Z .sup.1 and Z .sup.2 are the same or different and each represents a saturated or unsaturated hydrocarbon ring or heterocyclic ring. E .sup.1 and E .sup.2 are the same or different and each represents a hydroxyl group, an amino group or a carboxyl group. R .sup.1a and R .sup.2a are the same or different and are hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, hydroxyaryl group, halogen atom, nitro group, cyano group Or a substituted amino group is shown. R .sup.1b and R .sup.2b are the same or different and each represents an alkylene group. R .sup.1c and R .sup.2c are the same or different and are hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group or substituted amino group Indicates. n1 and n2 are the same or different and represent an integer of 0 to 4. m1 and m2 are the same or different and represent an integer of 0 to 4. p1 and p2 are the same or different and represent an integer of 1 to 4. q1 and q2 are the same or different and represent an integer of 0 to 4. Z .sup.1 and Z .sup.2 are a saturated or unsaturated hydrocarbon ring or a heterocyclic ring. Examples of the saturated or unsaturated hydrocarbon ring include saturated hydrocarbon rings such as cyclopentane ring and cyclohexane ring; cyclopentene ring, cyclohexene ring, cyclopentadiene ring, cyclohexadiene ring, aromatic hydrocarbon ring (benzene ring, naphthalene) Ring, anthracene ring and the like) and the like. Examples of the saturated or unsaturated heterocycle include saturated heterocycles such as tetrahydrothiophene ring, tetrahydrofuran ring, pyrrolidine ring and piperidine ring; aromatic heterocycles (thiophene ring, furan ring, pyrrole ring, pyridine ring, etc.) An unsaturated heterocyclic ring is mentioned. Z .sup.1 and Z .sup.2 are preferably an aromatic hydrocarbon ring or an aromatic heterocycle, more preferably an aromatic hydrocarbon ring, and particularly preferably a benzene ring or a naphthalene ring. Z .sup.1 and Z .sup.2 may be the same or different [0029-0060].
It would have been obvious to one skilled in the art to modify the composition of example 1 by replacing the 9,9-[4-(2-hydroxyethoxy)phenyl]fluorene with 9,9-bis(4-hydroxynaphthyl)fluorene based upon Z1 and z2 being phenyl or naphthalene and q1 and q2 being 0-4 with a reasonable expectation of forming a dispersible zirconia particles..
Further it would have been obvious to modify the resulting composition by replacing the zirconium precursors with oxide precursors of oxide of titanium, zinc, iron, or aluminum based upon the disclosure at [0024-0027] with a reasonable expectation of forming dispersible oxide particles.
Claims 1-5,7,9-11,13-16 and 20-22 are rejected under 35 U.S.C. 103 as being unpatentable over Ogihara et al. 20140193757, in view of Rahman et al. 20200087534 and Hanabatake et al. JP-h11327125.
Rahman et al. 20200087534 teaches in synthesis example 1, A solution was prepared consisting of 12.76 g (0.075 mole) 2-phenylphenol, 15.62 g (0.075 mole) 9-Anthracene Methanol, 9.76 (0.075 mole) divinylbenzene dissolved in 25 g cyclopepentyl methyl ether (CPME) and 90 g diethylene glycol dimethyl ether (DEGME) and the mixture was stirred for 5 minutes in a 250 mL, 4 neck flask equipped with an overhead mechanical stirrer, condenser, thermo watch, Dean Stark trap and an nitrogen purge. After this time, 1.14 g of triflic acid (3% wt of monomers) was added to the stirred mixture and it was stirred for another 5 minutes. The temperature of the stirred mixture was then raised to 140.degree. C. and heated for 3 hours. After cooling the reaction mixture and diluting it with 250 mL of CPME, it was transferred to a separatory funnel, and it was washed with two aliquots of deionized (DI) water (2.times.200 mL). The polymer was precipitated by drowning into hexane. The polymer was filtered, washed and dried. The polymer was dissolved in THF and isolated using hexane two additional times to remove all monomer and oligomers. This process yielded 40% finished polymer from the starting materials. The wt average molecular wt of the polymer was 1,859 with a polydispersity of 1.40. The polymer has the structure ([0184], page 10)
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Examples 1-4 use zirconia (ZrO2) dispersions in PGMEA, which are spin coated upon a wafer, baked at 250,350 or 400 degrees C for 60 seconds to form a good quality coating [0185-0188]. Example 5 combines 1.5g of the polymer of synthesis example 1 and 7 g of the nanoparticle dispersion, which was spin coated, baked at 250 degrees C for 60 seconds to yield a quality film [0191]. The filling of this composition was good (see example 6 [0193]), while compositions without the polymer did not yield good filling and had a lot of voids (comparative example [0192]) Examples used other ratios of the polymer and the nanoparticles [0197-0205]. Underlayers containing high amount of refractory elements can be used as Hard Masks. Such Hard masks are useful when the overlying photoresist is not capable of providing high enough etch resistance to dry etching that is used to transfer the image into the underlying semiconductor substrate. This is made possible because the organic photoresist is different than the underlying hard mask and it is possible to find an etch gas mixture which will allow the transfer of the image in the photoresist into the underlying hard mask. This patterned hard mask can then be used with appropriate etch conditions and gas mixtures to transfer the image from the hard mask into the semiconductor substrate, a task which the photoresist by itself with a single etch process could not have accomplished. Spin on hard masks based on silicon such as TEOS (tetraethoxysilane) and other similar silicon compounds based on low Mw materials may be used, but these are generally materials which can only form thin coatings on a substrate and are consequently unable to fill voids in patterned films containing topography such as Via and Trench patterns. Higher Mw Polymers containing refractory element are limited in their etch resistance because to maintain solubility of these Polymers in spin casting solvent, requires that they have incorporated into their structures organic solubility enhancing moieties at the cost of a decreased etch resistance. An example of such materials are oligomeric or polymeric complexes of carboxylates of metal oxides such as Zirconium oxide and the like. The present invention relates to a novel spin coatable hard mask coating compositions which are comprised of metal oxide nanoparticles, a specific high carbon polymer which is both soluble and compatible with the nanoparticle dispersion in the same solvent forming a stable solution, able to coat films with high metal content and improve etch resistance towards oxygen plasmas. These novel compositions are useful as in Via or Trench filling applications, particularly when these features have a high aspect ratio. Coating from these novel compositions have both a high temperatures stability and a high refractory metal oxide content after cure. This imparts to these cured films a high etch resistance toward oxygen plasmas because of this high metal content. Crucially, these novel spin coating composition are also solutions are stable and spin-coatable from standard spin coating solvents, while still maintaining in the cured film a very high content of metal oxide [0006-0007]. The metal oxide nanoparticles of the above described novel composition are selected from the group consisting of Zirconium oxide nanoparticles, Hafnium oxide nanoparticles, Aluminum oxide nanoparticles, Tungsten nanoparticles, Titanium oxide nanoparticles, Copper oxide nanoparticles, Cuprous oxide nanoparticles, Tin oxide nanoparticles, Cerium oxide nanoparticles, Indium Tin oxide nanoparticles, Zinc oxide nanoparticles, Yttrium oxide nanoparticles, Lanthanum oxide nanoparticles and Indium oxide nanoparticles [0085]. In one embodiment, of the inventive composition, the wt ratio in the composition of the metal nanoparticles component to the high carbon polymer may be from about 50:50 to about 99:1. In one aspect it may be about 60:40. In another aspect it may be about 70:30. In another aspect it may be about 80:20. In another aspect it may be about 90:10. In another aspect from about 10:1 to about 1:2. In another aspect it may from about 10:1 to about 1:1. In another aspect of this embodiment the wt ratio may be from about 8:2 to about 1:2. In still another aspect of this embodiment the wt ratio may be from about 7:3 to about 1:2. In still another aspect of this embodiment the wt ratio may be from about 7:3 to about 1:1. In still another aspect of this embodiment the wt ratio may be about 7:3. In still another aspect of this embodiment the wt ratio may be about 1:1. In all the above embodiments the combination of solvent, high carbon polymer component(s), optional additives and metal nanoparticles may not exceed 100 wt. %. Moreover, in the above embodiments it is envisaged if the if composition contains more than one type of metal oxide nanoparticles and/or more than one type of high carbon polymer component (comprised of structure (1), (2) and (3)) the above ratio ranges pertain to the wt ratio of the total wt of different metal nanoparticles to the total wt of the different described of high carbon polymer comprised of structure (1), (2) and (3) having either different ratios and or different types of specific repeat unit having structure (1) (2) or (3) may be present (i.e. 2 or more) in the composition in which case the above described wt. % composition of nanoparticles represents the total wt. % of all the different types of nanoparticles present.
Hanabatake et al. JP-H11327125 (machine translation attached) teaches polymerizable compositions which are resistant to etching, in particular oxygen plasma etching as well as having improved heat resistance due to the addition of oxide particles which are small enough to be transparent [0008]. These are 1-100 nm in diameter and are used in amounts of at least 5 wt% [0009]. As the inorganic fine particles, oxygen plasma resistance, It can be selected in a range that does not impair heat resistance, dry etching resistance, etc. For example, simple metals (gold, silver, copper, platinum, aluminum, etc.), inorganic oxides, inorganic carbonates, inorganic sulfates, phosphates, etc. Can be used. As the inorganic oxide, Examples of silica (colloidal silica, aerosil, glass, etc.), alumina, titania, zirconia, zinc oxide, copper oxide, lead oxide, yttrium oxide, tin oxide, indium oxide, magnesium oxide, etc [0036-0037]. The inorganic fine particles are 5 parts by weight or more based on 100 parts by weight of the photosensitive resin. The upper limit of the amount of the inorganic fine particles may be an amount capable of forming the photosensitive resin composition into a film (for example, usually 1,000 parts by weight or less). The proportion of inorganic fine particles is 10 to 500 parts by weight (e.g., 10 to 400 parts by weight), preferably 20 to 300 parts by weight, More preferably, 30 to 300 parts by weight (for example, 30 to 200 parts by weight), especially about 50 to 150 parts by weight, High oxygen plasma resistance can be obtained even with about 0 to 50 parts by weight. When the content of the inorganic fine particles is 20% by weight or more, the oxygen plasma resistance can be greatly improved, and when the content of the inorganic fine particles is 50% by weight or more, the film is resistant to being substantially etched by oxygen plasma [0047].
Ogihara et al. 20140193757 does not teach composition with the ratio of oxide particles within the range of 9:1 to 1:9. The exemplified monomer is a diacrylate.
It would have been obvious to one skilled in the art to modify the composition of sol 15 or sol 19 of Ogihara et al. 20140193757 by replacing the diacrylate used with compounds
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Based upon their equivalence taught within Ogihara et al. 20140193757 as well as increasing the amount of the high refractive index monomer B-III monomer and/or decreasing the amount of the oxide particles to be within the 9:1 to 1:9 based upon the ranges of 50:50 to about 90:10 taught in Rahman et al. 20200087534 with a describe to having the metal oxide contact being sufficient to provide etch resistance as taught by Hanabatake et al. JP-H11327125 (within the 10-90 wt% range) with a reasonable expectation of forming a useful resist underlayer.
Further it would have been obvious to replace the inorganic particles used to aluminum, gallium, yttrium, titanium, zirconium, hafnium, bismuth, tin, vanadium, and tantalum based upon the disclosed equivalence in Ogihara et al. 20140193757 and Rahman et al. 20200087534.
(with respect to claims 22, Air has an oxygen content of 20.9% (according to the CRC Handbook or Chemistry and physics)
The applicant argues that the combination of the flow accelerator (monomer/polymer) and the metal oxide allows for excellent dry etching resistance, high planarizability and fill properties. The examiner points out that Ogihara et al. 20140193757 and Rahman et al. 20200087534, specifically describe the presence of the metal oxides and the etch characteristics are measured in the examples of Ogihara et al. 20140193757. The effect of the addition of the organic component on the fill/planarization properties of the composition is specifically discussed at [0192-0193] of Rahman et al. 20200087534, so the effect of including both is clearly already appreciated in the art. The advantages advanced in the arguments do not represent anything not already appreciated in the art. There may be a basis for the degree of these, but there is no evidence in the record which provides such a showing, particularly for the broad scope of coverage sought. The rejection stands.
In the response of 2/23/2026, the applicant argues that the ratio of the organic fluorene compounds and the metal oxide particles provides as balance of etch resistance and coatability. The position is that coatability of combinations fluorene compounds and metal oxides is established in Ogihara et al. 20140193757, although the ratio used in the examples is slightly outside the range recited in the claims. The utility of these composition as resist underlayers is also established. The amounts of the metal oxide particles recited in the claims is obvious over the combination of Rahman et al. 20200087534 which teaches useful and Hanabatake et al. JP-H11327125 who teaches metal particles contents with desirable etch resistance. The applicant argues that the sols resulting from hydrolysis the examiner disagrees, noting this is typically used to produce small oxide particles noting that even the title describes metal oxides and the dispersion are described as sols in table 2. One portion of the specification cited by the applicant describes the benefit of having both a hydroxy group and a (polymerizable?) crosslinking group. The claims are not limited to this.
The applicant points to the UDL-8 and comparative UDL-6. This comparison of composition including polymer, so this does not apply to the embodiments not including polymers or including the smaller compounds which will plasticize the polymer. This is also true for the comparative UDL-7, although the examiner is only relying upon Rahaman et al for the range of metal oxide content. The applicant is invited to directly compare with the examples of Ogihara et al. 20140193757 which are 91:9. The rejection does not suggest replacing the fluorene compounds of Ogihara et al. 20140193757, but could add them as resin additives. The amounts of the metal oxides to provide sufficient etchability is also taught in Hanabatake et al. JP-H11327125, which is newly cited..
Claims 1-5,7-11, and 13-22 are rejected under 35 U.S.C. 103 as being unpatentable over Ogihara et al. 20140193757, in view of Rahman et al. 20200087534 and Hanabatake et al. JP-H11327125 , further in view of Urakawa et al. 20230099775 and Kawasaki et al. JP 2013199388.
In addition to the basis above, it would have been obvious to one skilled in the art to modify the embodiments rendered obvious by the combination of Ogihara et al. 20140193757, Rahman et al. 20200087534 and Hanabatake et al. JP-H11327125 by using monomers which have one allyloxy moiety and a hydroxy moiety which is obvious from the teachings of Urakawa et al. 20230099775, which would have the advantage of improving the disperability of the metal oxide as taught by Hanabatake et al. JP-H11327125.
Claims 1-5,7,9-11, and 13-22 are rejected under 35 U.S.C. 103 as being unpatentable over Ogihara et al. 20140193757, in view of Rahman et al. 20200087534 and Hanabatake et al. JP-H11327125 , further in view of either (Hatakeyama et al. 20170199457, Daiseuke et al. 20170184968, Hatakeyama et al. JP 2007199653 or Kanao et all. 20120252218)
Hatakeyama et al. 20170199457 exemplifies
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These are used in underlayers UDL-1, UDL-4, UDL-7-11 with solvents and a surfactant [0148-0149]. A silicon dioxide hardcoat layer is formed by coating a silicon containing polymer with an acid generator [0150]. The underlayer composition were coated on a silicon wafer and baked at 200 degrees C for 60 seconds and then at 350 and 450 degrees C [0152]. The coating of the underlayer, the silicon oxide films and the resist is taught at [0152-0158]. This was then exposed, post baked, developed in TMAH and the layers etched [0161-0173].
Daiseuke et al. 20170184968 teaches compounds (pages 33-38)
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These are used in underlayer compositions UDL-1, UDL-4, UDL-5, UDL-10 to UDL-12 which also include surfactants and solvents (table 5). These are coated upon silicon substrates and their filling of specific substrate topography measured by coating them and baking at 250 or 450 degrees C for 60 seconds. [0144--0147]. An example teaches each of the underlayer compositions by coating them on a silicon wafer heating at 450 degrees C for 60 seconds, forming a SiON hardmask by CVD, coating an Ar layer and then a resist which is dried at 100 degrees C for 60 seconds, and then a topcoat. This is exposed using an ArF immersion exposure apparatus, post baked, at 100 degrees C for 60 seconds and then developed in TMAH, the resist was used to pattern the dry etch of the Ar coating and the hardmask. The hardmask was then used to control the etch of the underlayer [0150-0161,0162-0164]. In the underlayer composition components are described at [0182-0164], including other compounds/polymers to improve spin coating, filling properties, and etch resistance (high carbon denisity additives) [0087], acid generators and crosslinking agents [0188-0189], surfactants [0190], quenchers [0191] and other additives ( plasticizers) [0192-0194].
Hatakeyama et al. JP 2007199653 (machine translation attached) exemplifies the additive
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on page 46. Underlayer 9 combines this with polymer 1, a crosslinking agents (CR1), a thermal acid generator (AG) and PGMEA (table 1, page 48). Additives include blending polymers, crosslinkers, thermal acid generator, basic compounds and solvents [0054-0092].
Kanao et all. 20120252218 exemplifies
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These were used in underlayer compositions 1,2,4-10,12-15,17,18 and 20 in combination with a solvent mixture (PGMEA/cyclohexane). Underlayer compositions 17,18,20 added a thermal acid generator and a crosslinker.(table 5). The coat5ing of the underlayer, a silicon middle layer, a resist layer, topcoat and the exposure and development of the resist are disclosed. The etch characteristic were also evaluated [0203-0211]. The fill characteristics were evaluated [0212]. Additives to the underlayer including solvents, surfactants, basic compounds, crosslinkers, acid generators and the like are disclosed [0100-0111].
The combination of Ogihara et al. 20140193757 and Rahman et al. 20200087534 does not teach compounds bounded by formulae I, II or III, other than the ethoxyethoxy and oxyallyl monomers taught by Ogihara et al. 20140193757 (structures reproduced above).
It would have been obvious to modify underlayer coating compositions rendered obvious by the combination of Ogihara et al. 20140193757, Hanabatake et al. JP-H11327125 and Rahman et al. 20200087534 by replacing at least a portion of the fluorene based compound/monomer with one of the fluorene based non-polymeric monomer/compounds taught by either ( Hatakeyama et al. 20170199457, Daiseuke et al. 20170184968, Hatakeyama et al. JP 2007199653 or Kanao et all. 20120252218) with a reasonable expectation of forming a useful resist underlayer based upon the prior use of these compounds in resist underlayers.
Further, it would have been obvious to one skilled in the art to modify the resulting compositions by using them in known multilayer resist structures, such as the trilayer resists with the silicon intermediate layer taught by Rahman et al. 20200087534, Hatakeyama et al. 20170199457, Daiseuke et al. 20170184968, Hatakeyama et al. JP 2007199653 or Kanao et all. 20120252218 based upon the use of the metal oxide underlayers is two and three layer structures in Ogihara et al. 20140193757 and Rahman et al. 20200087534.
The applicant did not advance any arguments beyond those addressed above, so no further response is warranted.
Claims 1-7 and 9-22 are rejected under 35 U.S.C. 103 as being unpatentable over Ogihara et al. 20140193757, in view of Rahman et al. 20200087534 and Hanabatake et al. JP-H11327125, further in view of either of (Hatakeyama et al. 20170199457, Kori et al. 20210269597 or Hatakeyama et al. 20100099044)
Hatakeyama et al. 20100099044 exemplifies polymer 1.
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which is dissolved in PGMEA in underlayer composition 1. It is also used in underlayer composition 6, where it is combined with PGMEA, crosslinking agent (CR1) and thermal acid generator (triethylammonium nonafluorobutylsulfonate, AG1). A silicon wafer is coated with SiO2, the underlayer composition, a spin on glass (silicon dioxide, SOG) layer, a resist layer, a resist topcoat. The resist is exposed using an ArF immersion exposure apparatus, post baked, developed and the layers etched [0214-0229]. Additives for the underlayer include other polymers, crosslinker, thermal acid generator, basic compound, solvents and surfactants [0096-0109].
The combination of Ogihara et al. 20140193757, Hanabatake et al. JP-H11327125 and Rahman et al. 20200087534 does not teach compounds bounded by formulae I, II or III, other than the ethoxyethoxy and oxyallyl monomers taught by Ogihara et al. 20140193757 (structures reproduced above).
It would have been obvious to modify underlayer coating compositions rendered obvious by the combination of Ogihara et al. 20140193757, Hanabatake et al. JP-H11327125and Rahman et al. 20200087534 by replacing at least a portion of the fluorene based compound/monomer with one of the fluorene based low MW polymeric compounds taught by either (Hatakeyama et al. 20170199457, Kori et al. 20210269597 or Hatakeyama et al. 20100099044) with a reasonable expectation of forming a useful resist underlayer based upon the prior use of these compounds in resist underlayers.
Further, it would have been obvious to one skilled in the art to modify the resulting compositions by using them in known multilayer resist structures, such as the trilayer resists with the silicon intermediate layer taught by Rahman et al. 20200087534, Hatakeyama et al. 20170199457, Kori et al. 20210269597based upon the use of the metal oxide underlayers is two and three layer structures in Ogihara et al. 20140193757 and Rahman et al. 20200087534.
The applicant did not advance any arguments beyond those addressed above, so no further response is warranted.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Martin J Angebranndt whose telephone number is (571)272-1378. The examiner can normally be reached 7-3:30 pm EST.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Mark F Huff can be reached at 571-272-1385. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 April 10, 2026
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