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. Rejections of the previous office action not repeated below are withdrawn in view of the amendment and arguments. Responses to the arguments 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 1,2,4-5,10,11 and 20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015).
Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) teaches the formation of Ti2Zr4O4(OMc)16, where OMc is methacrylate by the reaction of Ti4Zr4O6(OBu)4(OMc)16 with acetylacetone (abstract). See figure 2 and the results and discussion in the left column on page 2890.
This is a new ground of rejection which exemplifies the Ti2Zr4O4(OMc)16 cluster/nanoparticle which is among those recited in claims 2, 10 and 20.
Claims 1,2,4-5,10,11 and 20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Moraru et al., “Methacrylate-substituted mixed metal clusters derived from zigzag chains of [ZrO8]/[ZrO7] and [TiO6] polyhedra”, Eur. J. Inorg. Chem., pp 1295 (2001)
Moraru et al., “Methacrylate-substituted mixed metal clusters derived from zigzag chains of [ZrO8]/[ZrO7] and [TiO6] polyhedra”, Eur. J. Inorg. Chem., pp 1295 (2001) teaches the formation of crystals of Ti2Zr6O6(OMc)20 which were manually separated from the others. (page 1300, left column). The formation of Ti or zirconium oxide clusters having acrylate or methacrylate functionality using an excess of (meth)acrylic acid is disclosed (page 1295/left column)
This is a new ground of rejection which exemplifies the Ti2Zr6O6(OMc)20 cluster/nanoparticle which is among those recited in claims 2, 10 and 20.
Claims 1,2,4-5,10,11 and 20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002)
Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) describes previously formed zirconium containing clusters including Ti2Zr6O6(OMc)20 (first page, section (B) ). The formation of Zr4O2(methacrylate)12 was formed by adding a 7 fold molar excess of methacrylic acid to Zr(OBu)4 in butanol (first page, section (A)). The use of ligand exchange is disclosed as a third possibility (section (3), last page) with methacrylic (really acrylic acid ?) benzoic or 2-bromoisobutyric acid being used in a rapid ligand exchange. The formation of Ti2(Zr/Hf)6O6(OMc)20
This is a new ground of rejection which exemplifies the Ti2Zr6O6(OMc)20 cluster/nanoparticle which is among those recited in claims 2, 10 and 20.
Claims 1,2,4-5,10,11 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015), in view of Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015)
Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) teaches carboxylates of the general formula (MaOb(OR/OH)c(OOCR)d (M= Ti, Zr) by the reaction of zirconium alkoxides, titanium alkoxides or mixtures of these with carboxylic acids (page 208/left column). The molecular structure of Ti2Zr4O5(OH)2(OPr)(OPiv)11 is illustrated in figures 5 and 6. Ti3Zr3O4(OH)3(OBu)3(OPiv)10 is disclosed at the bottom right column of page 210 and in figures 7 and 8)
Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) does not teach or exemplify the full range of Ti2Zr4 oxides.
With respect to claims 1,2,4-5,10,11 and 20, it would have been obvious to one skilled in the art to extend the teachings of Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) to other Ti2Zr4 oxides, such as the Ti2Zr4O5 taught by Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) which have 14 ligands by using an excess of acrylic acid or methacrylic acid to induce a ligand exchange as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), followed by a reaction with acetyl acetone as taught in Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) so that all the ligands are acrylate or methacrylate with a reasonable expectation of forming a fully (meth)acrylated Ti2Zr4O5 cluster/nanoparticle.
With respect to claims 1,2,4-5,10,11 and 20, alternatively it would have been obvious to one skilled in the art to extend the teachings of Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) to other Ti2Zr4 oxides, such Ti2Zr4O6 bounded by the formula (MaOb(OR/OH)c(OOCR)d (M= Ti, Zr) of Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) which are similar to the Ti2Zr4O5 particles exemplified taught by Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) which have 14 ligands by have 6 oxygens like the Ti2Zr6O6(OMc)20 of Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) by using an excess of acrylic acid or methacrylic acid to induce a ligand exchange as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), followed by a reaction with acetyl acetone as taught in Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) so that all the ligands are acrylate or methacrylate with a reasonable expectation of forming a fully (meth)acrylated Ti2Zr4O5 cluster/nanoparticle.
Claims 1,2,4-5,10,11 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015), in view of Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015), further in view of Sarma et al. 20150234272, Toriumi et al. 20170277036, Lee et al. 20150056745 and Mizuno et al. 20080152933.
Sarma et al. 20150234272 in figure 10A teaches a resist based upon ZrO2-dimethylacrylic acid and 5 wt% of a non-ionic PAG which exposed used EUV was developed in 4-methyl-2-pentanol. Figure 10B teaches a resist including ZrO2-methylmethacrylic acid/ZrO2-dimethylacrylic acid which was exposed using EUV and developed in 4-methyl-pentanol. There is also a resist which is a ZrO2-methylmethacrylic acid/HfO2-dimethylacrylic acid which was exposed using EUV and developed in 4-methyl-pentanol. ZrO2-methylmethacrylic acid and non-ionic PAG which was exposed using EUV and developed in 4-methyl-pentanol. The HfO2/benzoate particles have a particles size of 3.2 nm [0124]. The exposure of HfO2-methacrylic acid particles combined with N-hydroxynaphthalimide using EUV, followed by development in 4-methyl-2-pentanol is disclosed [0133]. A photoresist composition was prepared by dispersing HfO.sub.2-benzoate nanoparticles in PGMEA at 5-10 wt % of the final dispersion and adding a small amount (1-7 wt % per gram of nanoparticle) of a photoacid generator, N-hydroxynaphthalimide triflate. The hybrid nanoparticles were spin coated on bare silicon wafers using standard protocols as described in Krysak et al., Development of an inorganic nanoparticle photoresist for EUV, e-beam, and 193 nm lithography, Proceedings of SPIE 7972, (Pt. 1, Advances in Resist Materials and Processing Technology XXVIII), 2011, 7972, 79721C1-C6, and Trikeriotis et al., Development of an inorganic photoresist for DUV, EUV, and electron beam imaging, Proceedings of SPIE 7639, (Pt. 1, Advances in Resist Materials and Processing Technology XXVII), 2010, 7639, 76390E1-E10, forming uniform films without any crystalline domains (see FIG. 6) [0126]. The nanoparticle core is selected from titanium (Ti), zirconium (Zr), and/or hafnium (Hf and oxide of these. The nanoparticle of the invention comprises 35 wt % to 75 wt % (e.g., 35, 40, 45, 50, 55, 60, 65, 70, 75 wt %, etc.) core (i.e., the core constitutes 35-75 wt % of the entire nanoparticle), including any and all ranges and subranges therein. In some embodiments, the nanoparticle comprises 35-75 wt % titanium oxide, zirconium oxide, or hafnium oxide, or combinations thereof [0074-0076]. In some embodiments, the invention provides a photoresist composition comprising a nanoparticle that includes a coating having a ligand selected from methacrylic acid, trans-2,3-dimethylacrylic acid, ethylacrylic acid, propylacrylic acid and methylbutyric acid, and carboxylates thereof (i.e., carboxylates of any of the listed acids) [0101]. Synthesis of an Embodiment of the Inventive Nanoparticle --HfO.sub.2 Core with Benzoate Ligand Coating: Hafnium isopropoxide, benzoic acid and PGMEA were purchased from Sigma Aldrich. Solvents like THF and acetone were obtained from Fisher Scientific. A typical synthesis consists of reacting 3g of hafnium isopropoxide and 5g of benzoic acid dissolved in 20m1 of THF respectively. The reactants were stirred at 65.degree. C. for 2 hours followed by addition of 2 ml of DI water, to initiate sol-gel reaction. After 18 hours of reaction time, the reaction mixture was precipitated and washed with a mixture of acetone/water (1:4, vol) and the nanoparticles were dried for 24 hours under vacuum. The mild reaction conditions of sol-gel chemistry allowed for efficient incorporation of the organic moieties into the inorganic components. HfO.sub.2-benzoate nanoparticles were isolated as white amorphous powders as confirmed from x-ray diffraction.
Nanoparticle particle size was determined by dynamic light scattering techniques (FIG. 2A), where an HfO.sub.2-benzoate dispersion of 10 wt % in PGMEA was prepared for the measurements, giving an average particle size of 3.2 nm with a narrow size distribution. From calculations based on atomic composition and correlating them with mass loss results as obtained from TGA, it has been determined that each HfO.sub.2 nanoparticle core is covered with .about.5 benzoate ligands at their surface. [0118-0124].
Toriumi et al. 20170277036 teaches that core may be a fine particle of an oxide of a metal selected from the group consisting of Ti, Zr and Hf, for example. Specific examples thereof are titanium oxide fine particles, zirconium oxide fine particles and hafnium oxide fine particles. It is desirable in practical use to select appropriate type of particles from those metal oxide particles mentioned with consideration of resist characteristics such as the optical property and the resistance to dry-etching [0014]. In recent years, with progress of the miniaturization of patterns, the thickness of the resist, which is a photosensitive composition used for pattern formation, is reduced. Therefore, when etching is carried out on an underlying layer using a micro-patterned resist as a mask, such a drawback arises prominently that the etching resistance of the resist is insufficient. In order to reinforce the etching resistance of this resist, various resist materials containing metal oxides having resistance to etching are examined [0006]. The unsaturated carboxylic acid can include vinylbenzoic acid [0019]. The particles are formed by the hydrolysis reaction of zirconium propoxide using hydrochloric acid in the presence of 3-(trimethoxysilyl)propyl methacrylic acid, and later methacrylic acid the resault yielded a zirconium oxide particle with a silylated shell, stabilized with methacrylic acid [0077-0079]
Lee et al. 20150056745 teaches the addition of phenylacetic acid compounds of formula (2) as stabilizers for titanium dioxide nanoparticles.
PNG
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100
146
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Greyscale
where R2 is hydrogen, C1-20 alkyl;, C2-20 alkenyl, C2-20 alkynyl or C6-30 aryl [0013-0014].
Mizuno et al. 20080152933 in example 5 teaches the surface treatment of the ZrO.sub.2 nano-particles was carried out using 10 g of 4-vinylbenzoic acid, in place of 25 g of biphenyl-4-carboxylic acid used in Example 2. Except for this, a curable resin-fine particle composite material was produced similarly to as described in Example 2.
The combination of Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015), in view of Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015 does not teach the full range of polymerizable carboxylic acids.
It would have been obvious to modify the processes rendered obvious by the combination of Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015), in view of Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015 by replacing the acrylate or methacrylate carboxylic acids with any of trans-2,3-dimethylacrylic acid, ethylacrylic acid, propylacrylic acid and methylbutyric acid taught by Sarma et al. 20150234272, vinylbenzoic acid taught by Toriumi et al. 20170277036 and Mizuno et al. 20080152933 or the C2-20 alkene phenylacetates taught by Lee et al. 20150056745 which embrace 4-vinylpheynlacetate, 4-(2-methylvinyl)phenylacetate or 4-(3methyl-2-propenyl)phenylacetate with a reasonable expectation fop forming a useful polymerizable Ti2Zr4O or Ti2Zr6O cluster/nanoparticle, noting that the replacement of the ligands with benzoic acid or other carboxylate ligands is clearly taught in Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002).
Claims 1-5,10-13 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sullivan et al. 20130011630, in view of Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002)
Sullivan et al. 20130011630 in example 5 describes titanium/Zirconium nanoparticle hardmask formed by the reaction of 1.94 g of Ti(tetra)N-butoxide (0056 moles) and 2.71 g zirconium (tetra)n-butoxide (0.0077 moles) in butyl alcohol and then 4.17 g of methacrylic acid was added. The solution was allowed to form particles for a week, which were then isolated by decanting and vacuum drying [0069-0070]. These were then dispersed ion PGMEA to form a 5.6% solids solution and spin coated upon a hot plate. [0071-0072]. The motivation is to form hardmasks with increased resistance to reactive ion etching (RIE) relative to silicon oxide films [0008]. The composition use metal oxide precursor compounds of aluminum, titanium, zirconium, vanadium, germanium, aluminum, hafnium, gallium, thallium, antimony, lead, bismuth, indium, tin, boron, germanium, arsenic, tellurium, rare earth metals (e.g., scandium, yttrium, and the lanthanides), or a combination thereof, which are used to form sol-gel or metal oxide nanoparticles which are considered metal oxide polymers to form the hardmask compositions [0018]. When forming nanoparticles or clusters, the ligands ae carboxylic acids, alkoxides, acetoacetals or pentanediones [0028]. Suitable ligands for use in the hardmask materials include those selected from the group consisting of alcohols (alkoxides), phenols (phenoxides), beta-diketones, beta-diketoesters, aromatic or aliphatic carboxylic acids (carboxylates), thiols, and derivatives thereof. The ligands may also contain an additional functional group that allows for other chemical reactions to occur, such as an acrylate that can be polymerized. Particularly preferred ligands include acetoacetates, pentanedionates, and alkoxides [0027]. The transfer of the pattern in the imaging layer using an etch or ion implantation process is disclosed [0044-0046]. The etch rate of the hardmask material is disclosed at [0052]. Suitable solvent systems for use in forming the hardmask composition will include a solvent selected from the group consisting of propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate, propylene glycol n-propyl ether, gamma-butyrolactone, cyclopentanone, cyclohexanone, n-butyl acetate, and mixtures thereof [0030].
With respect to claims 1-5,10-13 and 20, it would have been obvious to one skilled in the art to modify the compositions and processes of preparing them in example 5 of Sullivan et al. 20130011630 which uses an excess of acrylic acid or methacrylic acid by adding more acrylic acid or methacrylic acid to induce a ligand exchange as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), followed by a reaction with acetyl acetone as taught in Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) to form a Ti2Zr4O or Ti2Zr6O cluster/particle where all the ligands are acrylate or methacrylate with a reasonable expectation of forming a fully (meth)acrylated Ti2Zr4O5 cluster/nanoparticle which can then be dissolved in a solvent such as the PGMEA used in example 5 with a reasonable expectation of forming a useful hardmask composition.
Further it would have been obvious to use other disclosed solvents or concentrations of the metal oxide particles with a reasonable expectation of forming a useful coating solution.
In the arguments of 6/18/2026, the applicant argues that Sullivan et al. 20130011630 does not yield nanoparticles with only methacrylic acid as the ligands. The applicant achieves this by a treatment with acetyl acetone. The examiner has added Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) which teach the formation Ti2Zr4 and Ti2Zr6 oxide clusters with only methacrytlic acid ligands, which may be achieved by a ligand exchange treatment using a sufficient excess of the methacrylic acid as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002)and is definitely achieved by subsequent treatment with acetyl acetone (aka acetyl acetonate). These secondary references clearly exemplify Ti2Zr6O6(OMc)20 and Ti2Zr4O4(OMc)16 which are among the species recited in claims 2,10 and 20.
Claims 1-5,10-13 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sullivan et al. 20130011630, in view of Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), further in view of Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015).
The combination of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) does not teach or exemplify the full range of Ti2Zr4 oxides.
With respect to claims 1-5,10-13 and 20, it would have been obvious to one skilled in the art to modify the hardmasks rendered obvious by the combination of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) by forming other Ti2Zr4 oxides, such as the Ti2Zr4O5 taught by Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) which have 14 ligands by using an excess of acrylic acid or methacrylic acid to induce a ligand exchange as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), followed by a reaction with acetyl acetone as taught in Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) so that all the ligands are acrylate or methacrylate with a reasonable expectation of forming a fully (meth)acrylated Ti2Zr4O5 cluster/nanoparticle.
With respect to claims 1-5,10-13 and 20, alternatively it would have been obvious to one skilled in the art to modify the hardmasks rendered obvious by the combination of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) by forming other Ti2Zr4 oxides, such Ti2Zr4O6 bounded by the formula (MaOb(OR/OH)c(OOCR)d (M= Ti, Zr) of Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) which are similar to the Ti2Zr4O5 particles exemplified taught by Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) which have 14 ligands by have 6 oxygens like the Ti2Zr6O6(OMc)20 of Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) by using an excess of acrylic acid or methacrylic acid to induce a ligand exchange as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), followed by a reaction with acetyl acetone as taught in Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) so that all the ligands are acrylate or methacrylate with a reasonable expectation of forming a fully (meth)acrylated Ti2Zr4O5 cluster/nanoparticle.
Claims 1-5,10-13 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sullivan et al. 20130011630, in view of Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), further in view of Toriumi et al. 20170277036, Lee et al. 20150056745 and Mizuno et al. 20080152933.
The combination of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) does not teach the full range of polymerizable carboxylic acids.
It would have been obvious to modify the compositions and processes of preparing them rendered obvious by the combination of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) by replacing the acrylate or methacrylate carboxylic acids with any of trans-2,3-dimethylacrylic acid, ethylacrylic acid, propylacrylic acid and methylbutyric acid taught by Sarma et al. 20150234272, vinylbenzoic acid taught by Toriumi et al. 20170277036 and Mizuno et al. 20080152933 or the C2-20 alkene phenylacetates taught by Lee et al. 20150056745 which embrace 4-vinylpheynlacetate, 4-(2-methylvinyl)phenylacetate or 4-(3methyl-2-propenyl)phenylacetate with a reasonable expectation of forming a useful polymerizable a Ti2Zr4O or Ti2Zr6O cluster/nanoparticle, noting that the replacement of the ligands with benzoic acid or other carboxylate ligands is clearly taught in Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002).
Claims 1-5,10-13 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sullivan et al. 20130011630, in view of Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015), Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015), further in view of Toriumi et al. 20170277036, Lee et al. 20150056745 and Mizuno et al. 20080152933.
The combination of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015), Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) does not teach the full range of polymerizable carboxylic acids.
It would have been obvious to modify the compositions and processes of preparing them rendered obvious by the combination of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015), Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) by replacing the acrylate or methacrylate carboxylic acids with any of trans-2,3-dimethylacrylic acid, ethylacrylic acid, propylacrylic acid and methylbutyric acid taught by Sarma et al. 20150234272, vinylbenzoic acid taught by Toriumi et al. 20170277036 and Mizuno et al. 20080152933 or the C2-20 alkene phenylacetates taught by Lee et al. 20150056745 which embrace 4-vinylpheynlacetate, 4-(2-methylvinyl)phenylacetate or 4-(3methyl-2-propenyl)phenylacetate with a reasonable expectation of forming a useful polymerizable a Ti2Zr4O or Ti2Zr6O cluster/nanoparticle, noting that the replacement of the ligands with benzoic acid or other carboxylate ligands is clearly taught in Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002).
Claims 1-6,8-18 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sarma et al. 20150234272, in view of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018).
Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018) teaches Zr based methacrylate oxo clusters having the formula Zr6O4(OH)4Mc12 and Ti based clusters having the formula Ti8O8Mc16. These are coated onto wafers, dried, exposed using EUV and developed in Chloroform (section 2.1 to 2.3).
Sarma et al. 20150234272 does not exemplify the use of polymerizable ligands functionalized Ti-Zr nanoparticle in a resist.
With respect to claims 1-6,8-18 and 20, it would have been obvious to one skilled in the art to modify the resists and processes of using them taught in the examples of Sarma et al. 20150234272 which use a photoacid generator as a photoinitiator by replacing the methacrylate stabilized ZrO2, TiO2 or HfO2 nanoparticles with methacrylic acid stabilized TiO2-ZrO2 nanoparticles of Sullivan et al. 20130011630 which have only methacrylic acid ligands due to the use of excess methacrylic acid as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), followed by a reaction with acetyl acetone as taught in Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) to form a Ti2Zr4O or Ti2Zr6O particle where all the ligands are methacrylate with a reasonable expectation of forming a useful photoresists based upon the direction to Ti, Hf, and/or Zr oxide nanoparticles in Sarma et al. 20150234272 at [0074-0076], the disclosed equivalence of acrylic acid and methacrylic acid as photoactive ligands in Sarma et al. 20150234272 at [0101] and the exemplified use of Ti and Zr oxo resists in Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018). Further, it would have been obvious to expose them using EUV and develop them in the disclosed developers/solvents with a reasonable expectation of forming a useful resist pattern and use the result to pattern the underlying using etching as taught by Sullivan et al. 20130011630 with a reasonable expectation of success.
With respect to claims 1-6.8-18 and 20, it would have been obvious to one skilled in the art to modify the resists and processes of using them taught in the examples of Sarma et al. 20150234272 by replacing the methacrylate stabilized ZrO2, TiO2 or HfO2 nanoparticles with the acrylic acid or dimethylacrylic acid stabilized TiO2-ZrO2 nanoparticles of Sullivan et al. 20130011630 which have only acrylic acid or dimethylacrylic acid ligands due to the use of excess acrylic acid or dimethylacrylic acid as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), followed by a reaction with acetyl acetone as taught in Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) to form a Ti2Zr4O or Ti2Zr6O particle where all the ligands are acrylate or methylacrylate with a reasonable expectation of forming a useful photoresists based upon the direction to Ti, Hf, and/or Zr oxide nanoparticles in Sarma et al. 20150234272 at [0074-0076], the disclosed equivalence of acrylic acid and methacrylic acid as photoactive ligands in Sarma et al. 20150234272 at [0101] and the exemplified use of Ti and Zr oxo resists in Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018). Further, it would have been obvious to expose them using EUV and develop them in the disclosed developers with a reasonable expectation of forming a useful resist pattern and use the result to pattern the underlying using etching as taught by Sullivan et al. 20130011630 with a reasonable expectation of success.
In the arguments of 6/18/2026, the applicant argues that the processes in Sarma, Sullivan and Castellanos do not yield nanoparticles with only methacrylic acid as the ligands. The applicant achieves this by a treatment with acetyl acetone. The examiner has added Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) which teach the formation Ti2Zr4 and Ti2Zr6 oxide clusters with only methacrytlic acid ligands, which may be achieved by a ligand exchange treatment using a sufficient excess of the methacrylic acid as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002)and is definitely achieved by subsequent treatment with acetyl acetone (aka acetyl acetonate). These secondary references clearly exemplify Ti2Zr6O6(OMc)20 and Ti2Zr4O4(OMc)16 which are among the species recited in claims 2,10 and 20.
Claims 1-6,8-18 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sarma et al. 20150234272, in view of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018), further in view of Toriumi et al. 20170277036, Mizuno et al. 20080152933 or Lee et al. 20150056745
The combination of Sarma et al. 20150234272, Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018) does not teach the full range of polymerizable carboxylic acids.
It would have been obvious to modify the resists and processes of using them rendered obvious by the combination of Sarma et al. 20150234272, Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018) by replacing the acrylate or methacrylate carboxylic acids with any of trans-2,3-dimethylacrylic acid, ethylacrylic acid, propylacrylic acid and methylbutyric acid taught by Sarma et al. 20150234272, vinylbenzoic acid taught by Toriumi et al. 20170277036 and Mizuno et al. 20080152933 or the C2-20 alkene phenylacetates taught by Lee et al. 20150056745 which embrace 4-vinylpheynlacetate, 4-(2-methylvinyl)phenylacetate or 4-(3methyl-2-propenyl)phenylacetate with a reasonable expectation fop forming a useful polymerizable Ti2Zr4O or Ti2Zr6O cluster/nanoparticle, noting that the replacement of the ligands with benzoic acid or other carboxylate ligands is clearly taught in Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002).
Claims 1-6,8-18 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sarma et al. 20150234272, in view of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018), further in view of Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015).
The combination of Sarma et al. 20150234272,Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018) does not teach or exemplify the full range of Ti2Zr4 oxides.
With respect to claims 1-5,10-13 and 20, it would have been obvious to one skilled in the art to modify the photoresist/hardmasks rendered obvious by the combination of Sarma et al. 20150234272,Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018) by forming other Ti2Zr4 oxides, such as the Ti2Zr4O5 taught by Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) which have 14 ligands by using an excess of acrylic acid or methacrylic acid to induce a ligand exchange as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), followed by a reaction with acetyl acetone as taught in Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) so that all the ligands are acrylate or methacrylate with a reasonable expectation of forming a fully (meth)acrylated Ti2Zr4O5 cluster/nanoparticle.
With respect to claims 1-5,10-13 and 20, alternatively it would have been obvious to one skilled in the art to modify the photoresists/hardmasks rendered obvious by the combination of Sarma et al. 20150234272,Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) and Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018) by forming other Ti2Zr4 oxides, such Ti2Zr4O6 bounded by the formula (MaOb(OR/OH)c(OOCR)d (M= Ti, Zr) of Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) which are similar to the Ti2Zr4O5 particles exemplified taught by Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) which have 14 ligands by have 6 oxygens like the Ti2Zr6O6(OMc)20 of Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002) by using an excess of acrylic acid or methacrylic acid to induce a ligand exchange as taught by Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), followed by a reaction with acetyl acetone as taught in Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) so that all the ligands are acrylate or methacrylate with a reasonable expectation of forming a fully (meth)acrylated Ti2Zr4O5 cluster/nanoparticle.
Claims 1-6,8-18 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Sarma et al. 20150234272, in view of Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018) and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015), further in view of Toriumi et al. 20170277036, Mizuno et al. 20080152933 or Lee et al. 20150056745
The combination of Sarma et al. 20150234272, Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018) and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) does not teach the full range of polymerizable carboxylic acids.
It would have been obvious to modify the resists and processes of using them rendered obvious by the combination of Sarma et al. 20150234272, Sullivan et al. 20130011630, Kreutzer et al. “On the question of site-selective ligand exchange in carboxylate-substituted metal oxo clusters), Eur. J. Inorg. Chem., pp 2889-2894 (2015) and Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002), Castellanos et al., “Ti, Zr, and Hf-based molecular hybrid materials as EUV photoresists”, Proc. SPIE 10583, Article 105830A (12 pages) (2018) and Artner et al., “New zirconium and zirconium-titanium oxo cluster types by expansion or metal substitution of the octahedral Zr6O8 structural motif., Inorg. Chim. Acta, Vol. 432 pp 208-212 (2015) by replacing the acrylate or methacrylate carboxylic acids with any of trans-2,3-dimethylacrylic acid, ethylacrylic acid, propylacrylic acid and methylbutyric acid taught by Sarma et al. 20150234272, vinylbenzoic acid taught by Toriumi et al. 20170277036 and Mizuno et al. 20080152933 or the C2-20 alkene phenylacetates taught by Lee et al. 20150056745 which embrace 4-vinylpheynlacetate, 4-(2-methylvinyl)phenylacetate or 4-(3methyl-2-propenyl)phenylacetate with a reasonable expectation fop forming a useful polymerizable Ti2Zr4O or Ti2Zr6O cluster/nanoparticle, noting that the replacement of the ligands with benzoic acid or other carboxylate ligands is clearly taught in Schubert, U., “Zirconium and Titanium nanoclusters for use as an ablative solid rocket motor (SRM) insulation, Final report Contract F61775-02-WE037, 5 pages (10/2002).
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 July 9, 2026
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