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 .
DETAILED ACTION
Claims 1-23 of J. Park et al., US 18/212,376 (Jun. 21, 2023) are pending. Claims 7-10 and 12-23 drawn to the non-elected invention/species are withdrawn from consideration pursuant to 37 CFR 1.142(b). Claims 1-6 and 11 are under examination on the merits and are rejected.
Election/Restrictions
Applicant elected Group (I), claims 1-18, without traverse in the Reply to Restriction Requirement filed on January 23, 2026. Claims 19-23, to non-elected inventions of Groups (II) and (III), are withdrawn from consideration pursuant to 37 CFR 1.142(b). The restriction/election requirement is made FINAL.
Pursuant to the election of species requirement Applicant elected, without traverse, the species of chemical formula 2-1:
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for prosecution on the merits to which the claims shall be restricted if no generic claim is finally held to be allowable. In the Reply, Applicant indicates that claims 1-6 and 11 of elected Group (I) read on the elected species (i.e., claims 7-10 and 12-18 do not read on the elected species) The elected species was searched and determined to be unpatentable pursuant to § 102. The search/examination was extended to the additional species cited in the § 102 rejection and to the full scope of claim 1, Chemical Formula 1, where deuterium is incorporated beyond its natural isotopic abundance (see more detailed discussion below). MPEP § 803.02 (III)(C)(2). The provisional election of species requirement is given effect and claims 7-10 and 12-18 of elected Group (I) are withdrawn from consideration as not reading on the elected species. MPEP § 803.02(III)(A).
Claim Rejections - 35 USC § 102 (AIA )
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.
§ 102(a)(1) Rejection over M. Shirai et al., JP 2012201652 A (2012) (“Shirai”)
Claims 1-6 and 11 and the elected species are rejected under 35 U.S.C. 102(a)(1) as being anticipated by M. Shirai et al., JP 2012201652 A (2012) (“Shirai”). An English-machine language translation (Google Translate) is attached as the second half of reference Shirai. Shirai thus consists of 20 total pages (including the English-language portion). Accordingly, this Office action references Shirai page numbers in the following format “xx of 20”.
Shirai teaches that zirconium amide compounds are useful as raw materials in chemical vapor deposition and atomic layer deposition. Shirai at page 13 of 20, [0004]. In working Example 1, Shirai teaches preparation of 5.35 g (18.5 mmol) (cyclopentadienyl)tris(dimethylamido)zirconium (CpZr(NMe2)3)in reaction using cyclopentadiene:
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Shirai at pages 17-18 of 20, [0053]. It is a statistically certainty that Shirai’s 5.35 g of the above compound (having 1.12 [Symbol font/0xB4] 1022 discrete molecules) necessarily comprises the elected species (where all five valences of the cyclopentadiene ring are occupied by deuterium). This is because the natural isotopic abundance of Hydrogen 1H is 99.985 % and that of 2H is 0.015 %. W. Meier-Augenstein et al., Stable Isotope Analysis: General Principles and Limitations, In Wiley Encyclopedia of Forensic Science, 1-15 (2012); MPEP § 2112(IV); see also, MPEP § 2112(II) (citing Toro Co. v. Deere & Co., 355 F.3d 1313, 1320, 69 USPQ2d 1584, 1590 (Fed. Cir. 2004) (“[T]he fact that a characteristic is a necessary feature or result of a prior-art embodiment (that is itself sufficiently described and enabled) is enough for inherent anticipation”).1
§ 102(a)(1) Rejection over D. Kissounko et al., 126 Journal of the American Chemical Society, 1776-1783 (2007) (“Kissounko”)
Claims 1 and 3-6 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by D. Kissounko et al., 126 Journal of the American Chemical Society, 1776-1783 (2007) (“Kissounko”). Kissounko discloses the following compound 6-d1 in the following excerpt.
Cp*Ti(NDiPr)3 (6-d1). This complex was prepared in a similar way as 6 from 5 (0.372 g, 1.18 mmol) and iPrND2 (0.56 g, 11.80 mmol) to afford the product 6-d1 as yellow crystals (0.201 g, 49.2%).
Kissounko at page 1782, col. 2. Where compound 6-d1 has the following structure.
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See, Kissounko at page 1777, Scheme 2 (depicting the structure of non-deuterium enriched compound 6); see also, CAS Abstract and Indexed Compound from D. Kissounko et al., 126 Journal of the American Chemical Society, 1776-1783 (2007).
Kissounko compound 6-d1 meet each and every limitation of claim 1, where M is titanium, R1 to R6 are deuterium or an unsubstituted C1-C6 alkyl group; R7 to R11 are an unsubstituted C1-C6 alkyl group; and where the above compound meets the claim 1 proviso of:
Claim 1 . . . provided that at least one of R7 to R11 is necessarily deuterium or at least one of R1 to R6 necessarily includes deuterium . . .
The additional deuterium limitations of claims 3-6 are met for the same reasons discussed for Shirai above. That is, deuterium would necessarily be present at the claimed positions by virtue its natural abundance of 0.015 %.
Extension of Search
The search was further extended to the full scope of claim 1, Chemical Formula 1, where deuterium is incorporated beyond its natural isotopic abundance. Subject to an updated search, other than Kissounko compound 6-d1 (as discussed above) the art of record does not disclose any additional compounds falling within the scope of claim 1, where deuterium is incorporated beyond its natural abundance. The closest art of record is J. Niinistö et al., 18 Journal of Materials Chemistry, 5243-5247 (2008). Niinistö teaches that although widely applied in atomic layer deposition (ALD) for metal oxide film formation, alkylamido-type precursors, such as Zr(NEtMe)4 have problems with thermal stability in ALD processes (where ALD requires high temperatures).2 Niinistö at page 5243, col. 1. Niinistö teaches that CpZr(NMe2)3 is advantageous for zirconium oxide film formation because cyclopentadienyl (Cp) group lends increased thermal stability. Niinistö at paragraph bridging pages 5243-5244; Id at page 5247, col. 2. Niinistö’s CpZr(NMe2)3 necessarily comprises deuterium at its natural abundance and would thus comprise at least some d5-CpZr(NMe2)3, which is the elected species. Niinistö’s teaches synthesis of 49 g of CpZr(NMe2)3 by reaction of Li(NMe2) with CpZrCl3. Niinistö at page 5244, col. 1. Niinistö’s CpZr(NMe2)3 is not deuterated beyond deuterium’s natural abundance.
With respect to deuteration of vapor deposition precursors beyond the natural abundance, R. Jilek et al., US 2022/0411446 (2022) teaches that compounds of the formula RSnL3, wherein R is a deuterated hydrocarbyl group and L is a hydrolysable ligand are useful for forming a RSnL3 films (for example, trideuteromethyltin-tris(tert-pentoxide ) on an EUV photoresist substrate. Jilek at page 1, [0010]; Id. at page 11, [0089] (Example 3). The RSnL3 film (formed by non-destructive vapor deposition such as ALD) is then exposed to UV or EUV to decomposed selected areas (by which the radiation sensitive Sn-C bond is cleaved to give a condensed network comprising SnO-Sn and Sn-OH bonds) and then either the exposed or unexposed areas are removed by solvent development to form a photoresist pattern on the substrate. Jilek at page 2, [0026]; Id. at page 8, [0064]. Jilek speculates that substitution of deuterium atoms into the radiation sensitive organotin compositions RSnL3 is thought to be advantageous due to alteration of kinetic reaction pathways (where presumably Jilek is referring to light-induced reaction pathways) in view of the kinetic isotope effects of deuterium versus hydrogen. Jilek at page 2, [0029]. Jilek does not teach or mention the claimed metals (i.e., titanium, zirconium, or hafnium).
X. Li et al., US 2002/0076576 (2002) (“Li”) teaches deuterated semiconductor organic compounds used in optoelectronic devices. Li at page 1, [0007]. Li teaches that carbon-deuterium chemical bond is stronger, more stable, and reacts more slowly than the carbon-hydrogen chemical bond, so that the deuterated organic system has better thermal stability, and longer lifetime in optoelectronic devices. Li at page 2, [0009]. Li is limited to organic species and does not teach or mention the claimed metals (i.e., titanium, zirconium, or hafnium).
Here, the claimed compounds of Chemical Formula 1, wherein deuterium is incorporated beyond its natural abundance would not be obvious because motivation is lacking to make such substitution. However, the Examiner has not considered whether there is written description support for such an amendment to the instant claims. For example, Niinistö discloses the non-deuterium-enriched compounds of claim 1 for use as precursors for forming metallic oxide films. One of ordinary skill does not have a reasonable expectation (in view of the above secondary art) that substitution of hydrogen for deuterium in Niinistö’s CpZr(NMe2)3 would impart increased thermal stability (or other useful properties) to the extent that the substituted compound is more suitable for its intended use in the formation of zirconium oxide films by destructive chemical vapor deposition techniques. MPEP § 2143.02; see footnote 1. For example, while one of ordinary skill could reasonably postulate that a deuterium-enriched cyclopentadiene (Cp) ring, in isolation, would be more thermally stable than the non-enriched species, it is not clear to one of ordinary skill that deuterium enrichment of CpZr(NMe2)3 imparts increased thermal stability to the full compound (for example, to the Zr bonds) such that it has increased stability in the heated vapor phase and thereafter decomposes on the substrate to form the zirconium oxide film.
Conclusion
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ALEXANDER R. PAGANO
Examiner
Art Unit 1692
/ALEXANDER R PAGANO/Primary Examiner, Art Unit 1692
1 The natural isotopic abundance of deuterium is 0.015 % (15 of every 1000 are D), which converted to a decimal probability is 0.00015. Thus, (using the standard binomial probability formula) the decimal probability that one position of the cyclopentadienyl ring (Cp) of CpZr(NMe2)3 is occupied by deuterium is 0.00015. Since there are five independent positions on the cyclopentadienyl ring (Cp) of CpZr(NMe2)3 that can each be occupied by either hydrogen or deuterium, the probability (P5) that all five are deuterium is the probability raised to the fifth power (0.00015)5 = 7.59 [Symbol font/0xB4] 10-20. Thus, the amount of D5-CpZr(NMe2)3 in Shirai’s 5.35 g (0.018 mol) sample (i.e., deuterium at all five positions of the Cp ring) is calculated by multiplying the moles of CpZr(NMe2)3by the probability, or (0.018) mols [Symbol font/0xB4] (0.00015)5 = 1.37 [Symbol font/0xB4] 10-21 mols of D5-CpZr(NMe2)3 or about 780 molecules.
2 The ALD process is limited by the thermal decomposition temperature of the precursor. M. Leskelä et al., 409 Thin Solid Films, 138-147 (2002). A known issue with organometallic ALD precursors is thermal decomposition in the heated vapor phase before deposition and decomposition upon the substrate to form the desired metallic oxide film. See e.g., KR-20200114741 A (2020) (see page 17 of 24, [0007].