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 1-3, 7-9, 12-15, 19 and 20 of B. Kim et al., US 18/861,891 (Oct. 31, 2024) are pending and under examination on the merits. Claims 1-3, 7-9, 12-15, 19 and 20 are rejected.
Withdrawal Claim Rejections 35 U.S.C. 112(b)
Rejection of claims 7-9 and 12 under 35 U.S.C. 112(b), as indefinite because the value of GPC ([Symbol font/0x44]GPC, %) can have multiple and variable values depending upon the conditions of atomic layer deposition (ALD) is withdrawn for the following reasons. Claim 7, which is illustrative, recites as follows:
Claim 7. The method for forming a Group 4 metal element-containing film of claim 1, wherein when the Group 4 metal element-containing compound represented by one of the Formula 2-1, Formula 2-2, or Formula 2-3 is used to form a zirconium (Zr)-containing film by atomic layer deposition (ALD)
at a process temperature of 250°C to 400 °C,
the change in GPC ([Symbol font/0x44]GPC, %) with respect to temperature as represented by the following Equation A is 30% or lower:
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in Equation A, GPC250 is the GPC at 250°C, and GPCtemp is the GPC at a process temperature.
Upon reconsideration of the § 112(b) rejection, the following analysis applies. Dependent claim 7 further limits claim 1 by requiring employment of a composition comprising one of Formula 2-1, Formula 2-2, or Formula 2-3 in the claim 1 method and requiring a process temperature of 250°C to 400 °C. The claim 7 recitation of “the change in GPC ([Symbol font/0x44]GPC, %) with respect to temperature as represented by the following Equation A is 30% or lower” is simply the natural or intended result of employing Formula 2-1, Formula 2-2, or Formula 2-3, in the claim 1 method, at the recited process temperature. MPEP § 2111.04; see Claim Interpretation above respecting the specification’s teachings on [Symbol font/0x44]GPC, % in the previous Office action. Claim 7 is thus clear to one of ordinary skill.
The same analysis applies to claims 8, 9, and 12.
Withdrawal Claim Rejections - 35 USC § 112(d)
Rejection of dependent claims 7-9 and 12 under 35 U.S.C. 112(d) as being of improper dependent form for failing to further limit the subject matter of claim 1 upon which they depend is withdrawn under the rationale for discussed above. Claims 7-9 and 12 further limit claim 1 by reciting specific precursor compounds and process temperatures to be employed in the method of claim 1.
Withdrawal Claim Rejections - 35 USC § 102 (AIA )
Rejection of claims 1-3, 7-9, 12, and 15 under 35 U.S.C. 102(a)(1)/(2) as being anticipated by S. Kim et al., US 2022/0205099 (2022) (“Kim”) is withdrawn in view of Applicant’s amendments. Kim does not teach the claim 1 and 15 limitations of
Claim 1 . . . wherein structural regioisomer impurities are present in an amount of 5% or less relative to the vaporized Group 4 metal element-containing precursor compound as determined by 1H-NMR spectroscopy.
Claim 15 . . . wherein structural regioisomer impurities are present in an amount of 5% or less relative to the Group 4 metal element-containing precursor compound as determined by 1H-NMR spectroscopy
or the narrower range recitations in new claims 19 and 20. As such, there is no anticipation.
The specification does not define or use the term “structural regioisomer impurities”, but rather uses the term “structural isomer”. See e.g., specification at page 6, [50]-[51]. In view of the plain meaning of “regioisomer”, the term “structural regioisomer impurities” is interpreted, consistently with the specification, as a modified claim 1 precursor compound in which the alkyl groups are arranged in a different positional relationship on the cyclopentadiene ring than as depicted in claim 1. MPEP § 2111, specification at page 6, [50]-[51].
The plain meaning of “are present” (as bolded above) requires that at least some “structural regioisomer impurities” are in fact present, but in a non-zero amount of 5% or less. MPEP § 2111.
Withdrawal Claim Rejections - 35 USC § 103
Rejection of claims 1-2, 7-9, 12, and 14-15 under AIA 35 U.S.C. 103 as being unpatentable over S. Kim et al., US 2022/0205099 (2022) (“Kim”) in view of J. Lee et al., US 5,434,324 (1995) (“Lee”) is withdrawn in view of Applicant’s amendments.
Rejection of claim 13 as obvious over Kim and Lee as above in further view of J. Niinistö, 18 Journal of Materials Chemistry, 5243-5247 (2008) (“Niinistö”) is withdrawn in view of Applicant’s amendments. The cited art does not teach or suggest the claim 1 and 15 limitations of
Claim 1 . . . wherein structural regioisomer impurities are present in an amount of 5% or less relative to the vaporized Group 4 metal element-containing precursor compound as determined by 1H-NMR spectroscopy.
Claim 15 . . . wherein structural regioisomer impurities are present in an amount of 5% or less relative to the Group 4 metal element-containing precursor compound as determined by 1H-NMR spectroscopy
or the narrower range recitations in new claims 19 and 20.
Claim Rejections 35 U.S.C. 112(a) -- New Matter
The following is a quotation of the first paragraph of 35 U.S.C. 112(a):
(a) IN GENERAL.—The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor or joint inventor of carrying out the invention.
Amendments narrowing the claims by introducing elements or limitations which are not supported by the as-filed disclosure is a violation of the written description requirement of 35 U.S.C. 112(a). MPEP § 2163.05(II). Ipsis verbis disclosure is not necessary to satisfy the written description requirement; If a skilled artisan would have understood the inventor to be in possession of the claimed invention at the time of filing, even if every nuance of the claims is not explicitly described in the specification, then the adequate description requirement is met. MPEP § 2163(II)(A)(3)(a) (citing Vas-Cath, Inc. v. Mahurkar, 935 F.2d 1555, 1560, 19 USPQ2d 1111, 1114 (Fed. Cir. 1991). The failure to meet the written description requirement of 35 U.S.C. 112(a) commonly arises when the claims are changed after filing to either broaden or narrow the breadth of the claim limitations, or to alter a numerical range limitation or to use claim language which is not synonymous with the terminology used in the original disclosure. MPEP § 2163.05.
The Claim 1 and 15 Amended Range Respecting “structural regioisomer impurities” Is New Matter
Claims 1-3, 7-9, 12-15, 19 and 20 are rejected under 35 U.S.C. 112(a) as failing to comply with the written description one the grounds that the application as filed does not support the claim 1 or 15 amendments of:
Claim 1 . . . wherein structural regioisomer impurities are present in an amount of 5% or less relative to the vaporized Group 4 metal element-containing precursor compound as determined by 1H-NMR spectroscopy.
Claim 15 . . . wherein structural regioisomer impurities are present in an amount of 5% or less relative to the Group 4 metal element-containing precursor compound as determined by 1H-NMR spectroscopy
or the narrower range recitations in new claims 19 and 20.
The specification does not define or use the term “structural regioisomer impurities”, but rather uses the term “structural isomer”. See e.g., specification at page 6, [50]-[51]. In view of the plain meaning of “regioisomer”, the term “structural regioisomer impurities” is interpreted, consistently with the specification, as a modified claim 1 precursor compound in which the alkyl groups are arranged in a different positional relationship on the cyclopentadiene ring than as depicted in claim 1. MPEP § 2111, specification at page 6, [50]-[51].
The plain meaning of “are present” (as bolded above) requires that at least some “structural regioisomer impurities” are in fact present, but in a non-zero amount of 5% or less. MPEP § 2111.
Applicant argues that support for the above amendment can be found at least at paragraphs [0038], [0039] and [0053] of the specification. Reply at page 9.
Paragraph [0053], cited by Applicant does not appear relevant to the subject claim amendment. Paragraphs [0038]-[0039] of US 2025/0109496, cited by Applicant recite as follows:
[0038] In particular, the Group 4 metal element-containing precursor compound represented by Formula 1 may be in a structure of a single composition. Here, the term "single composition" refers to a substance that does not contain structural isomers. It may not mean a 100% pure substance. For example, it may contain impurities of 5% or less. In addition, the term "impurities" may refer to all substances except for the Group 4 metal element-containing precursor compound represented by Formula 1.
[0039] Specifically, the Group 4 metal element-containing precursor compound represented by Formula 1 may be in a structure of a single composition (single substance structure) when analyzed by a 1H-NMR spectrum, in which structural isomers or mixtures thereof are not contained,
and the content of impurities is, for example, 5% or less, 3% or less, 2% or less, 1 % or less, or 0.5% or less.
Thus, the Group 4 metal element-containing precursor compound represented by Formula 1 has a high purity of 95% or more, is present in a liquid state at room temperature, which is advantageous in the preparation process, and has excellent thermal stability; thus, it is possible to easily form various Group 4 metal element-containing films.
Here the cited specification portion refers to a range 5% or less with respect to all impurities (i.e., any substance other than the claimed precursor). The specification does not recite the range of 5% or less with respect to a “structural regioisomer”. The cited specification portions therefore do not support the subject claim 1 amendment.
With respect to changing numerical range limitations, an analysis must take into account which ranges one skilled in the art would consider inherently supported by the discussion in the original disclosure. MPEP § 2163.05(B)(III) (citing In re Lukach, 442 F.2d 967, 169 USPQ 795 (CCPA 1971) and In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976)).
The specification does not literally recite this range or even any example compositions where at least some “structural regioisomer impurities” are in fact present, but in a non-zero amount of 5% or less. It is noted that particular embodiment of the specification is the claim 1 precursors as “single composition”, i.e., a composition not comprising any regioisomers, as originally claimed. Specification at page 6, lines 7-10; Id. a page 6, lines 13-15; Id. at page 29, lines 27-29. However, this embodiment does not fall within the subject claim range because a non-zero amount of “structural regioisomer impurities” is also required.
Subject Matter Free of the Art of Record
Subject to the new matter rejection, claims 1-3, 7-9, 12-15, 19 and 20 are free of the art of record.
The closest art of record is S. Kim et al., US 2022/0205099 (2022) (“Kim”) in view of J. Lee et al., US 5,434,324 (1995) (“Lee”).
Kim teaches film-forming methods as follows:
[0008] . . methods for forming a Group IV transition metal containing film, the method comprising the steps of:
[0009] a) exposing a substrate to a vapor of a Group IV transition metal containing film forming composition;
[0010] b) exposing the substrate to a co-reactant; and
[0011] c) repeating the steps of a) and b) until a desired thickness of the Group IV transition metal containing film is deposited on the substrate using a vapor deposition process,
[0012] wherein the Group IV transition metal containing film forming composition comprises a precursor
having the formula:
M(R1R2Cp) (L1),
wherein, M is a Group IV transition metal selected from Zr, Hf or Ti.
Kim at page 1, [0008]-[0012].
Kim teaches that the process may be an atomic layer deposition (ALD). Kim at page 1, [0035]. Kim teaches that the co-reactant may be selected from O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen radicals thereof or mixtures thereof, or H2, H2CO, N2H4, NH3, an amine, a hydrazine N(SiH3)3, radicals thereof or mixtures thereof. Kim at page 1, [0019]. Thus, Kim teaches the claim 1 method steps of
Claim 1 . . . subjecting a composition for film deposition comprising a vaporized Group 4 metal element-containing precursor compound . . . to a reaction with a reaction gas to form a Group 4 metal element-containing film on a substrate . . .
Kim teaches the following metallocene species are useful in the disclosed film forming method.
Zr(Me(nPr)Cp)(NMe2)3;
Zr(Me(nBu)Cp)(NMe2)3;
Zr(Me(iBu)Cp)(NMe2)3;
Hf(Me(nPr)Cp)(NMe2)3;
Hf(Me(nBu)Cp)(NMe2)3; and
Hf(Me(iBu)Cp)(NMe2)3.
Kim page 5, [0107]; Id. at [0108]. Kim’s above metallocenes can be drawn as different regioisomers with respect to the placement of the alkyl groups on the cyclopentadiene ring.
For example, the structures can be drawn as the following structures:
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in conformance with Kim Table 1, which Table indicates that the two alkyl substituents R1 and R2 of Kim general formula M(R1R2Cp)(L1) are positioned on the cyclopentadiene ring (Cp) as separated by one Cp-ring carbon. Kim at page 11, Table 1. Kim’s compounds (as drawn above) are the same species employed in the method of instant claim 1 and claimed in claim 15.
Differences between Kim and Claims 1 and 15
Kim does not teach the claim 1 and 15 limitations of
Claim 1 . . . wherein structural regioisomer impurities are present in an amount of 5% or less relative to the vaporized Group 4 metal element-containing precursor compound as determined by 1H-NMR spectroscopy.
Claim 15 . . . wherein structural regioisomer impurities are present in an amount of 5% or less relative to the Group 4 metal element-containing precursor compound as determined by 1H-NMR spectroscopy
which limitations are present in dependent claims 2-3, 7-9, 12-15, or the narrower range recitations in new claims 19 and 20. As such, there is no anticipation.
The specification does not define or use the term “structural regioisomer impurities”, but rather uses the term “structural isomer”. See e.g., specification at page 6, [50]-[51]. In view of the plain meaning of “regioisomer”, the term “structural regioisomer impurities” is interpreted, consistently with the specification, as a modified claim 1 precursor compound in which the alkyl groups are arranged in a different positional relationship on the cyclopentadiene ring than as depicted in claim 1. MPEP § 2111, specification at page 6, [50]-[51].
The plain meaning of “are present” (as bolded above) requires that at least some “structural regioisomer impurities” are in fact present, but in a non-zero amount of 5% or less. MPEP § 2111.
The Claims are Not Obvious in View of Kim
claims 1-3, 7-9, 12-15, 19 and 20 are not obvious in view of Kim because one of ordinary skill is not motivated to include, in a composition of the claimed metallocene, at least some “structural regioisomer impurities” but in a non-zero amount of 5% or less.
Secondary Reference J. Lee et al., US 5,434,324 (1995) (“Lee”)
Lee teaches a synthetic scheme to prepare 1-methyl-3-n-propylcyclopentadiene. Lee at col. 2, line 48 to col. 3, line 35. In the working Example, Lee teaches synthesis of 1-methyl-3-n-propylcyclopentadiene (along with 28% exo isomers) where 1HNMR was used to determine a yield of 77±4%, present in the organic layer upon workup and where the product structure was confirmed by GC/MS. Lee at column 3, lines 30-35. The Examiner summarizes Lee’s working example as follows:1
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.
Note that Lee teaches that the exo-isomers are not reactive in the formation of metallocenes:
The synthesis of 1-methyl-3-alkylcyclopentadienes by the reaction of 3-methyl-2-cyclopentene-1-one with alkyl Grignard reagents such as methyl, ethyl or isopropyl magnesium halides, followed by alcohol formation and dehydration using strong acids such as HCl or p-toluene sulfonic acid is described in the literature. These processes give about a 50/50 mixture of endo and exo isomers. The exo isomers are not useful in forming metallocenes such that when such isomer mixtures are used in making metallocenes, the yield of metallocene is less than 50%. We have now disclosed a process which favors the formation of the desirable endo isomers.
Lee at col. 1, lines 16-27 (emphasis added). Thus, Lee’s exo isomer formation is inconsequential because (per above), Lee teaches that the exo does not react to form a metallocene.
In any case, Lee purports to form the methyl-3-n-propylcyclopentadiene comprising only one regioisomer with respect to the positional relationship of the alkyl groups.
One of ordinary skill is motivated to combine Lee with Kim so as to provide a source of dialkylcyclopentadienyl ligand and would thereby arrive Kim’s above-cited metallocenes as a single regioisomer (i.e., zero percent of structural regioisomer impurities) for use in Kim’s disclosed film-forming method. However, such combination still does not teach the cited claim 1 and 15 limitations which require at least some “structural regioisomer impurities” in a non-zero amount of 5% or less.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). 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.
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ALEXANDER R. PAGANO
Examiner
Art Unit 1692
/ALEXANDER R PAGANO/Primary Examiner, Art Unit 1692
1 Note that Lee’s procedure is the same procedure disclosed in the instant specification for 1-methyl-3-n-Propylcyclopentadiene. Specification at page 20 (Preparation Example 1). That is, the specification teaches preparation of compound 4-1, as follows, that can be used as starting material to prepare the claimed complexes “as a single composition”. Specification at page 20.
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Specification at page 20 (Preparation Example 1).
Prosecution Insights