DETAILED ACTION
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 .
Election/Restrictions
Newly submitted claim 26 is directed to an invention that is independent or distinct from the invention originally claimed for the following reasons:
New Claim 26 recites a molybdenum precursor comprising a nitrosyl group-containing ligand.
Since applicant has received an action on the merits for the originally presented invention, including a distinct molybdenum precursor -- bis(ethylbenzene)molybdenum -- this invention has been constructively elected by original presentation for prosecution on the merits. Accordingly, Claim 26 is withdrawn from consideration as being directed to a non-elected invention. See 37 CFR 1.142(b) and MPEP § 821.03.
To preserve a right to petition, the reply to this action must distinctly and specifically point out supposed errors in the restriction requirement. Otherwise, the election shall be treated as a final election without traverse. Traversal must be timely. Failure to timely traverse the requirement will result in the loss of right to petition under 37 CFR 1.144. If claims are subsequently added, applicant must indicate which of the subsequently added claims are readable upon the elected invention.
Should applicant traverse on the ground that the inventions are not patentably distinct, applicant should submit evidence or identify such evidence now of record showing the inventions to be obvious variants or clearly admit on the record that this is the case. In either instance, if the examiner finds one of the inventions unpatentable over the prior art, the evidence or admission may be used in a rejection under 35 U.S.C. 103 or pre-AIA 35 U.S.C. 103(a) of the other invention.
Applicant is reminded that upon the cancelation of claims to a non-elected invention, the inventorship must be corrected in compliance with 37 CFR 1.48(a) if one or more of the currently named inventors is no longer an inventor of at least one claim remaining in the application. A request to correct inventorship under 37 CFR 1.48(a) must be accompanied by an application data sheet in accordance with 37 CFR 1.76 that identifies each inventor by his or her legal name and by the processing fee required under 37 CFR 1.17(i).
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 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 nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim(s) 1-6, 8-12,14-16, 22-23, and 27 is/are rejected under 35 U.S.C. 103 as being unpatentable over Yu et al. (US 2019/0390340) in view of Kim et al. (WO 2020/101336).
Regarding Claims 1-6 and 8-10, Yu et al.(US’340) teach a method of depositing molybdenum on a substrate by a cyclical deposition process, the method comprising providing a substrate in a reaction chamber [0024, 0031-0032,0035,0102-0103]; providing a molybdenum precursor to the reaction chamber in a vapor phase (e.g. bis(ethylbenzene)molybdenum [0102]); and providing a reactant (e.g. iodoethane or diiodomethane) to the reaction chamber in a vapor phase to form molybdenum on the substrate (Claims 4, 10); wherein the molybdenum is formed on the substrate as elemental molybdenum (i.e. “deposited metal film”) [0103], and the molybdenum precursor comprises a molybdenum atom and hydrocarbon ligand (e.g. bis(ethylbenzene)) molybdenum [0102]), and the reactant comprises a halogenated hydrocarbon (alkyl halide) with an organic group R comprising 1-6 carbons [0091], including a species in which more than halogen atom is substituted for hydrogen atoms (e.g. 2 iodine atoms for 2 hydrogen atoms in CH2I2- (diiodomethane)) and another species with more than one carbon and in which a halogen is substituted for a hydrogen (e.g. iodoethane) (Claim 4) . Additionally, US’340 teaches that the organic group R can be any of an alkenyl or aryl (i.e. alkene or arene) [0090]. US’340 teaches that the halogens are released during decomposition of the precursor so that they are available for reaction [0123]. US’340 fails to teach a species of hydrocarbon ligand which both a) EITHER 1) substitutes two halogen atoms for two hydrogen atoms in the case of alkenyl, alkynyl, or aryl groups OR 2) substitutes three halogen atoms for three hydrogen atoms in other case AND ALSO b) includes more than one carbon. Even though US’340 would have itself provided sufficient guidance to a person of ordinary skill in the art to motivate substituting halogens for hydrogens (including two iodine atoms for two hydrogen atoms) on hydrocarbon ligands of at least 1-6 carbons up to the number of hydrogens available for substitution in order to provide a desired concentration of halogen for a reaction, Kim et al. (WO’336) is analogous art for the deposition of a molybdenum film using an alkyl halide (e.g. alkyliodide) as a reactant [0001] and teaches specific reactants, including alkyl groups with 1-3 substitutions of iodine on alkyl groups, including an ethane with substitutions of an iodine atoms for each of two hydrogen atoms on different carbons (e.g. ICH2CH2I, or diiodoethane and ICH2CH2CH2I, or diiodopropane) [30,85]. The combination of US’340 in view of WO’336 fails to teach specifically the recited number of halo-substitutions on the specific carbons; however, the recited limitations on the number of halo-substitutions on specific carbons is an obvious extension of the suggestion in US’340 and WO’336 to substitute halogens, and in particular iodine, for hydrogens in groups including alkyl, alkenyl, or aryl groups. Moreover, the recited limitation requiring three or more halogen atoms at least two of which are on different carbons is considered a prima facie obvious duplication of parts and/ or steps. MPEP 2144.04.VI.B, and the number of substitutions is an exercise in routine optimization to provide a desired amount of halogen per molecule of reactant.
Regarding Claim 11, US’340 teaches that the molybdenum precursor is supplied in pulses, reactant supplied in pulses and the reaction chamber is purged between consecutive pulses of molybdenum precursor and reactant [0032].
Regarding Claim 12, US’340 teaches a pulse of a first process gas for a first period of time 706 (first reactant pulse for a first reactant pulse length for a first predetermined number of deposition cycles) followed by a pulse of a second process gas for a second period of time 710 (providing a second reactant pulse for a second reactant pulse length for a second predetermined number of deposition cycles) after which the cycle may be repeated (Fig. 7; [0085, 0098-0100]). In claim 12, the first and the second number of deposition cycles can each be one cycle. US’340 fails to particularly require performing a different first and second time for different pulses of reactants. However, it teaches that pulse times may vary [0088] and that the period of time for soaking the substrate in alkyl halide gas may be any suitable amount to allow alkyl halide to form an adequate absorption layer on the substrate surface and provides a variety of possible ranges of time [0146, 0149]. Thus, US’340 provides evidence that pulse time is a result-effective variable, known in the prior art to affect adequate adsorption. It would have been obvious to a person of ordinary skill in the art at the time of invention to pulse reactants for different durations, including a first longer pulse followed by a second shorter pulse, through routine optimization. In addition, the combination of references fails to teach performing a specific sequence of first providing more than one of a first reactant pulse before providing one or more of a second reactant pulse.
Regarding Claim 14, US’340 teaches that the range of temperature can include a temperature between 200 and 400 C, between 250 and 350 C, or between 300 to 400 C [0095,0128].
Regarding Claim 15, US’340 teaches atomic layer deposition (ALD) and chemical vapor deposition (of which ALD is a type) (Abstract; [0085,0139,0163]).
Regarding Claim 16, US’340 teaches that the cyclical deposition comprises thermal deposition (Abstract; [0085]).
Regarding Claim 22, Yu et al. (US’340) describes a thermal ALD process which would have itself suggested heating the molybdenum precursor before providing the precursor to the reaction chamber, since it was conventional in thermal ALD at the time of invention to do so. However, US’340 fails to plainly teach heating the precursor before introducing it into the reaction chamber. WO’336 teaches heating the precursor before introducing it into a process chamber [0058]. It would have been obvious to a person of ordinary skill in the art at the time of invention to modify the process of the combination of references by heating the precursor before introducing it into the reaction chamber, because the step was conventional for thermal ALD at the time of invention and WO’336 teaches the step for forming a molybdenum thin film from a precursor.
Regarding Claim 23, US’340 teaches maintaining the substrate at a temperature a deposition temperature less than the decomposition temperature of the metal precursor and substrate temperatures up to 600 C [0095]. US’340 fails to teach a temperature to heat a metal precursor before introducing it to the reaction chamber. WO’336 also teaches a range of substrate temperature, substantially overlapping that of US’340 (80-500 C) [0055], suggests selecting a substrate temperature based on decomposition of a molybdenum precursor, as in US’340 [0063], and teaches heating a molybdenum precursor to a temperature of 70 C for a specific molybdenum precursor [0101]. The combination of US’340 in view of WO’336 fails to teach heating a molybdenum precursor to a temperature of 100 C or greater. However, the teaching of US’340 to heat a substrate to a temperature less than the decomposition temperature of the molybdenum precursor combined with the teachings of US’340 and WO’336 of a substrate temperature in the range of 80-500 C would have suggested a range of temperatures to which to heat a molybdenum precursor to a temperature range of about 80 C-500 C, below a decomposition temperature of at least some molybdenum precursors, including a substantial range above 100 C. Thus, it would have been obvious to a person of ordinary skill in the art at the time of invention to modify the process of the combination of references by heating a molybdenum precursor to at least 100 C by routine optimization. Moreover, generally, differences in temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such temperature is critical, and there is no evidence that temperature to which to heat a molybdenum precursor is critical so long as the temperature is between its vaporization temperature and its decomposition temperature.
Regarding Claim 27, US’340 teaches repeated cycles of precursor and reactant to obtain a metal layer of a desired thickness (Fig. 7;[0032]). US’340 fails to teach 5 to 30 cycles. It would have been obvious to a person of ordinary skill in the art at the time of invention to modify the process of the combination of references with as many cycles of precursor and reactant as desired to achieve a desired thickness. Moreover, increasing cycles is a prima facie obvious duplication of steps. MPEP 2144.04. With regard to relative pulse length, see rationale in the rejection of Claim 12 above for optimizing the pulse duration of a given reactant pulse.
Claim(s) 7 is/are rejected under 35 U.S.C. 103 as being unpatentable over Yu et al. (US 2019/0390340) in view of Kim et al. (WO 2020/101336) as applied to Claim 1 above, and further in view of Groening (US 3,761,576).
Regarding Claim 7, US’340 teaches halogenated hydrocarbons (alkyl halide) with an organic group R comprising 1-6 carbons [0091], including a species in which more than halogen atom is substituted for hydrogen atoms (e.g. 2 iodine atoms for 2 hydrogen atoms in CH2I2- (diiodomethane)) and another species with more than one carbon and in which a halogen is substituted for a hydrogen (e.g. iodoethane) (Claim 4). WO’336 is analogous art for the deposition of a molybdenum film using an alkyl halide (e.g. alkyliodide) as a reactant [0001] and teaches specific reactants, including alkyl groups with 1-3 substitutions of iodine on alkyl groups, including an ethane with substitutions of an iodine atoms for each of two hydrogen atoms on different carbons (e.g. ICH2CH2I, or diiodoethane; ICH2CH2CH2I, or diiodopropane; and triiodomethane) [30,80,85]. The combination of US’340 in view of WO’336 fails to teach specifically a species represented by the recited chemical formula. Groening (US’576) is analogous art in the field of vapor deposition of a metal containing film by reacting a metal-containing precursor with a carbon-containing reactant (Abstract). In addition to teaching dihalogenated hydrocarbon reactants, US’576 also suggests trihalogenated hydrocarbons as precursors for analogous reactions with metallic precursor; such trihalogenated hydrocarbons include 1,1,2-trichloroethane, a species of the recited formula. Thus, it would have been obvious to a person of ordinary skill in the art at the time of invention to modify the process of the combination of US’340 in view of WO’336 with halogenated hydrocarbon reactants with the recited formula, because US’576 suggests that such reactants were known for similar processes. In addition, the number of substitutions of halogens is an exercise in routine optimization to provide a desired amount of halogen per molecule of reactant with a desired reactivity.
Claim(s) 24 is/are rejected under 35 U.S.C. 103 as being unpatentable over Yu et al. (US 2019/0390340) in view of Kim et al. (WO 2020/101336) as applied to Claim 1 above, and further in view of Panda et al. (US 2020/0126844).
Regarding Claim 24, US’340 teaches annealing a substrate [0006,0030,0068,0082] and annealing the metal film [0118]. The combination of US’340 in view of WO’336 fails to teach forming a capping layer on the metal followed by annealing the substrate after forming the capping layer. Panda et al. (US’844) teach a particular application of molybdenum deposition by vapor deposition as bit line metal 240 for a memory structure (Abstract; Fig. 2; [0007,0034,0057]) on which is deposited a capping layer 250 (e.g. silicon nitride) [0007] to prevent roughening of the bit line metal surface [0024]. Thus, it would have been obvious to a person of ordinary skill in the art at the time of invention to modify the process of the combination of US’340 in view of WO’336 by forming a capping layer of silicon nitride on the molybdenum, because US’844 teaches an application for depositing metallic molybdenum by vapor deposition (ALD or CVD) to form a bit line metal surface on which a capping layer of silicon nitride is formed to prevent roughening of the bit line metal surface.
Response to Arguments
Applicant’s amendment to the claims, filed 12 November 2025, with respect to the rejection of Claims 7 and 25 under 35 USC 112(a) and of Claim 7 under 35 USC 112 (b) have been fully considered and overcome the previous rejection under these paragraphs. The rejection of Claims 7 and 25 under 35 USC 112(a) and of Claim 7 under 35 USC 112 (b) have been withdrawn.
Applicant’s arguments, see Remarks, pp. 7-8, filed 12 November 2025, with respect to the rejection(s) of claim(s) 24-25 under 103 have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Panda et al. (US 2020/0126844).
Applicant's arguments, filed 12 November 2025, with respect to the rejections of Claims 1-12, 14-16, and 22-24 under 35 USC 103 have been fully considered but they are not persuasive.
In response to Applicant’s argument that Yu differs from Applicant’s claim 12, which recites providing a first reactant pulse for a first reactant pulse length for a first predetermined number of deposition cycles and providing a second reactant pulse for a second reactant pulse length for a second predetermined number of deposition cycles (Remarks, p. 6, last paragraph to p. 7, first paragraph), the argument is not persuasive, since Yu teaches multiple cycles of precursor and reactant (e.g. Fig. 7), and the first predetermined number of deposition cycles and second predetermined number of deposition cycles can each be one cycle. For reasons given in US’340, it would have been obvious to a person of ordinary skill in the art at the time of invention to modify a pulse length (duration) of a given cycle (including reactant pulse length) through routine optimization for the reasons given in the rejections (see, for example, rejection of Claims 12 and 27 above).
In response to Applicant’s argument that “The Office Action does not assert that the number of deposition cycles within which a pulse length is incorporated is a result-effective variable (Remarks, p. 7), while true, result-effectiveness is but one motivation for optimization. MPEP 2144.05.II.B. Moreover, although one way for Applicant to rebut a prima facie case of obviousness based on optimization is to show that a parameter is NOT recognized as a result-effective variable (MPEP 2144.05.II.C, Applicant has made no case, merely stating that Examiner has not used “result-effectiveness” as a rationale for duplicating cycles. In this case, US’340 plainly teaches as many cycles as necessary to achieve a desired thickness, which suggests a relation between cycles and thickness (Fig. 7; [0032]).
In response to Applicant’s argument that pulse time is not a result-effective variable, because it is not recognized as a variable which achieves a recognized result (Remarks, p. 7), US’340 reads, “A dose time should be long enough to provide a volume of compound sufficient to adsorb/chemisorb onto substantially the entire surface of the substrate and form a layer of a process gas component thereon,” which provides sufficient evidence of a relationship between pulse time and adsorption” and “The period of time that the substrate is exposed to the metal precursor gas may be any suitable amount of time necessary to allow the metal precursor to react with the adsorbed halogen on the substrate surface” [0106]. Thus, whether Applicant prefers to view US’340 as providing evidence that pulse time is a result-effective variable, known in the prior art to affect adsorption and/ or extent of reaction or as directly suggesting optimizing pulse time to achieve adequate adsorption and/ or reaction time, US’340 would have suggested optimizing pulse time for any pulse of reactant or precursor.
Allowable Subject Matter
Claim 25 is objected to as being dependent upon a rejected base claim, but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
The following is a statement of reasons for the indication of allowable subject matter:
No prior art has been identified as of the time of this Office Action which teaches or suggests a step of annealing after depositing a silicon nitride capping layer on molybdenum.
Conclusion
No claim is allowed.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ALEXANDER M WEDDLE whose telephone number is (571)270-5346. The examiner can normally be reached 9:30-6:30.
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ALEXANDER M WEDDLE
Examiner
Art Unit 1712
/ALEXANDER M WEDDLE/Primary Examiner, Art Unit 1712