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 Rejection of the previous action not repeated below are withdrawn in view of the arguments and amendments of the applicant. The ODP rejection over 11886118, 11851530 or 11692022 are withdrawn in view of the terminal disclaimer filed 11/13/2025. Responses to the arguments and amendment of the applicant are presented after the first rejection they are directed to.
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 1-5,7,10 and 13 are rejected under 35 U.S.C. 103 as being unpatentable over Hong et al. WO 2014035018.
Hong et al. WO 2014035018 in example 1-1, coats 45 parts zirconia, 20 parts HX-920UV (urethane acrylate), 31 parts 9,9-Bis [4- (2-Acryloyloxyethoxy) phenyl] fluorene (same structure as EA-0200 above) and 4 parts irgacure 184 (photoinitiator). Compositions 1-2 to 1.6 are similar.
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[59-62]. These are coated to form high reflective index layers in a laminated structure of a transparent substrate 1, a hard coating layer 2, a high refractive layer 3, a low refractive layer 4, and a conductive layer 5 [68-70].
The composition for coating the high refractive index layer may include a fluorene derivative resin, and the fluorene derivative resin may be a photocurable resin. The fluorene derivative resin includes a compound derived from fluorene, which is an aromatic hydrocarbon, and is used to improve low refractive index of organic materials and to improve heat resistance, substrate adhesion, and compatibility with inorganic materials. In addition, it may include a hydroxy group to solve the low solubility of the high density of the molecular structure and enable chemical bonding with the surface of the metal oxide particles. Specifically, the fluorene derivative resin is fluorene, fluorenone, 2-acetamide fluorene, 2-acetyl fluorene, 2-acetamino fluorene, 9-bromo fluorene, 9-bromo-9-phenyl Fluorene, 2,7-diamino fluorene, 2,7-di (acetamide) fluorene, 2,7-diacetyl fluorene, 9,9-bis [4- (2-hydroxyethoxy) phenyl Fluorene, 9,9 bis (3,4 dicarboxy phenyl) pulloene anhydride, 9,9-bis (3-methyl-4-hydroxy phenyl) fluorene, 9,9-bis (4-hydrate Hydroxy phenyl) fluorene, 9,9-bis (4-amino phenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis [4- (2-acrylic Loyloxy ethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxy-3-acryloyloxy propoxy) phenyl] fluorene, 9,9-bis (4-hydroxyphenyl ) Fluorene, 2-propenoic acid 1,1 '-[9H-fluorene-9-ylidenebis [4,1-phenyleneoxy (2-hydroxy-3,1- A pantil)]] may be any one selected from the esters and combinations therof. More specifically, the fluorene derivative resin may include about 1 part by weight to about 50 parts by weight based on 100 parts by weight of the total solids of the high refractive index coating composition. When the fluorene derivative resin is included in less than about 1 part by weight, the composition may not maintain a high refractive index, which may result in an excessive amount of metal oxide particles. In addition, when including the fluorene derivative resin in excess of about 50 parts by weight it is difficult to secure the pencil hardness of the high refractive layer, by maintaining the above range can have advantages in terms of refractive index control and physical properties.[38-40]. The composition for coating the high refractive index layer may include metal oxide particles. The metal oxide particles may exhibit conductivity by presenting a compound composed only of a metal element and an oxygen element in the form of particles, but the composition for coating the high refractive index layer is not conductive even though the metal oxide particles are included. In this case, the metal oxide particles are TiO2 , ZrO2 , Al2 O3 , SnO2 , ITO (indium-tin oxide), Sb2O5 , Nb2O3 , Y2O3 , SiO2 and combinations thereof It may be any one selected from the group consisting of. Specifically, the metal oxide particles may include about 5 parts by weight to about 80 parts by weight based on 100 parts by weight of the total solids of the high refractive index coating composition. When the metal oxide particles are included in less than about 5 parts by weight, the refractive index may be lowered. When the metal oxide particles are included in more than about 80 parts by weight, it may be difficult to secure physical properties of the composition. Therefore, by including the above-described fluorene derivative resin with the metal oxide particles can exhibit excellent high refractive index and physical properties. The average particle diameter of the metal oxide particles may be about 1 nm to about 100 nm, specifically about 1 nm to about 30 nm. The average particle diameter is an average value calculated by measuring the particle diameters of several particles, and when the average particle diameter of the metal oxide particles is out of the range, the surface roughness of the high refractive layer including the same may be high, and haze by scattering of light Haze may increase. Therefore, it may be easy to implement a high refractive layer excellent in optical properties by maintaining the above metal oxide particle average particle diameter range [41-44].
Hong et al. WO 2014035018 does not exemplify a composition using metal oxide particles other than zirconia or fluorene compounds other than 9,9-Bis [4- (2-Acryloyloxyethoxy) phenyl] fluorene.
It would have been obvious to modify the composition 1-1 to 1-6 by replacing the 9,9-Bis [4- (2-Acryloyloxyethoxy) phenyl] fluorene with 9,9-bis (4-hydroxyphenyl ) Fluorene based upon the equivalence at [38-40]. Further it would have been obvious to replace the zirconia (ZrO2) with TiO2, Al2 O3 , SnO2 , ITO (indium-tin oxide), Sb2O5 based upon the equivalence at [41-44] and/or to use these in different percentages within the disclosed ranges with a reasonable expectation of success in forming a curable high refractive index layer based upon the cited disclosures.
The applicant did not direct any arguments specifically at this rejection, therefore no response is warranted.
Claims 1-5,7-11,13-16 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.
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].
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.
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 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.
Claims 1-5,7-11 and 13-23 are rejected under 35 U.S.C. 103 as being unpatentable over Ogihara et al. 20140193757, in view of Rahman et al. 20200087534, further in view of either (Kori et al. 20210311395, Kori et al. 20200332062 or Kori et al. 20210269597)
Kori et al. 20210311395 (matured into 11886118) teaches compounds
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These are used in underlayer compositions UDL-4 to UDL-12, where UDL10 to UDL 12 dissolve them in a high boiling solvent in combination with polyethyleneglcyol methylether acetate [0333]. These are coated upon silicon substrates (examples 3 and 4 measure their filling of specific substrate topography by coating them and baking at 400 degree C for 60 seconds. [0338-0341]. Example 5 teaches each of the underlayer compositions by coating them on a silicon wafer including a 300nm SiO2 film, heating at 400 degrees C for 60 seconds, forming a SiO2 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 [0342-0371]. Example 6 coats the underlayers and then coats the resist directly on them and patterns the result [0372-0375]. In the underlayer composition components are described at [0185-0198], including high boiling solvents which provide thermal flowability and yield high filling and planarizing compositions [0188-0191], acid generators [0192-0193], surfactants [0194], crosslinking agents [0195-0196], plasticizers [0197-0198]. In addition, examples of the atmosphere during the baking include such inert gases as nitrogen, argon, and helium. The inventive material is capable of forming a sufficiently cured organic film without generating a sublimation product, even when the baking is performed under such an inert gas atmosphere. Moreover, the inventive material can be cured without generating a by-product even in film formation in an inert gas for preventing substrate corrosion [0209,0215,0225,0375]
Kori et al. 20200332062 (matured into 11692066) synthesized polymer A-21 (MW=940 Mw/Mn=1.02)
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This are used in underlayer UDL21 and UDL-26., where in UDL-26 the high boiling solvent is mixed with PGMEA [0294]. These are coated upon silicon substrates (examples 3 and 4 measure their filling of specific substrate topography by coating them and baking at 400 degree C for 60 seconds. [0299-0302]. Example 5 teaches each of the underlayer compositions by coating them on a silicon wafer including a 300nm SiO2 film, heating at 400 degrees C for 60 seconds, forming a SiO2 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 [0303-0314]. Example 6 coats the underlayers and then coats the resist directly on them and patterns the result [0315-0317]. In the underlayer composition components are described at [0182-0164], including high boiling solvents which provide thermal flowability and yield high filling and planarizing compositions [0185-0188], acid generators [0189-0190], surfactants [0191], crosslinking agents [0192-0193], plasticizers [0194-0195]. In this method for forming an organic film, for example, first of all, a substrate to be processed is spin-coated with the above-described inventive material for forming an organic film. After the spin coating, in the 2-stage baking, first, baking is performed in air at 300° C. or lower. Then, the second baking is performed under an atmosphere with an oxygen concentration of 1% or less. In the 1-stage baking, the first baking in air can be skipped. Note that examples of the atmosphere during the baking include such inert gases as nitrogen, argon, and helium. The inventive material for forming an organic film is capable of forming a sufficiently cured organic film without generating a sublimation product, even when the baking is performed under such an inert gas atmosphere [0204,0210,0214,0295].
Kori et al. 20210269597 (matured into 11851530) exemplifies compounds 5 and 6
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And polymers P7-P9 and P11-P12
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These are used in underlayer compositions UDL-7 to UDL-9 and UDL11-UDL-15, where UDL 13 to UDL-15 includes a high boiling solvent in addition to PGMEA [0271]. These are coated upon silicon substrates (examples 3 and 4 measure their filling of specific substrate topography by coating them and baking at 400 degree C for 60 seconds. [0276-0279]. Example 5 teaches each of the underlayer compositions by coating them on a silicon wafer including a 300nm SiO2 film, heating at 400 degrees C for 60 seconds, forming a SiO2 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 [0280-0308]. Example 6 coats the underlayers and then coats the resist directly on them and patterns the result [0309-0311]. In the underlayer composition components are described at [0151-0164], including high boiling solvents which provide thermal flowability and yield high filling and planarizing compositions [0154-0157], acid generators [0158-0159], surfactants [0160], crosslinking agents [0161-0162], plasticizers [0163-0164]. The inventive material for forming an organic film can be employed in, for example, a method for forming an organic film by which the surface of a stepped substrate used in a semiconductor device manufacturing process can be planarized, the method including: spin-coating a substrate to be processed with the above-described inventive composition for forming an organic film; heating the substrate coated with the composition for forming an organic film in air at a temperature of 50° C. or higher to 250° C. or lower for 10 to 600 seconds; then heating under an inert gas at a temperature of 250° C. or higher for 10 to 7200 seconds to form a cured film [0174,0274,0275].
It would have been obvious to modify underlayer coating compositions rendered obvious by the combination of Ogihara et al. 20140193757 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 (Kori et al. 20210311395, Kori et al. 20200332062 or Kori et al. 20210269597) 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, Kori et al. 20210311395, Kori et al. 20200332062 or Kori et al. 20210269597 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 and/or to use a heating in an inert atmosphere as taught in Kori et al. 20210311395, Kori et al. 20200332062 or Kori et al. 20210269597 to facilitate a full curing.
The applicant did not advance any arguments beyond those addressed above, so no further response is warranted.
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, 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 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 1-22 are rejected under 35 U.S.C. 103 as being unpatentable over Ogihara et al. 20140193757, in view of Rahman et al. 20200087534, 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 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 and 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.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Hirano et al. JP 2014028872 (machine translation attached, previously cited) teaches composition A-1 which is a dispersion of titanium dioxide particles and A-2 which ius a dispersion of zirconia particles in methyl isobutyl ketone/3-methoxy-1-butanol.
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[0173-0175]. In composition R11, 10 parts of A-2 is combined with 4.00 parts of bisphenylfluorene diacrylate (EA-0200)
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.
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Examples R9 and R10 use 5 parts A-1 or A-2 and 4 parts EA-0200
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[0194-0195].
EA-0200 is bounded by formula (I) where V is hydrogen and R is a (substituted) saturated hydrocarbon, where the substituent is the acrylate moiety.
The formula 1
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where R .sup.1 represents a hydrogen atom, a hydroxyl group, a phenyl group, a tolyl group, an amino group, a carboxy group, or an alkyl group represented by — (CH .sub.2 ) .sub.n CH .sub.3 ;
R .sup.2 is .sub.-C (A) = CH 2, -CO-C (A) = CH 2, - (B) -O-CO-C (A) = CH 2, - (B) -C (A) = .sub.CH 2, -O- (B) -O -CO-C (A) = CH 2, -O- (B) -C (A) = CH 2, -SH, - (B) -CO-C (A ) = CH .sub.2 , —O— (B) —CO—C (A) = CH .sub.2. Indicate (A) is —H or —CH .sub.3 ; (B) is (CH .sub.2 ) .sub.n , (OCH .sub.2 CH .sub.2 ) .sub.n , (OCH .sub.2 CH .sub.2 CH .sub.2 ) .sub.n , (OCH .sub.2 CH (OH) CH .sub.2 ) .sub.n , or (OCOCH .sub.2 CH .sub.2 CH .sub.2 CH .sub.2 .sub.N ) and R .sup.3 represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group. j, k and m are each independently an integer of 0 to 4, j + k is an integer of 0 to 5, and n is an integer of 1 to 20. [0083].
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Martin J Angebranndt whose telephone number is (571)272-1378. The examiner can normally be reached 7-3:30 pm EST.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 November 26, 2025