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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 6-18-26 has been entered.
Response to Arguments
With respect to the rejection of Claims 1, 3-5, 7-8, 11-13, and 16 under 35 U.S.C. 103 as being unpatentable over Haukka et al. in view of Harkness et al., as understood the traversal relies on arguments. Applicant argues “Applicants' claimed invention recites a typically asymmetrical ratio in the number of executions between the first and second sub-cycles of the super cycle. Such a typically asymmetrical sub-cycle design is derived in consideration of the difference in characteristics between platinum and the non-platinum metal, particularly the fact that each metal has different nucleation densities and growth rates.” [Remarks, Page 7-8]. This is unpersuasive. It is noted that the “typically asymmetrical” refers to the claim limitation “the first sub-cycle is performed 2 to 30 times and then the second sub-cycle is performed 1 to 3 times”, which is not required to be asymmetrical. Therefore Applicants’ arguments are not commensurate with the scope of the claims. Applicant appears to be arguing that a broad claim is patentable because the prior art does not teach a single, narrow, embodiment.
Applicant further argues “Pending claim 1, as amended, limits the final composition of the catalyst to 75- 85 at% platinum and 15-25 at% non-platinum metal (i.e., a Pt3M structure). The asymmetric sub-cycles of Applicants' claimed invention (2-30 platinum cycles vs. 1-3 non-platinum cycles) are not simple physical variables for increasing film thickness as in Haukka, but rather highly sophisticated chemical control variables for precisely adjusting the desired stoichiometric ratio at the atomic level.” [Remarks, Page 8-9]. This is unpersuasive. Pending Claim 1, as amended, does not in fact limit the final composition of the catalyst to 75- 85 at% platinum and 15-25 at% non-platinum metal as Applicant alleges, this limitation is presented in Claim 17, which stands rejected under different prior art. The rejections are MAINTAINED.
With respect to the rejection of Claims 2, 6, 9, and 17 under 35 U.S.C. 103 as being unpatentable over Haukka et al. in view of Harkness et al., in further view of Minjauw et al., as understood the Applicant argues for the patentability of these dependent claims by arguing for the patentability of the independent claim upon which they depend (Claim 1). As such the response can be found within the response to Claim 1 (above). The rejections are MAINTAINED.
With respect to the rejection of Claim 10 under 35 U.S.C. 103 as being unpatentable over Haukka et al. in view of Harkness et al., in further view of Minjauw et al., in further view of Ono et al., as understood the Applicant argues for the patentability of Claim 10 by arguing for the patentability of the independent claim upon which it depends (Claim 1). As such the response can be found within the response to Claim 1 (above). The rejections are MAINTAINED.
Claim Interpretation
Claim 1 recites “a first sub-cycle and a second sub-cycle; wherein the first sub-cycle comprises: injecting a platinum precursor into the reactor … and wherein the second sub-cycle comprises: injecting a non-platinum metal precursor into the reactor”. Additionally the specification discloses “Terms such as first, second, etc., may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present disclosure, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.” [0063]. Therefore it is understood that the first sub-cycle does not necessarily mean that the platinum precursor must be used before the non-platinum precursor. In other words the second sub-cycle may be performed before the first sub-cycle without departing from the scope of Claim 1.
Claim Rejections - 35 USC § 103
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.
Claims 1, 3-5, 7-8, 13, and 16 are rejected under 35 U.S.C. 103 as being unpatentable over US 20140087076 A1 Haukka et al. in view of US 20150207153 A1 Harkness et al. Claim 1 requires “A method for manufacturing an alloy catalyst comprising: applying a support in a reactor”. Haukka et al. discloses “In some embodiments, in each ALD cycle the substrate is alternately contacted with a noble metal precursor and a second reactant, such that a thin noble metal film is formed on the substrate.” [0011]. Substrate is synonymous with support.
Claim 1 further requires “depositing an alloy of platinum and a non-platinum metal on the support through a super cycle comprising a first sub-cycle and a second sub-cycle; wherein the first sub-cycle comprises: injecting a platinum precursor into the reactor so that the platinum precursor is adsorbed onto the support”. Haukka et al. discloses a first layer adsorbing onto the support “Each ALD cycle comprises alternating and sequential provision of a first and second reactant. A first reactant is conducted into the chamber in the form of vapor phase pulse and contacted with the surface of the substrate. Conditions are selected such that no more than about one monolayer of the precursor is adsorbed on the substrate surface in a self-limiting manner.” [0040] and a platinum containing layer “However, in other embodiments, the final metal structure may comprise two or more different noble metals. For example, the growth can be started with the deposition of platinum and ended with the deposition of ruthenium metal, producing a graded alloy.” [0052]
Claim 1 further requires “injecting a first purge gas into the reactor; depositing platinum on the support by injecting a reaction gas into the reactor; and injecting a second purge gas into the reactor”. Haukka et al. discloses “purging the reaction chamber to remove excess noble metal precursor and reaction by products, if any, providing a pulse of a second reactant, such as an oxygen, ozone, ammonia or ammonia plasma containing gas onto the substrate; and purging the reaction chamber to remove excess second reactant and any gaseous by-products formed in the reaction between the metal precursor layer on the first surface of the substrate and the second reactant.” [0045-0047].
Claim 1 further requires “wherein the second sub-cycle comprises: injecting a non-platinum metal precursor into the reactor so that the non-platinum metal is adsorbed onto the support; injecting a third purge gas into the reactor; depositing the non-platinum metal on the support by injecting a reaction gas into the reactor; and injecting a fourth purge gas into the reactor.”. Haukka et al. discloses multiple layer growth steps “The pulsing and purging cycle is repeated until a thin film of the desired thickness has been formed.” [0048] and that these steps can include different noble metals to form an alloy “The thin film typically comprises multiple monolayers of a single noble metal. However, in other embodiments, the final metal structure may comprise two or more different noble metals. For example, the growth can be started with the deposition of platinum and ended with the deposition of ruthenium metal” [0052]. In other words Haukka et al. implicitly discloses repeating the steps of precursor, purge, reaction gas, purge with a non-platinum noble metal such as ruthenium.
Claim 1 further requires “the method further comprises heat treating a resultant of the super cycle.”. Haukka et al. does not disclose heat treating the resultant of the super cycle. Harkness et al. is similarly directed at forming platinum alloys by atomic layer deposition “The thin film catalyst coating can be applied to the support material by a number of methods … A particularly preferred technique is atomic layer deposition.” [0012], “The one or more first metals are suitably selected from the group consisting of the platinum group metals (platinum, palladium, rhodium, ruthenium, iridium and osmium), gold or silver, or a base metal … in particular platinum.” [0019], and “In a second embodiment, at least some of the one or more first metals and at least some of the remaining second metal form an alloy.” [0026]. Regarding a post cycle heat treatment Harkness et al. discloses “Formation of such an alloy may require a further processing step, for example heat treatment at a temperature of from 150° C. to 1500° C., suitably 300° C. to 1000° C.” [0026]. It would have been obvious to one of ordinary skill in the art to have combined the method of Haukka et al. with the heat treatment of Harkness et al. because they are both similarly directed to methods of forming platinum containing alloys by atomic layer deposition. The motivation to have combined the method of Haukka et al. with the heat treatment of Harkness et al. is given by Harkness et al. Harkness et al. discloses that the heat treatment can control the degree of alloying “The extent of the alloying can be controlled by the ratio of the one or more first metals: second metal, the temperature of the heat treatment, the time of the heat treatment and the atmosphere of the heat treatment process.” [0026], and therefore one of ordinary skill in the art would have used the heat treatment of Harkness et al. for at least the reason of having greater control over the degree of alloying in the final product.
Claim 1 further requires “the heat treating is performed in a gas atmosphere comprising at least one of hydrogen (H2), ammonia (NH3), nitrogen (N2), argon (Ar) or any combination thereof.”. Harkness et al. discloses using hydrogen in a post-ALD process to reduce the metals of the layer “Alternatively, a two-step process may be used, wherein a compound of the second metal, for example the nitride, is applied to the support material, suitably by one of the techniques described above and preferably by atomic layer deposition, followed by a reduction process to reduce the second metal compound to the second metal. The reduction process may be carried out using any suitable reducing agent, for example hydrogen.” [0021].
Claim 1 further requires “the first sub-cycle is performed 2 to 30 times and then the second sub-cycle is performed 1 to 3 times; or the second sub-cycle is performed 1 to 3 times and then the first sub-cycle is performed 2 to 30 times.”. Haukka et al. does not particularly limit the number of cycles performed, disclosing “The pulsing and purging cycle is repeated until a thin film of the desired thickness has been formed.” [0048]. In other words the number of cycles performed and thickness of the resulting layer is a result-effective variable. One of ordinary skill in the art would have been able to choose any number of cycles and sub cycles to get the alloy composition and thickness to the desired amount, and doing so would have been obvious to try.
Claim 1 further requires “the super cycle is repeatedly performed 1 to 10 times.”. Haukka et al. does not particularly limit the number of cycles performed, disclosing “The pulsing and purging cycle is repeated until a thin film of the desired thickness has been formed.” [0048]. In other words the number of cycles performed and thickness of the resulting layer is a result-effective variable. One of ordinary skill in the art would have been able to choose any number of cycles to get the thickness to the desired amount, and doing so would have been obvious to try.
Claim 3 requires “the support comprises at least one of a carbon- based support, a metal oxide-based support or any combination thereof.”. Haukka et al. discloses “The substrate preferably comprises an oxide or nitride surface, more preferably a metal oxide or metal nitride surface. In some embodiments the substrate comprises an Al2O3 surface.” [0012].
Claim 4 requires “the platinum precursor comprises at least one of trimethyl(methylcyclopentadienyl) platinum(IV) (MeCpPtMe3), platinum(II) bis(acetylacetonate) (Pt(acac)2, [(1,2,5,6,-ƞ)-1,5-hexadiene] dimethyl platinum (II) (HDMP), dimethyl(N,N-dimethyl-3-butene-1-amine-N) platinum (DDAP), or any combination thereof.”. Haukka et al. discloses “When depositing platinum films, preferred metal precursors include (trimethyl)methylcyclopentadienylplatinum, platinum (II) acetylacetonato, bis(2,2,6,6-tetramethyl3,5-heptanedionato platinum(II) and their derivatives.” [0057], of which trimethyl(methylcyclopentadienyl) platinum is common. Additionally platinum (II) acetylacetonato is understood to be a typo of platinum (II) acetylacetonate which is equivalent to platinum(II) bis(acetylacetonate).
Claim 5 requires “the reaction gas comprises at least one of oxygen (O2), ozone (O3), air, hydrogen (H2), oxygen plasma (O2 plasma) or any combination thereof.”. Haukka et al. discloses “a second reactant, such as an oxygen, ozone, ammonia or ammonia plasma containing gas” [0046].
Claim 7 requires “the first purge gas, the second purge gas, the third purge gas and the fourth purge gas each comprises at least one of argon (Ar), helium (He), nitrogen (N2) or any combination thereof.”. Haukka et al. discloses “Excess first reactant and reaction byproducts, if any, are purged from the reaction chamber, often with a pulse of inert gas such as nitrogen or argon.” [0040].
Claim 8 requires “the non-platinum metal comprises at least one of palladium (Pd), gold (Au), silver (Ag), copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), tungsten (W), iridium (Ir) or any combination thereof.”. Haukka et al. discloses “For example, the growth can be started with the deposition of platinum and ended with the deposition of ruthenium metal, producing a graded alloy. In other embodiments the thin film is a compound thin film comprising one or more noble metals.” [0052]. While only a Ru-Pt alloy is explicitly disclosed the phrase “a compound thin film comprising one or more noble metals” should be understood to include alloys of platinum with palladium, gold, silver, copper, rhodium, and iridium in addition.
Claim 13 requires “the super cycle is performed in a temperature of 100 °C to 400 °C.”. Haukka et al. discloses “The halide or metalorganic treatment is preferably conducted at a treatment temperature such that the halide or metalorganic reactants have sufficient vapor pressure but below the temperature at which they begin to decompose. In preferred embodiments the treatment temperature is between about 0° C. and about 1000° C., more preferably between about 100° C. and about 400° C.” [0033].
Claim 16 requires “the heat treating is performed in a temperature of 400°C to 1,100°C.”. Harkness et al. discloses “Formation of such an alloy may require a further processing step, for example heat treatment at a temperature of from 150° C. to 1500° C., suitably 300° C. to 1000° C.” [0026], which encompasses the range claimed.
Claims 2, 6, 9, and 17 are rejected under 35 U.S.C. 103 as being unpatentable over US 20140087076 A1 Haukka et al. in view of US 20150207153 A1 Harkness et al., in further view of US 20210095372 A1 Minjauw et al. Regarding Claim 2, Haukka et al. in view of Harkness et al. discloses all of the limitations of Claim 1. Claim 2 further requires “the reactor comprises a fluidized bed reactor or a rotary reactor.”. Minjauw et al. is similarly directed to methods of forming thin films of a ruthenium and platinum alloy (“The present disclosure includes methods that may be utilized to deposit ruthenium-containing films and in particular deposition methods utilized for depositing a ruthenium-platinum alloy” [0024]). Minjauw et al. discloses a rotary reactor may be used “In some embodiments, the reactor is a spatial ALD reactor, in which the substrates moves or rotates during processing.” [0033].
It would have been obvious to one of ordinary skill in the art to have combined the method of Haukka et al. and Harkness et al. with the method of Minjauw et al. because both are similarly directed to methods of forming a ruthenium-platinum alloy by atomic layer deposition.
The motivation to have combined the method of Haukka et al. and Harkness et al. with Minjauw et al. is given by Minjauw et al. when they disclose that rotary reactors can improve uniformity (“In some embodiments in which a batch reactor is used, wafer-to-wafer non-uniformity is less than 3% (1sigma), less than 2%, less than 1% or even less than 0.5%.” [0034]).
Regarding Claim 6, Haukka et al. in view of Harkness et al. discloses all of the limitations of Claim 1. Claim 6 further requires “the depositing of the platinum on the support is performed by a powder atomic layer deposition method.”. As understood by the examiner ‘powder atomic layer deposition’ refers to atomic layer deposition onto a substrate/support which is a powder. Minjauw et al. discloses powdered substrates “A substrate may comprise, but is not limited to, wafers, glasses, polymers, plastics, solid substances, fibers and powders.” [0019].
Regarding Claim 9, Haukka et al. in view of Harkness et al. discloses all of the limitations of Claim 1. Claim 9 further requires “the depositing of the non-platinum metal on the support is performed by a powder atomic layer deposition method.”. As understood by the examiner ‘powder atomic layer deposition’ refers to atomic layer deposition onto a substrate/support which is a powder. Minjauw et al. discloses powdered substrates “A substrate may comprise, but is not limited to, wafers, glasses, polymers, plastics, solid substances, fibers and powders.” [0019].
Regarding Claim 17, Haukka et al. in view of Harkness et al. discloses all of the limitations of Claim 1. Claim 17 further requires “the alloy catalyst comprises: 75 to 85 at% of the platinum; and 15 to 25 at% of the non-platinum metal.”. Minjauw et al. discloses “In some embodiments, the ruthenium-platinum alloy may comprise a platinum content of greater than 5 atomic %, or greater than 10 atomic %, or greater than 15 atomic %, or greater than 25 atomic %, or greater than 50 atomic %, or greater than 75 atomic %, or even greater than 90 atomic %.” [0075]. In other words, Minjauw et al. discloses 5-90 at% platinum and 95-10 at% of a non-platinum metal, which overlaps with the range claimed.
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over US 20140087076 A1 Haukka et al. in view of US 20150207153 A1 Harkness et al., in further view of US 20210095372 A1 Minjauw et al., in further view of US 20250027197 A1 Ono et al. US 20250027197 A1 qualifies as prior art under 35 U.S.C. 102(a)(2) by claiming priority to provisional US 63/284170 filled on 11/30/2021. Regarding Claim 10, Haukka et al. discloses all of the limitations of Claim 1. Claim 10 further requires “the support is maintained in a fluidized state by continuously injecting gas into the reactor while performing the super cycle.”. Ono et al. is similarly directed to methods of forming platinum containing alloys by atomic layer deposition (“The disclosed PGM precursors may be used in a chemical deposition method, such as ALD or CVD, individually or in mixtures, different platinum precursors, and metal precursor(s) in solution or not in solution to form Pt-containing films or islets such as Pt metal, platinum ruthenium alloys, platinum titanium alloys, platinum ruthenium compounds, platinum titanium compounds, etc.” [0069]). Ono et al. discloses maintaining the support in a fluidized state “Vapors of Pt(allyl)(iPr-amd), flown at a rate of 2 sccm for 60 s, would be introduced into the a fluidized powder reactor” [0129].
It would have been obvious to one of ordinary skill in the art to have combined the methods of Haukka et al., Harkness et al., Minjauw et al., and Ono et al. because all three methods are similarly directed to forming platinum-ruthenium alloys by atomic layer deposition. The motivation to have used the fluidized powder reactor of Ono et al. is given by Ono et al. Ono et al. discloses that maintaining the support in a fluidized state prevents agglomeration “It has been observed that the powder particles in fluidized beds tend to stick to each other forming larger particle blocks, agglomerates. In order to hinder the formation of agglomerates, a vibrating gas flow is used, a carefully selected gas flow that vibrates is hence fed into the reaction chamber. According to the principle of Helmholtz resonance, an incoming gas flow is forced over and into a cavity causing vibrations into the outgoing gas flow. The outgoing vibrating gas flow is guided into the reaction chamber in order to hinder the formation of agglomerates.” [0008].
Conclusion
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/JOSHUA MAXWELL SPEER/
Examiner
Art Unit 1736
/DANIEL BERNS/Primary Examiner, Art Unit 1736
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