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, and 12-15 of B. Kim et al., US 18/861,891 (Oct. 31, 2024) are pending and under examination on the merits.
Claim Interpretation
Examination requires claim terms first be construed in terms in the broadest reasonable manner during prosecution as is reasonably allowed in an effort to establish a clear record of what applicant intends to claim. See, MPEP § 2111.
Interpretation “change in GPC ([Symbol font/0x44]GPC, %)” of Claims 7 and 12
Claims 7 and 12 recite a [Symbol font/0x44]GPC (%) limitation that functionally defines the metal film. Claim 7 is reproduced below.
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.
Claim 12 differs from claim 7 only in that hafnium is the “the compound represented by Formulae 3-1, Formula 3-2, or Formula 3-3 is used to form a hafnium (hf)-containing film”. Thus, claims 7 and 12 differ only in zirconium versus hafnium.
The growth per cycle (GPC) is Growth per cycle (GPC) is generally defined in the art as the incremental increase in the thickness of the film per cycle of deposition in an atomic layer deposition process. A. Philip et al., 82 Pramana Journal of Physics, 563-569 (2014) (see page 564 “2. Calculation of GPC”); J. van Ommen et al., Kirk-Othmer Encyclopedia of Chemical Technology, Atomic Layer Deposition, 1-42 (2021) (“Ommen”) (see pages 6-8). In this regard, J. Multia et al., 9 Advanced Materials Interfaces, 1-39 (published April 22, 2022) (“Multia”) teaches that:
The overall deposition process is typically examined and evaluated by monitoring the film growth rate as a function of different deposition parameters (precursor and purge pulse lengths, deposition temperature, etc.). The growth rate is expressed as a so-called growth-per-cycle (GPC) value calculated from the total film thickness divided by the number of precursor cycles applied. For ideal ALD and MLD processes, expected is to see a saturation behavior for the GPC value with increasing precursor pulse length (for both precursors), and also a linear dependence of the film thickness on the number of deposition cycles.
This is consistent with the specification. Specification at page 31, lines 13-16.
Consulting the most relevant portion of the specification, in Test Example 2, the specification teaches that each of the following example compounds (either as a single-compound or isomer mixture as indicated below):
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was tested under atomic layer deposition (ALD) conditions in a reaction chamber to form a zirconium oxide film on silicon substrate. Specification at pages 30-31, [260]-[272] (“Test Example 2”). In testing each compound, the silicon substrate was placed in the ALD reaction chamber heated to 120 °C and one of the above four compounds was transferred from a heated stainless-steel canister to the heated reaction chamber in a gaseous state using argon flow (at a flow rate of about 200 to 500 sccm). Id. at page 30. Next, reaction gas ozone (O3) pumped into the reaction chamber at a concentration of about 180 to 220 g/m3. Id. at page 30. The process pressure of the reaction chamber was maintained at 0.9 to 1.2 Torr. Test Example 2 teaches that separate ALD experiments (each ALD experiment consisted of the 100 cycles) were performed for each test compound at a specific process temperature within the range of about 250 °C to 400 °C (see Table 1 for specific temperatures used). Id. at page 30.
Test Example 2 teaches each cycle of the total 100 cycles of the atomic layer deposition were performed under the following conditions, where each ALD cycle successively adds a zirconium oxide layer upon the silicon substrate. Id. at page 30.
[264] The ALD gas supply cycle was repeated 100 times to form a zirconium (Zr)containing oxide film, in which each ALD gas supply cycle consists of the steps of
supplying the composition for film deposition in a gaseous state for about 5 to 30 seconds;
supplying argon (Ar) gas for about 5 to 30 seconds to remove the composition for film deposition (gas) remaining in the reactor;
supplying ozone (O3) as a reaction gas for about 5 to 30 seconds;
and supplying argon (Ar) gas for about 5 to 30 seconds to remove ozone (O3) remaining in the reactor.
Specification at page 30, [264]. Test Example 2 teaches that after the 100 cycles for the specific compound at the specific temperature, the total thickness of each zirconium (Zr) oxide film was measured, the GPC for each film calculated by dividing the film’s thickness by cycle number (i.e., 100 cycles), the [Symbol font/0x44]GPC (%) calculated by equation of claim 7. Specification at page 31, [266]-[272]. The data is summarized in Table 1 (page 34) and Fig. 2. The specification discusses the data. Specification at page 35, [284]-[288].
In view of the foregoing, the claim 7 and 12 recitation of:
claims 7 and 12 . . . 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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is broadly and reasonably interpreted, based on its plain language, and consistently with the specification, as the [Symbol font/0x44]GPC (%) per the above equation, when a single precursor compound (one of the compounds specified in claims 7 or 12) is subjected to two atomic layer deposition experiments (the first ALD experiment performed at 250 °C and the second ALD experiment performed at a second specific single temperature within the range of 251°C to 400 °C, where each ALD experiment is reasonably interpreted as performed for the same number of ALD cycles. Note that the neither the number of ALD cycles nor ALD conditions are specified by claims 7 or 12, thus are arbitrarily selected by the practitioner. The “GPCtemp” and “GPC250” are each calculated by dividing the total film thickness by the cycle number and then each of the calculated “GPCtemp” and “GPC250” are plugged into the above equation to arrive at [Symbol font/0x44]GPC (%) between the ALD experiment performed at GPC250 and the second ALD experiment performed at the second specific temperature selected between 251°C to 400 °C. The [Symbol font/0x44]GPC (%) calculated according to the equation of claim 7 and 12, must be 30% or lower to meet the limitations of claims 7 and 12.
Interpretation of the Claim 1 Phrase “in a structure of single composition”
Claim 1 recites:
Claim 1 . . . wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition.
With regard to the meaning of “a structure of a single composition”, the specification teaches that:
[50] In particular, the Group 4 metal element-containing precursor compound represented by Formula I 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.
[51] Specifically, the Group 4 metal element-containing precursor compound represented by Formula I 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 I 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.
Specification at page 6, [50]-[51] (emphasis added).
Consistent with the specification, the claim 1 phrase “wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition” is broadly and reasonably interpreted to mean the compound of claim 1, that is, a composition comprising one of:
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but not comprising a structurally isomeric form of the particular claim 1 with respect to the positional arrangement of the two alkyl groups. As shown above and in the specification, the double bonds are delocalized in the metallocenes and thus double bond placement is not an issue. Not comprising another isomer with respect to the positional arrangement of the two alkyl groups, in the context of this interpretation (where the specification states “does not contain” as bolded above), is reasonably interpreted by the Examiner as not containing a detectable amount of another isomer by 1H NMR. This is reasonable because the specification provides 1H NMR comparison data (discussed in more detail below) to emphasize this aspect, particularly by way of the working Examples. See for example, Comparative Example 5. Specification at pages 27-29. For example, with respect to formula 3-1, the subject limitation requires that the composition not comprise a detectable amount of the following regio(position)isomer by 1HNMR:
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Looking to the specification, in Preparation Example 1, the specification teaches preparation of compound 4-1, as follows, as a single isomer, that can be used as starting material to prepare the claimed complexes. Specification at page 20.
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Specification at page 20. The Examiner presumes, absent any indication in the specification otherwise, compound 4-1, as prepared in this Example, is isomerically pure. Thus, claimed organometallic complexes prepared from such isomerically pure 4-1 as the starting material (e.g., Example 1, specification at pages 23-24 teaching synthesis of claimed compound 2-1) would meet the claim 1 limitation of “wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition”.
One the other hand, the specification Preparation Example 4 teaches that the following synthesis (where the starting methylcyclopentadiene is presumed by the Examiner as a mixture of isomers)1 provides an isomeric mixture of compounds 4-1, 4-3 and 4-4.
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Specification at pages 21-22.
Rejections 35 U.S.C. 112(b)
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION. — The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
Pursuant to 35 U.S.C. 112(b), the claim must apprise one of ordinary skill in the art of its scope so as to provide clear warning to others as to what constitutes infringement. MPEP 2173.02(II); Solomon v. Kimberly-Clark Corp., 216 F.3d 1372, 1379, 55 USPQ2d 1279, 1283 (Fed. Cir. 2000). The meaning of every term used in a claim should be apparent from the prior art or from the specification and drawings at the time the application is filed. Claim language may not be ambiguous, vague, incoherent, opaque, or otherwise unclear in describing and defining the claimed invention. MPEP § 2173.05(a).
Superfluous Structure
Claims 1-3, 7-9, and 12-14 are rejected pursuant to 35 U.S.C. 112(b), as indefinite because it is unclear what the following generic structure depicted in claim 1 signifies:
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.
This structure hangs in claim 1 with no context and where variables R1-R8 are not defined. It is not clear whether this structure is intended as a claim limitation or just a carryover that was inadvertently not deleted during claim amendment. Claim 1 is complete in the absence of this structure and it appears it should be deleted by amendment. If Applicant intends this structure as a limitation, then claim 1 should so indicate and R1-R8 should be clearly defined.
Unclear Claim Term “change in GPC ([Symbol font/0x44]GPC, %)” of Claims 7 and 12
Claims 7-9 and 12 are rejected pursuant to 35 U.S.C. 112(b), as indefinite because the meaning of the claim 7 and 12 recitation of:
claims 7 and 12 . . . 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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is unclear to one of skill in the art because the value of GPC ([Symbol font/0x44]GPC, %) can have multiple and variable values depending upon the conditions of atomic layer deposition (ALD) selected by the claim practitioner. Infringement of claims 7 and 12 therefore cannot be unambiguously determined for a particular compound tested.
Interpretation of the claim 7 and 12 recitation of:
claims 7 and 12 . . . 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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was discussed in detail above. As noted above, neither the number of ALD cycles nor ALD conditions are specified by claims 7 or 12, thus are arbitrarily selected by the practitioner. For example, the reaction gas is not specified for either claim.
The art teaches that thin film formation by atomic layer deposition in which a precursor compound reacts with a counter reactant in the gas phase to coat a substrate with a thin film is generally performed as follows:
A general ALD process is illustrated in Fig. 1. It consists of sequential alternating pulses of gaseous chemical precursors that react with the substrate. These individual gas-surface reactions are called ‘half-reactions’ and appropriately make up only part of the materials synthesis. During each half-reaction, the precursor is pulsed into a chamber under vacuum (<1 Torr) for a designated amount of time to allow the precursor to fully react with the substrate surface through a self-limiting process that leaves no more than one monolayer at the surface. Subsequently, the chamber is purged with an inert carrier gas (typically N2 or Ar) to remove any unreacted precursor or reaction by-products. This is then followed by the counter-reactant precursor pulse and purge, creating up to one layer of the desired material. This process is then cycled until the appropriate film thickness is achieved.
R. Johnson et al., 17 Materials Today, 236-246 (2008) (see page 236, col. 1, emphasis added). This general procedure is consistent with instant specification Test Example 2, discussed in Claim Interpretation above. In Test Example 2, ozone was used as the counter reactant, with a claimed zirconium precursor of Example 1, to form a zirconium oxide film on a silicon substrate, using specified ALD conditions and 100 cycles. Specification at pages 30-31.
Accordingly, in the practice of claims 7 and 12, the following parameters must be selected by the practitioner:
• a substrate;
• precursor deposition pressure;
• counter reactant (a compound that reacts with the precursor compound to form the film, e.g., reaction gas such as ozone);
• counter reactant pressure
• a specific ALD reaction temperature; and
• pulse times for the reactant and counter reactant (the specific duration of time that a gaseous precursor is allowed to be present in the reaction chamber during a single cycle of the deposition process).
Selection of these parameters clearly affects the thickness of the film formed. See e.g., J. Niinistö et al., 18 Journal of Materials Chemistry, 5343-5247 (2008) (see, page 5245, Figs. 2-4); J. van Ommen et al., Kirk-Othmer Encyclopedia of Chemical Technology, Atomic Layer Deposition, 1-42 (2021) (“Ommen”) (see pages 6-7 discussing various factors that affect the GPC, such as number of cycles). 2
A claim may be rendered indefinite when a limitation of the claim is defined by reference to an object and the relationship between the limitation and the object is not sufficiently defined. MPEP § 2173.05(b)(II). That is, where the elements of a claim have two or more plausible constructions such that the examiner cannot readily ascertain positional relationship of the elements, the claim may be rendered indefinite. MPEP § 2173.05(b)(II).
In the instant case, these required atomic layer deposition (ALD) parameters for practice of claims 7 and 12 are not defined by the claim or the specification. As such, the value of in GPC ([Symbol font/0x44]GPC, %) can be manipulated and is variable for the same precursor compound tested. In other words, one of skill practicing claims 7 or 12 to get a particular value of [Symbol font/0x44]GPC, % under one set of ALD conditions of time, temperature, concentration of compound per cycle (e.g., pulse times, which control the amount of compound admitted to the reaction chamber), flow rate, identity of reaction gas (which reacts with the compound and therefore dictates the film composition), etc, can obtain a different value of ([Symbol font/0x44]GPC, %) under a second set of ALD conditions.
Claims 7 and 12 can have multiple value of [Symbol font/0x44]GPC, % therefore infringement cannot be unambiguously determined for a particular compound tested and these claims are therefore indefinite. Pursuant to 35 U.S.C. 112(b), the claim must apprise one of ordinary skill in the art of its scope so as to provide clear warning to others as to what constitutes infringement. MPEP 2173.02(II); Solomon v. Kimberly-Clark Corp., 216 F.3d 1372, 1379, 55 USPQ2d 1279, 1283 (Fed. Cir. 2000).
The issue is heightened because, there is close prior art as cited in the § 103 rejection below. In crafting § 112 indefiniteness rejections, the Examiner may consider close prior art respecting the term at issue. MPEP § 2173.05(b)(III)(A) (citing Amgen, Inc. v. Chugai Pharmaceutical Co., 927 F.2d 1200, 18 USPQ2d 1016 (Fed. Cir. 1991) (See Amgen at 1218 -- “[w]hen the meaning of claims is in doubt, especially when, as is the case here, there is close prior art, they are properly declared invalid”).
Applicant’s Argument
Applicant argues that in view of at least paragraphs [0191] - [0201] (Applicant cites publication US 2025/1019496) of the present application showing <Test Example 2> and paragraphs [0202]- [0209] of the present application showing <Test Example 3>, change in GPC ([Symbol font/0x44]GPC, %) would be understood by one of ordinary skill in the art, and claims 7 and 12 are therefore definite.
This argument is not persuasive because it is improper to import claim limitations from the specification. MPEP § 2111.01(II). For example, a particular embodiment appearing in the written description (in this case the procedures/conditions of Test Examples 2 or 3 as argued) may not be read into a claim when the claim language is broader than the embodiment of claims 7 and 12. MPEP § 2111.01(II) (citing Superguide Corp. v. DirecTV Enterprises, Inc., 358 F.3d 870, 875, 69 USPQ2d 1865, 1868 (Fed. Cir. 2004)).
Claim Rejections - 35 USC § 112(d)
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
A “claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers”. 35 U.S.C. 112(d). However, to be in proper dependent form, the dependent claim must “then specify a further limitation of the subject matter claimed”. 35 U.S.C. 112(d); MPEP § 608.01(n)(III).
§ 112(d) Rejection of Claims 7-9 and 12
Dependent claims 7-9 and 12 are rejected 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. MPEP § 608.01(n)(III). Claim 7 provides the further recitation:
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.
Emphasis added.
Claim 12 differs only in that it is directed to the hafnium species of claim 1.
Dependent claims 7-9 and 12 therefore purport to further limit claim 1 by excluding species of claim 1 that do not perform the claimed function.
However, as discussed above in the Withdrawal of the 35 U.S.C. 112(a) – Written Description Rejection, (see pages 9-10 of the Office action mailed Aug. 13, 2025) one of skill would be apprised, and Applicant ostensibly argues that (Reply filed July 29, 2025 at page 12), each of the claim 1 species would inherently demonstrate the claim 7 or 12 function; the claim 7 and claim 12 change in GPC is an inherent property in all the claim 1 compounds. Claims 7-9 and 12 therefore fail to limit base claim 1 because none of the zirconium or hafnium species of claim 1 can be excluded by dependent claims 7-9 or 12 pursuant to 35 U.S.C. 112(d). In other words, the scope of claim 1 is coextensive with that of claims 7-9 and 12.
Applicant’s Argument
Applicant argues that dependent Claims 7-9 and 12 are proper dependent form and therefore, withdrawal and reconsideration of the rejections under 35 U.S.C. §112(b) and §112(d). This argument is insufficient to merit withdrawal of the § 112(d) rejection.
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.
The Instant Claims
Independent claim 1 is directed to a method for forming a Group 4 metal element-containing film employing a precursor compound represented by one of the following Formulae, which have the following structures and CAS registry nos.
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,
where claim 1 further recites:
Claim 1 . . . wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition.
35 U.S.C. § 102(a)(1)/(2) over S. Kim et al., US 2022/0205099 (2022) (“Kim”)
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 maintained for the reasons given in the previous Office action.
To summarize the § 102 rejection, Kim’s working Example 6 is the only teaching where a precursor relevant to the instant claims (i.e., Kim’s compound Hf(Me(nPr)Cp)(NMe2)3, which corresponds to claim 1 [Formula 3-1]) was actually used in method to form a hafnium containing film. As persuasively argued by Applicant and recognized in the previous Office action, comparison 1NMR data shows that Kim’s compound Hf(Me(nPr)Cp)(NMe2)3, as used in Example 6 and as prepared in Kim Example 3, is actually a mixture of the following regioisomers:
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See 1HNMR data summarized in the Office action mailed Aug. 13, 2025 at page 28.
However, Kim draws/represents the structure of Hf(Me(nPr)Cp)(NMe2)3 in Kim Table 1 as a single isomer.
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Kim at page 11, Table 1 (circling added). The only issue is whether Kim meets the claim 1 limitation of:
Claim 1 . . . wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition.
This limitation is asserted to be met by Kim Example 6 because one of skill in the art can at once envisage Kim’s Hf(Me(nPr)Cp)(NMe2)3) as (per claim 1) a single because this is exactly the way Kim draws Hf(Me(nPr)Cp)(NMe2)3) in Kim Table 1. Kim at page 11, Table 1.
In this regard, a reference disclosure can anticipate a claim when the reference describes the limitations but does not expressly spell out the limitations as arranged or combined as in the claim, if a person of skill in the art, reading the reference, would ‘at once envisage’ the claimed arrangement or combination. MPEP § 2131.02(III). As here, where the claimed “single isomer” is not specifically named in Kim’s Example 6, but instead it is necessary to select portions of teachings within the reference and combine them, e.g., select various substituents from a list of alternatives given for placement at specific sites on a generic chemical formula to arrive at a specific composition, anticipation can only be found if the classes of substituents are sufficiently limited or well delineated. MPEP § 2131.02(III) (citing Ex parte A, 17 USPQ2d 1716 (Bd. Pat. App. & Inter. 1990)). If one of ordinary skill in the art is able to "at once envisage" the specific compound within the generic chemical formula, the compound is anticipated. MPEP § 2131.02(III).3
It is noted that above cited MPEP sections are directed to the case where a claimed compound is anticipated, whereas the issue here is whether a claimed method, in which the compound structure is the issue, is anticipated. However, the analysis should not change where, as here, an old compound is employed in an old method.
In sum, Kim Example 6 (teaching formation of a hafnium-containing film by an ALD temperature of approximately 250 °C to approximately 425 °C) contacting Hf(Me(nPr)Cp)(NMe2)3 with the “reaction gas” ozone meets each and every limitation of claims 1-3.
The limitations of claim 2 are clearly met because Kim Example 6 teaches that:
The canister containing Hf(Me(nPr)Cp)(NMe2)3 was maintained at 85° C. (VP-0.4 Torr). The ALD chamber pressure was set at 1 Torr. The ALD process temperature was set at temperatures ranging from approximately 250° C to approximately 425° C.
Kim at page 11, [0151].
And Kim teaches that the general film forming method is 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].
The temperature limitations of claim 3 “a temperature range of 150°C to 500°C” are met because as shown in Kim Fig. 6, Kim’s experiment was conducted as the specific temperatures of 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, 425 °C, and 450 °C, all of which fall within the claim 3 temperature range.
Claims 7-9 are anticipated by Kim Example 6 because claim 7 only modifies a functional aspect of the result obtained when “one of the Formula 2-1, Formula 2-2, or Formula 2-3 is used”.
Claim 7 . . . 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) . . .
The rejection, however, is based on the alternative of the hafnium compounds of claimed formulae 3-1, which alternative is still present in claim 7 by virtue of its claim 1 dependency.4 That is, when the limitations of base claim 1 are incorporated into dependent claim 7, the hafnium alternative of claim 7 (from base claim 1) is anticipated by Kim Example 6. The same rational applies to claims 8 and 9.
The limitations of claim 12 are met for the following reasons. Kim’s compound Hf(Me(nPr)Cp)(NMe2)3 used in Kim Example 6 is the same compound taught in instant specification Test Example 2 as meeting the claim 12 functional recitation.
claims 12 . . . 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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.
See the discussion of Test Example 2 in Claim Interpretation above; see also, § 112(b) rejection of claim 12. MPEP § 2112(V) (citing In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433-34 (CCPA 1977). Further, Kim teaches that the results of Example 6 are shown in FIG. 6, which is a graph showing the formed HfO2, film growth rate as a function of the chamber temperature using Hf(Me(nPr)Cp)(NMe2)3:
FIG. 6 is a graph showing the formed HfO2 film growth rate as a function of the chamber temperature using Hf(Me(nPr)Cp)(NMe2)3;
Kim at page 4, [0099]. Kim Fig. 6 shows for Example that the [Symbol font/0x44]GPC, % in Å/cycle remained relatively steady at about 0.70 Å/cycle between 300 °C and 375 °C. The limitations of claim 12 are therefore met.
The limitations of claim 15 (directed to a composition) 5 are met by Kim compounds. Hf(Me(nPr)Cp)(NMe2)3 and Hf(Me(nBu)Cp)(NMe2)3, as they are drawn in Table 1 as single isomers (and thus meet the claim 15 limitation of “in a structure of a single composition”). Kim at page 11, Table 1.
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Kim at page 11, Table 1 (circling added). Kim’s drawings of Hf(Me(nPr)Cp)(NMe2)3 and Hf(Me(nBu)Cp)(NMe2)3 clearly anticipate claim 15.
APPLICANT’S ARGUMENT RESPECTING THE § 102 REJECTION
Affidavit under 37 CFR 1.132 by inventor Jin Sik KIM, dated December 22, 2025 (the "Kim Declaration")
Applicant submits the declaration under 37 CFR 1.132 by inventor Jin Sik KIM, dated December 22, 2025 (the "Kim Declaration") to traverse the rejection. The Kim Declaration avers that the Hf(Me(nPr)Cp)(NMe2)3 and Hf(Me(nBu)Cp)(NMe2)3 disclosed by Kim a mixture of isomer compositions and is not single composition as required by claim 1. Kim Declaration at ¶ 6.
The Kim Declaration avers that as set forth in paragraphs [0145] and [0148] of Kim, in Examples 3 and 4 of Kim, the compounds are synthesized by reacting methyl cyclopentadiene with either 1-bromopropane or 1-bromobutane and the synthesized compounds of Kim should be inevitably a mixture of isomers rather than a single composition. Kim Declaration at ¶ 6.
The Kim Declaration avers that specification <Preparation Example 3> prepares a mixture of isomers from reaction of methylcyclopentadiene and 1-bromopropane, summarized by the Examiner as follows.
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Kim Declaration at ¶ 6 (citing specification at pages 21-22).
The Kim Declaration avers that in specification <Comparative Example 5>, the product of above <Preparation Example 3> is reacted with tetrakis(dimethylamido) hafnium (VI), which resulted in a mixture of the following compounds 3-1 and 3-4.
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3-1 3-4
Kim Declaration at ¶ 6 (citing specification at pages 27-28). The Kim Declaration concludes that reference S. Kim et al., US 2022/0205099 (2022) discloses a mixture of isomers whereas the instant claims are directed to (per claim 1) “a structure of a single composition”. Kim Declaration at ¶ 6, page 3, 1st paragraph. In this regard, Applicant’s argument states that:
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Reply at page 17.
Applicant’s Argument that Kim Does not Teach the Claim 1 Limitation of “in a structure of a single composition”
In summary, relying on the above Declaration, Applicant argues that prior art reference Kim employs Hf(Me(nPr)Cp)(NMe2)3 in Kim Example 6 (and as this species prepared in Kim Example 3) as mixture of isomers which does not meet the claim 1 limitation of:
Claim 1 . . . wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition.
Reply at pages 9-13.
Examiner Response
Applicant’s evidentiary argument respecting the conclusion that Kim employs Hf(Me(nPr)Cp)(NMe2)3 as a mixture of isomers is not addressed point-by-point because the Examiner is in agreement. That is, Kim Example 6 uses the following mixture of isomers:
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However, Applicant’s argument that Kim Example 6 is not anticipatory is not persuasive for the following reasons. The issue is whether Kim meets the claim 1 limitation of:
Claim 1 . . . wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition.
As discussed in detail above, this limitation is asserted to be met by Kim Example 6 because one of skill in the art can at once envisage Kim’s Hf(Me(nPr)Cp)(NMe2)3) as (per claim 1) a single isomer because this is exactly the way Kim draws Hf(Me(nPr)Cp)(NMe2)3) in Kim Table 1. Kim at page 11, Table 1.
Applicant’s further arguments respecting the invention’s advantages and unexpected results are not applicable to a § 102 rejection. MPEP § 2131.04 (evidence of secondary considerations, such as unexpected results or commercial success, is irrelevant to 35 U.S.C. 102 rejections and thus cannot overcome a rejection so based.)
Applicant’s Argument that Kim Is not an Enabling Disclosure
Applicant further argues that Kim’s disclosure does not enable one of ordinary skill in the art to make and use the claimed Group 4 metal element-containing precursor compound that is, per claim 1, “in a structure of a single composition”. Reply at pages 17-18. Applicant cites the MPEP statement that ‘that the mere naming or description of the subject matter is insufficient; rather, the cited art must demonstrate that the public was in possession of the claimed subject matter before the date of invention’. Reply at page 18 (citing MPEP 2121.01) Applicant argues that Kim merely describes synthesizing the mixture of isomers by reacting methyl cyclopentadiene with 1-bromopropane, which would produce an isomer mixture. Applicant further argues that Kim does not provide any guidance to one of skill to produce the instantly claimed precursor compound that is in a structure of a single composition.
Applicant relies on the declaration under 37 CFR 1.132 by inventor Jin Sik KIM, dated December 22, 2025 (the "Kim Declaration") so show inoperability of Kim.
The Kim Declaration avers that:
. . . Kim ls non-enabling with respect to "wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition," as recited in Claim 1. As mentioned above, Kim does not teach the Group 4 metal element-containing precursor compound that is in a structure of a single composition, nor does there any guidance in Kim instructing one of skill in the art to produce the claimed precursor compound that is in a structure of a single composition. Therefore, the disclosure of Kim does not enable "the Group 4 metal element-containing precursor compound is in a structure of a single composition," of Claim 1.
Kim Declaration at ¶ 6, paragraph bridging pages 6-7; see also Reply at page 18.
Examiner Response
This argument is not persuasive for the following reasons. When the reference relied on expressly anticipates or makes obvious all of the elements of the claimed invention, the reference is presumed to be operable and the burden is on applicant to rebut the presumption of operability. MPEP § 2121(I); see also MPEP § 716.07. Every patent is presumed valid (35 U.S.C. 282). MPEP § 716.07. Affidavits or declarations attacking the operability of a patent cited as a reference must rebut the presumption of operability by a preponderance of the evidence. MPEP § 716.07 (citing In re Sasse, 629 F.2d 675, 207 USPQ 107 (CCPA 1980)).
Here, the issue is whether the public was in possession of Kim’s Hf(Me(nPr)Cp)(NMe2)3 in the form of a single isomer, just as it is depicted in Kim Table 1, in view of the acknowledged fact that Kim (although drawing a single isomer) does not actually prepare or use this compound as a single isomer, but rather as an isomer mixture.
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Kim at page 11, Table 1 (depicting the structure, as above, as a single isomer).
In view of the numerous synthetic and purification techniques available as of the effective filing date, Applicant has not provided sufficient evidence to show that the public was not in possession of Hf(Me(nPr)Cp)(NMe2)3 in the form of a single isomer (as it is depicted in Kim Table 1) as of the instant effective filing date. Applicant’s statement that the Kim reference itself does not teach Hf(Me(nPr)Cp)(NMe2)3 in the form of a single isomer, does not touch on whether other prior art synthetic methods or separation techniques would provide this species. See MPEP § 2121.02(II) (citing In re Donohue, 766 F.2d 531, 226 USPQ 619 (Fed. Cir. 1985), the fact that an author of a publication did not attempt to make the compound disclosed, without more, will not overcome a rejection based on that publication).
For example, the art evidences that Hf(Me(nPr)Cp)(NMe2)3 in the form of a single isomer can be prepared using the methylalkylcyclopentadienes disclosed by J. Lee et al., US 5,434,324 (1995) (“Lee”).
Lee teaches a process for preparing alkyl substituted cyclopentadienes which favors the formation of the desirable endo isomers. Lee at col. 1, lines 26-27. 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). Lee teaches that his process produces a major portion of endo isomers and usually a 2.5 to 1 or higher ratio of endo to exo isomers. Lee at col. 2, lines 23-25. However, the exo isomer formation is inconsequential because (per above), Lee teaches that the exo does not react to form a metallocene. Lee further teaches that in theory there are 5 possible endo isomers. Lee at col. 1, lines 25-26. These five endo isomers are drawn by the Examiner as follows:
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However, these endo isomers are irrelevant in the formation of metallocenes because the cyclopentadiene double bonds are delocalized upon forming the metallocene and thus double bond placement within the cyclopentyl ring is not an issue (see Claim Interpretation above).
In any case, Lee teaches application of the following synthetic scheme:
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to prepare 1-methyl-3-n-propylcyclopentadiene (where the propyl and methyl groups are positioned on the cyclopentadiene ring (Cp) as separated by one Cp-ring carbon). Lee at col. 2, line 48 to col. 3, line 35. In the working Example, Lee teaches the yield of 1-methyl-3-npropylcyclopentadiene was 77±4%, where the structure of 1-methyl-3-n-propylcyclopentadiene was confirmed by GC/MS. Lee at column 3, lines 30-35. One of skill seeking to practice Kim’s Example 6 using the single isomer of Hf(Me(nPr)Cp)(NMe2)3 just as it is depicted in Kim Table 1, could readily employ the 1-methyl-3-n-propylcyclopentadiene (as prepared by Lee) in Kim’s Example 3 (Kim’s procedure at page 10, [0146]) instead of Kim’s isomeric methylpropyl cyclopentadiene mixture, thereby arriving at the single isomer of Hf(Me(nPr)Cp)(NMe2)3, just as it is depicted in Kim Table 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. Specification at page 20.
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Specification at page 20 (Preparation Example 1).
Applicant’s Argument Respecting J. Lee et al., US 5,434,324 (1995) (“Lee”)
Applicant argues that Lee merely describes the synthesis of substituted cyclopentadienes but is totally silent regarding using the synthesized cyclopentadienes (1-methyl-3-alkylcyclopentadienes) as a Group 4 metal element-containing precursor compound for forming a Group 4 metal element-containing film as claimed. Reply at page 19, last paragraph.
This argument is not persuasive because it is not probative of whether the public was in possession of Hf(Me(nPr)Cp)(NMe2)3 in the form of a single isomer (as it is depicted in Kim Table 1) as of the instant effective filing date. Kim already teaches use of the claimed Hf(Me(nPr)Cp)(NMe2)3 as a film forming precursor. In any case, Lee specifically states that “[a]lkyl substituted cyclopentadienes are used as monomers and in forming metallocenes of transition metals such as titanium, zirconium and hafnium”. Lee at col. 1, lines 10-15. One seeking to practice Kim’s Example 6 using the single isomer of Hf(Me(nPr)Cp)(NMe2)3 just as it is depicted in Kim Table 1, could readily employ the 1-methyl-3-n-propylcyclopentadiene (as prepared by Lee) in Kim’s Example 3 (Kim’s procedure at page 10, [0146]) instead of Kim’s isomeric methylpropyl cyclopentadiene mixture, thereby arriving at the single isomer of Hf(Me(nPr)Cp)(NMe2)3, just as it is depicted in Kim Table 1.
Applicant further argues that the method of Lee, not only 1-methyl-3-alkylcyclopentadienes, but also mixtures of 5 possible endo and 3 possible exo isomers are formed. Applicant argues that even assuming arguendo that one of ordinary skill in the art uses the methods described by Lee, as the resulting product prepared by the methods of Lee is a mixture of endo and exo isomers, when such a mixture of endo and exo isomers as described by Lee is used as a starting material, it is unpredictable through which reaction pathway the final product will be obtained.
This argument is not persuasive for the following reasons. As discussed above, Lee teaches (as does the instant specification) that that the exo-isomers are not reactive in the formation of metallocenes. Lee at col. 1, lines 19-27 (emphasis added). Further, the five endo isomers alluded to by Lee are the following:
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All of which would react similarly under the conditions of Kim’s procedure at page 10, [0146] to form the single isomer of Hf(Me(nPr)Cp)(NMe2)3, just as it is depicted in Kim Table 1. As stated by Lee “akyl substituted cyclopentadienes are used as monomers and in forming metallocenes of transition metals such as titanium, zirconium and hafnium”. Lee at col. 1, lines 10-15. The takeaway from the paragraph reproduced above (i.e., Lee at col. 1, lines 16-27) is that the all of the five endo isomers react similarly to give one metallocene product where the two double bonds are delocalized in the cyclopentyl ring.
Claim Rejections - 35 USC § 103
The following is a quotation of pre-AIA 35 U.S.C. 103(a) which forms the basis for all obviousness rejections set forth in this Office action:
(a) A patent may not be obtained though the invention is not identically disclosed or described as set forth in section 102, if the differences between the subject matter sought to be patented and the prior art are such that the subject matter as a whole would have been obvious at the time the invention was made to a person having ordinary skill in the art to which said subject matter pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries set forth in Graham v. John Deere Co., 383 U.S. 1, 148 USPQ 459 (1966), that are applied for establishing a background for determining obviousness under AIA 35 U.S.C. 103(a) are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or non-obviousness.
The § 103 Rejections
Claims 1-2, 7-9, 12, and 14-15 are rejected 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”).
Claim 13 is obvious over Kim and Lee as above in further view of J. Niinistö, 18 Journal of Materials Chemistry, 5243-5247 (2008) (“Niinistö”).
S. Kim et al., US 2022/0205099 (2022) (“Kim”)
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].
Kim discloses the following six species, among a listing, as precursor compounds for use in the practice of Kim’s above method.
Zr(Me(nPr)Cp)(NMe2)3;
Zr(Me(nBu)Cp)(NMe2)3;
Zr(Me(iPr)Cp)(NMe2)3;
Hf(Me(nPr)Cp)(NMe2)3;
Hf(Me(nBu)Cp)(NMe2)3; and
Hf(Me(iPr)Cp)(NMe2)3.
Kim page 5, [0107]; Id. at [0108]. Kim represents the structures of Hf(Me(nPr)Cp)(NMe2)3 and Hf(Me(nBu)Cp)(NMe2)3 in Table 1 as follows. Kim at page 11, Table 1.
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Kim at page 11, Table 1.
Further, Kim represents the structure of Zr(Me(Et)Cp)(NMe2)3 (not instantly claimed) as follows:
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Kim at page 11, [0149]. In view of the foregoing, particularly in view of Kim Table 1, one of ordinary skill would be apprised that species within the meaning of Kim’s following molecular formulae:
Zr(Me(nPr)Cp)(NMe2)3;
Zr(Me(nBu)Cp)(NMe2)3;
Zr(Me(iPr)Cp)(NMe2)3;
Hf(Me(nPr)Cp)(NMe2)3;
Hf(Me(nBu)Cp)(NMe2)3; and
Hf(Me(iPr)Cp)(NMe2)3,
(disclosed at Kim page 5, [0107]; Id. at [0108]) that are useful in Kim’s claimed method
are the following structures:
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which are drawn by the Examiner in conformance with Kim Table 1, which 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 above disclosed species are the same species employed in the method of instant claim 1.
Kim Teaches the following working Example 6 (using Hf(Me(nPr)Cp)(NMe2)3 as the ALD precursor) which as shown in Kim Table 1 as the following compound and which is the same compound of Formula 2-1 of instant claim 1:
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Kim at page 11, Table 1.
Kim’s Example 6 ALD procedure is as follows:
Example 6: ALD Using Hf(Me(nPr)Cp)(NMe2)3
[0151] Thermal ALD using precursor Hf(Me(nPr)Cp)(NMe2)3 and co-reactant O3 was performed on Si bare wafer . The canister containing Hf(Me(nPr)Cp)(NMe2)3 was maintained at 85 °C. (VP[Symbol font/0x7E]0.4 Torr). The ALD chamber pressure was set at 1 Torr. The ALD process temperature was set at temperatures ranging from approximately 250 °C to approximately 425 °C. These results are shown in FIG. 6 which is a graph showing the formed HfO2, film growth rate as a function of the chamber temperature using Hf(Me(nPr)Cp)(NMe2)3. Thermal ALD deposition occurred at temperatures ranging from approximately 300 °C to approximately 400 °C, where non-uniformity is low.
Kim at page 11, [0151] (emphasis added). However, although Kim draws only one regioisomer, Applicant argues that one of ordinary skill would assume that the Hf(Me(nPr)Cp)(NMe2)3 used in Kim Example 6, was prepared according to Kim Example 3, and is thus an isomeric mixture. Reply filed July 29, 2025 at page 15. As discussed in detail in the § 102 rejection above (in reply to Applicant’s arguments), the Examiner acknowledges that comparison 1NMR data shows that Kim’s compound Hf(Me(nPr)Cp)(NMe2)3 as prepared in Kim Example 3, is a mixture of the following regioisomers:
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Differences between Kim and Claim 1
Kim teaches each and every limitation of claim 1 for the reasons given in the § 102 rejection above. Applicant argues that Kim differs to the extent that that Kim’s working Example 6 performs an ALD process on Hf(Me(nPr)Cp)(NMe2)3 as a mixture of the following regioisomers:
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and therefore, Applicant argues that Kim does not meet the claim 1 limitation of.
Claim 1 . . . wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition.
J. Lee et al., US 5,434,324 (1995) (“Lee”).
Lee teaches a process for preparing alkyl substituted cyclopentadienes which favors the formation of the desirable endo isomers. Lee at col. 1, lines 26-27. 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).
Lee teaches that his process produces a major portion of endo isomers and usually a 2.5 to 1 or higher ratio of endo to exo isomers. Lee at col. 2, lines 23-25. However, the exo isomer formation is inconsequential because (per above), Lee teaches that the exo does not react to form a metallocene. Lee further teaches that in theory there are 5 possible endo isomers. Lee at col. 1, lines 25-26. These five possible endo isomers are drawn by the Examiner as follows:
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However, the Examiner notes that these endo isomers are irrelevant in the formation of metallocenes because the cyclopentadiene double bonds are delocalized upon forming the metallocene and thus double bond placement within the cyclopentyl ring is not an issue (see Claim Interpretation above). In any case, Lee teaches application of the following synthetic scheme:
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to prepare 1-methyl-3-n-propylcyclopentadiene (where the propyl and methyl groups are positioned on the cyclopentadiene ring (Cp) as separated by one Cp-ring carbon). Lee at col. 2, line 48 to col. 3, line 35. In the working Example, Lee teaches the yield of 1-methyl-3-npropylcyclopentadiene was 77±4%, where the structure of 1-methyl-3-n-propylcyclopentadiene was confirmed by GC/MS. Lee at column 3, lines 30-35.
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. Specification at page 20.
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Specification at page 20 (Preparation Example 1).
Obviousness Rationale
One of ordinary skill is motivated to perform Kim Example 6, with any of the following claimed compounds:
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because Kim directly teaches their utility in Kim’s disclosed method of methods for forming a Group IV transition metal containing film.
For example, one of ordinary skill is motivated to perform Kim working Example 6 (using Hf(Me(nPr)Cp)(NMe2)3 as the ALD precursor, as already taught by Kim Example 6) which compound is shown in Kim Table 1 as the following structure and which is the same compound of Formula 2-1 of instant claim 1:
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(Kim at page 11, Table 1), where per claim 1, the Hf(Me(nPr)Cp)(NMe2)3:
Claim 1 . . . wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition.
because Kim depicts the Hf(Me(nPr)Cp)(NMe2)3 as a “single composition” (i.e., a single isomer). See Claim Interpretation above.
One of ordinary skill can prepare Kim’s Hf(Me(nPr)Cp)(NMe2)3 as a “single composition” (i.e., a single isomer) based on well-known synthetic/purification techniques. For example, one of ordinary skill seeking to practice Kim’s Example 6 using the single isomer of Hf(Me(nPr)Cp)(NMe2)3 just as it is depicted in Kim Table 1, could readily employ the 1-methyl-3-n-propylcyclopentadiene (as prepared by Lee) in Kim’s Example 3 (Kim’s procedure at page 10, [0146]) instead of Kim’s isomeric methylpropyl cyclopentadiene mixture, thereby arriving at the single isomer of Hf(Me(nPr)Cp)(NMe2)3, just as it is depicted in Kim Table 1.
Claims 7-9 are obvious over Kim Example 6 because claim 7 only modifies a functional aspect of the result obtained “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)”. The rejection, however, is based on the alternative of the hafnium compounds of claimed formulae 3-1, which alternative is still present in claim 7 by virtue of its claim 1 dependency.6 That is, when the limitations of base claim 1 are incorporated into dependent claim 7, the hafnium alternative of claim 7 is obvious over Kim Example 6 for the reasons discussed above. The same rational applies to claims 8 and 9.
The limitations of claim 12 are met for the following reasons. Kim’s compound Hf(Me(nPr)Cp)(NMe2)3 used in Kim Example 6 is the same compound taught in instant specification Test Example 2 as meeting the claim 12 functional recitation.
claims 12 . . . 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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.
See the discussion of Test Example 2 in Claim Interpretation above; see also, § 112(b) rejection of claim 12. MPEP § 2112(V) (citing In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433-34 (CCPA 1977).
Further, Kim teaches that the results of Example 6 are shown in FIG. 6, which is a graph showing the formed HfO2, film growth rate as a function of the chamber temperature using Hf(Me(nPr)Cp)(NMe2)3:
FIG. 6 is a graph showing the formed HfO2 film growth rate as a function of the chamber temperature using Hf(Me(nPr)Cp)(NMe2)3;
Kim at page 4, [0099]. Kim Fig. 6 shows for Example that the [Symbol font/0x44]GPC, % in Å/cycle remained relatively steady at about 0.70 Å/cycle between 300 °C and 375 °C. The limitations of claim 12 are therefore met.
Claim 13 is obvious for the following reasons. Claim 13 recites “wherein the Group 4 metal element-containing film is formed on a substrate having at least one groove having an aspect ratio of 1 or more and a width of 1 μm or less”. J. Niinistö, 18 Journal of Materials Chemistry, 5243-5247 (2008) (“Niinistö”) teaches that mixed alkylamido-cyclopentadienyl compounds of zirconium, (RCp)Zr(NMe2)3 (R = H, Me or Et) are introduced as precursors for atomic layer deposition (ALD) of high permittivity zirconium oxide thin films. Niinistö at Abstract. Niinistö teaches that good film conformality was observed, as step coverages of 80–90% were measured for films deposited onto high aspect ratio (60 : 1) trenches. Niinistö at Abstract.
Niinistö teaches forming ZrO2 films as follows. Niinistö at page 5243, col. 2. ZrO2 thin films were deposited in a flow-type horizontal hot-wall ALD reactor. Id. The precursors applied, (RCp)Zr(NMe2)3 (R = H, Me, Et), were evaporated from open crucibles kept at 60, 65 and 70 [Symbol font/0xB0]C, respectively. Id. Ozone, used as the oxygen source in all depositions, was generated from O2. Id. Films were deposited onto as-received Si(100) substrates measuring 5 [Symbol font/0xB4] 5 cm2 and for selected samples, TiN/Si substrates were also used. Id. Niinistö further teaches that to study the film conformality, the (RCp)Zr(NMe2)3/O3 processes were applied onto trenches with an aspect ratio of 60 : 1. In Fig. 5, Niinistö depicts the trenches, wherein the width is in the range of 14 nm to 17 nm. Thus, teaches the instant claim 13 limitation of ““wherein the Group 4 metal element-containing film is formed on a substrate having at least one groove having an aspect ratio of 1 or more and a width of 1 μm or less””.
Niinistö summarizes the study by reciting that liquid Zr precursors, viz. mixed alkylamido-cyclopentadienyl compounds with the structure of (RCp)Zr(NMe2)3 where R = H, Me or Et, can be effectively applied together with ozone in ALD of ZrO2 thin films for microelectronic applications. Niinistö at page 5247, col. 2. Niinistö further states that the leakage current density was in the region of 10-7 A cm-2, as required by future DRAM technology nodes. Niinistö at page 5247, col. 2.
In summary, Niinistö teaches ALD (atomic layer deposition) formation of ZrO2 films by reacting precursors (RCp)Zr(NMe2)3 (R = H, Me or Et), which includes:
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in an ALD reaction chamber with ozone, wherein the ZrO2 films are deposited onto high aspect ratio (60 : 1) trenches and wherein the trench width is in the range of 14 nm to 17 nm. Niinistö further fairly teaches that the ZrO2 films are suitable for DRAM technology nodes. One of ordinary skill is motivated to employ the method of Kim as proposed above with DRAM substrates (which as taught by Niinistö, meet the claim 13 limitations) because Kim specifically teaches use of his disclosed method for DRAM substrates. That is, Kim teaches that the substrate may be planar or patterned or may be an organic patterned photoresist film. Kim at page 2, [0067]. Kim further teaches that the substrate may include layers of oxides which are used as dielectric materials in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications (for example, ZrO2 based materials, HfO2 based materials, TiO2 based materials, rare earth oxide-based materials, ternary oxide based materials, etc.) or nitride-based films (for example, TaN, TiN, NbN) that are used as electrodes. Kim at page 2, [0067].
The limitations of claim 14 are met by practice of Kim as proposed above because Kim teaches that “[t]ypical film thicknesses may vary from several angstroms to several hundreds of microns, and typically from 2 to 100 nm, depending on the specific deposition process”. Kim at page 8, [0133]. Thus, one of ordinary skill is motived to employ the Kim film forming method of Kim Example 7, as proposed above, to form a film within the claim 14 range of 1 nm to 500 nm. In the case where the claimed ranges overlap or lie inside ranges disclosed by the prior art a prima facie case of obviousness exists. MPEP § 2144.05(I) (citing In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976)).
The compositions7 encompassed by claim 15 are obvious over the following six Kim compounds.
Zr(Me(nPr)Cp)(NMe2)3;
Zr(Me(nBu)Cp)(NMe2)3;
Zr(Me(iPr)Cp)(NMe2)3;
Hf(Me(nPr)Cp)(NMe2)3;
Hf(Me(nBu)Cp)(NMe2)3; and
Hf(Me(iPr)Cp)(NMe2)3,
(disclosed at Kim page 5, [0107]);
where, per claim 15:
Claim 15 . . . wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition.
This is because, as discussed above, Kim represents the hafnium compounds, Hf(Me(nPr)Cp)(NMe2)3 and Hf(Me(nBu)Cp)(NMe2)3, in Table 1 as single isomers (per claim 15 “single compositions”) as follows. Kim at page 11, Table 1.
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Kim at page 11, Table 1. Further, Kim represents the structure of Zr(Me(Et)Cp)(NMe2)3 (not instantly claimed) as follows:
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Kim at page 11, [0149].
Based on the disclosure of Kim, one of skill can at once envisage that Kim discloses the cited six Kim compounds as having the same structure as the six compounds of claim 15; where, per claim 15:
Claim 15 . . . wherein the Group 4 metal element-containing precursor compound is in a structure of a single composition.
because this is the way Kim draws the compounds; that is, Kim draws the compounds as single isomers.
APPLICANT’S ARGUMENT RESPECTING THE § 103 REJECTION
Applicant argues that as discussed above regarding the rejection under 35 U.S.C. § 102(a)/(b), Kim does not teach or suggest every feature as recited in Claim 1. Applicant does not present any new arguments regarding the § 103 rejection. All § 102 arguments are already fully addressed above. Applicant’s argument respecting unexpected results (which Applicant presented under its § 102 arguments) is addressed below.
Applicant’s Argument of Unexpected Results
Applicant argues that the claimed species “in a structure of a single composition” exhibit unexpected results over reference Kim. Reply at page 14; Kim Declaration at pages 4-5. Applicant specifically proffers specification Table 2, which summarizes the <Test Example 3> comparison of claimed single isomer 3-1 with the product of <Comparative Example 2> (i.e., CpHf(NMe2)3, in an ALD film forming experiment. 8 . Reply at page 14 (citing <Test Example 3> at pages 31-37 (Table 2 at page 36)).
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CpHf(NMe2)3
The Examiner notes however that the proffered CpHf(NMe2)3 can only be a single isomer. Applicant proffers that:
As can be seen from FIG. 3, Table 2, and paragraphs [0210] and [0213] of the present application, as the composition for film deposition comprising a hafnium (Hf)-containing precursor compound as claimed was used, the self-limiting film growth of ALD could be achieved in a wide temperature range, especially at high temperatures. In addition, when the composition for film deposition of Example 3 of the present application was used (claimed single structure of Formula 3-1 as reproduced below), the GPC does not vary.
Reply at page 15.
Examiner Response
The proffered results are not persuasive for the following reasons. An affidavit or declaration under 37 CFR 1.132 also must compare the claimed subject matter with the closest prior art to be effective to rebut a prima facie case of obviousness. MPEP § 716.02(e).
Here, the proffered results are not the closest prior art. That is, the Kim’s Example 6 chemical vapor deposition (which was conducted with the isomer mixture of Kim Example 3) was cited against the claims in the § 103 rejection:
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However, Applicant proffers a comparison between claimed single isomer 3-1 and CpHf(NMe2)3, where CpHf(NMe2)3 was not cited against the claims, not disclosed by Kim, and can only be a single isomer. The proper comparison is an ALD experiment between Kim’s above Example 3 isomer mixture and the claimed single isomer 3-1. Here, because the closest prior art was not compared, there is no nexus between the § 103 rejection and the proffered results. MPEP § 716.02(e).
Conclusion
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ALEXANDER R. PAGANO
Examiner
Art Unit 1692
/ALEXANDER R PAGANO/Primary Examiner, Art Unit 1692
1 See e.g., S. Csicsery, Methycyclopentadiene Isomers, Journal of Organic Chemistry, 518-521 (1960).
2 For example, at page 7 Ommen teaches: “In the beginning of the ALD growth, when the substrate material is necessarily exposed on the surface, the GPC often varies with cycles. Compared to the linear growth regime, depending on the amount and reactivity of adsorption sites on the surface, the GPC in the first cycle(s) can then be higher (Fig. 5a.2) or lower (Fig. 5a.3, a.4)”.
3 One of ordinary skill in the art must be able to draw the structural formula or write the name of each of the compounds included in the generic formula before any of the compounds can be "at once envisaged." MPEP § 2131.02(III). One may look to the preferred embodiments to determine which compounds can be anticipated. Id. (citing In re Petering, 301 F.2d 676, 133 USPQ 275 (CCPA 1962)).
4 A “claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers”. 35 U.S.C. 112(d).
5 The claim 15 preamble recitation of “A composition for film deposition” does not distinguish over Kim’s disclosure of the above prior art compounds. This preamble does not impose any structural limitations on the claimed composition and therefore is interpreted as a statement of suggested use that cannot distinguish over the art. See MPEP § 2111.02(II). Further, the claim 15 preamble language “A composition” does not distinguish over Kim. Neither claim 15 nor the specification require that a “composition” comprise materials or components in addition to the claimed compound. See for example, specification at 5, [42]; Id. at page 6, [49]-[50]. Thus, under its broadest reasonable interpretation, consistent with the specification, a “composition” encompasses a one-component composition (i.e., a composition that consists only of the claimed compound). MPEP § 2111.
6 A “claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers”. 35 U.S.C. 112(d).
7 The claim 15 preamble recitation of “A composition for film deposition” does not distinguish over Kim’s disclosure of the above prior art compounds. This preamble does not impose any structural limitations on the claimed composition and therefore is interpreted as a statement of suggested use that cannot distinguish over the art. See MPEP § 2111.02(II). Further, the claim 15 preamble language “A composition” does not distinguish over Kim. Neither claim 15 nor the specification require that a “composition” comprise materials or components in addition to the claimed compound. See for example, specification at 5, [42]; Id. at page 6, [49]-[50]. Thus, under its broadest reasonable interpretation, consistent with the specification, a “composition” encompasses a one-component composition (i.e., a composition that consists only of the claimed compound). MPEP § 2111.
8 The specification states that in <Comparative Example 2>, “[a] product of cyclopentadienyl-tris(dimethylamido) hafnium (CpHf(NMe2)3 or CpHf) by UP Chemical was used”. Specification at page 27, [223].