DETAILED ACTION
In the amendment filed on July 14, 2026, claims 1 – 20 are pending. Claims 1, 13 have been amended.
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 103
The rejections of the claims under 35 USC § 103 in the previous Office Action are withdrawn due to Applicant amendment.
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.
Claim(s) 1 – 12 is/are rejected under 35 U.S.C. 103 as being unpatentable over Shanbhag et al. US 20190185999 A1 (hereinafter “Shanbhag”) in view of Wang et al. US 20070134416A1 (hereinafter “Wang”) and Shih et al. US 20050274396 A1 (hereinafter “Shih”).
Regarding claims 1, 4, 5, 8, 10, 11:
Shanbhag is directed to a method of forming a protective coating of a chamber component ex-situ (Abstract; [0005]). Shanbhag discloses that their method comprises:
providing a chamber component that requires cleaning, such as an aluminum showerhead or ceramic components [meeting claim 10] ([0037], [0041], [0050], [0052], [0066]; Fig.1A);
wet cleaning the surface of the coated chamber component by exposure to e.g. HF or NO3 to remove surface contaminants prior to coating ([0037], [0049], [0115] – [0016]); and
depositing the protective coating by atomic layer deposition [conformal coating technique, meeting claim 11] ([0055] – [0059]).
Shanbhag further discloses that the protective coating that is deposited may be two or more distinct and different protective coatings ([0064] – [0065]). Among the coatings that may be part of the two or more protective coatings, Shanbhag discloses that each coating can be inter alia aluminum oxide (Al2O3), yttrium oxide (Y2O3), or yttrium fluoride (YF3). In a particular example, Shanbhag discloses a protective bilayer film, that is aluminum oxide coated/layered [first metal oxide layer] with yttrium oxide [second layer] ([0065]).
While Shanbhag does not expressly teach acts of individually depositing the layers of a bilayer (i.e. the act of depositing a first layer and a separate act of depositing a second layer) it would have been readily apparent to one of ordinary skill in the art that Shanbhag implies such steps in view of their discussion of their deposition process, changing only what reactants are used to provide a given layer ([0068] – [0076]).
Shanbhag does not expressly teach a specific embodiment of their method where a metal oxide layer is deposited on a chamber surface followed by a yttrium [rare earth] fluoride layer; and does not expressly teach a step of removing surface oxidation on the rare earth fluoride using a wet clean process, wherein the wet clean process comprises placing the chamber component in a bath comprising hydrogen fluoride and water for about 5 minutes to about 4 hours, and wherein the hydrogen fluoride is at a concentration of about 0.5% to about 50% v/v.
With regards to a specific embodiment of their method where a metal oxide layer is deposited on a chamber surface followed by a yttrium [rare earth] fluoride layer:
However, Shanbhag discloses forming an aluminum oxide layer onto a showerhead and pedestal in an embodiment of their method [meeting claim 18] ([0155]). Furthermore, Shanbhag discloses that yttrium fluoride is as suitable a coating as yttrium oxide in a bilayer of protective coatings as discussed above.
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have envisioned an embodiment of Shanbhag or otherwise have modified an embodiment of Shanbhag wherein a first layer comprising aluminum oxide and a second layer of yttrium oxide are independently deposited as a bilayer because Shanbhag discloses that their method of deposition can apply to the formation of both materials, and because as taught by Shanbhag, the use of yttrium fluoride is known to be suitable for the purpose of being a protective coating, alongside yttrium oxide. The courts have held that the selection of a known material/device/product based for its intended use supports a prima facie case of obviousness. Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945), Ryco, Inc. v. Ag-Bag Corp., 857 F.2d 1418, 8 USPQ2d 1323 (Fed. Cir. 1988).
With regards to the step of removing surface oxidation on the rare earth fluoride using a wet clean process, wherein the wet clean process comprises placing the chamber component in a bath comprising hydrogen fluoride and water for about 5 minutes to about 4 hours, and wherein the hydrogen fluoride is at a concentration of about 0.5% to about 50% v/v.
Wang is directed to a cleaning method for removing contaminants from the surface of a chamber/chamber component protective coating (Abstract; [0003], [0005] – [0008]). Wang discloses that their cleaning method comprises:
depositing a film of a plasma resistant coating onto an aluminum alloy surface of a processing component, wherein the plasma resistant coating may contain an oxide or fluoride of e.g. yttrium, such as yttrium aluminum garnet ([0016, [0019]]); and
wet-cleaning the surface of the plasma resistant coating with a dilute acid solution of e.g. HNO3 to remove any and all contaminants and undesired byproducts from the protective coating as well as provide fluorination, thus restoring the surface of the protective coating to its initial state [removing surface oxidation] ([0025] – [0026]).
The cleaning process aids in removing trace impurities and loose particles that may exist and can contaminate process chambers ([0024]).
Furthermore analogous art, Shih is directed to a method of cleaning quartz surfaces (Abstract). The method comprises a step of immersing a component into a bath including and 1 wt% HF acid and HNO3 acid solution [with water] (Abstract; [0027], [0050]). The amount of HF may range between 1wt% to 5wt%HF and the amount of HNO3 may range between 5wt% to 20wt% with the balance water ([0027]). The component may be immersed for e.g. between 10 minutes to about 20 minutes ([0028]). Both components aid in cleaning away different types of contamination, such as organic contaminants thus ensuring a thorough cleaning of the component.
In view of the prior art as a whole, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the method of Shanbhag by including a step of immersing the chamber component in a bath comprising hydrogen fluoride and water for about 5 minutes to about 4 hours, and wherein the hydrogen fluoride is at a concentration of about 0.5% to about 50% v/v because as taught by Shih and Wang, the use of such a cleaning solution helps reduce potential contaminants from being reintroduced into process chambers, and would include the removal of surface oxidation by re-fluorination, as taught by Wang.
Additionally, with HF having a density of 1.15g/mL at standard conditions, the weight percent of HF in the solution with water ranges from 0.89% to 4.70% v/v within the particular solutions of HF disclosed in Shih.
Regarding claims 2 and 3, 9:
Shanbhag discloses that the purity of the protective coatings may be between 99.9 – 99.999% pure for each of the recited coating materials in a given layer ([0088] – [0090]). At such levels of purity with yttrium fluoride as the top layer, there is a reasonably expectation that the level of impurities, including oxygen radicals, is less than 0.1 percent.
Regarding claim 12, 6, 7:
Shanbhag discloses that the thickness for a given sublayer, including for a bilayer may be evenly divided (1:1; which is larger than 1:10) ([0065]). Additionally, Shanbhag discloses that the final thickness may be between 1 nm to 10 mm, with more specific ranges of e.g. 100nm to 500nm, meeting claim 7 where the bilayer is evenly split in thickness between the two layers ([0013], [0048]). With regards to claim 6, Shanbhag discloses overlapping ranges. In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d 1362, 1365-66(Fed. Cir. 1997). See MPEP 2144.05.
Claims 13 – 18, 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Shanbhag in view of West et al. US 20050048876 A1 (hereinafter “West”).
Regarding claims 13, 14, 15, 17,18:
Shanbhag is directed to a method of forming a protective coating of a chamber component ex-situ (Abstract; [0005]). Shanbhag discloses that their method comprises:
providing a chamber component that requires cleaning ([0050], [0052]; Fig.1A);
wet cleaning the surface of the coated chamber component by exposure to e.g. HF or NO3 to remove surface contaminants ([0115] – [0016]); and
depositing the protective coating by atomic layer deposition ([0055] – [0059]).
Shanbhag further discloses that the protective coating that is deposited may be two or more distinct and different protective coatings ([0064] – [0065]). Among the coatings that may be part of the two or more protective coatings, Shanbhag discloses that each coating can be inter alia aluminum oxide (Al2O3), yttrium oxide (Y2O3), or yttrium fluoride (YF3). In a particular example, Shanbhag discloses a protective bilayer film, that is aluminum oxide coated/layered [first metal oxide layer] with yttrium oxide [second layer] ([0065]).
While Shanbhag does not expressly teach acts of individually depositing the layers of a bilayer (i.e. the act of depositing a first layer and a separate act of depositing a second layer) it would have been readily apparent to one of ordinary skill in the art that Shanbhag implies such steps in view of their discussion of their deposition process, changing only what reactants are used to provide a given layer ([0068] – [0076]).
Shanbhag does not expressly teach a specific embodiment of their method where a metal oxide layer is deposited on a chamber surface followed by a yttrium [rare earth] fluoride layer. Shanbhag also does not expressly teach that the deposition of the first layer and then the deposition of the second layer are subsequent to the performance of the recited wet clean process.
With regards to the specific embodiment of their method where a metal oxide layer is deposited on a chamber surface followed by a yttrium [rare earth] fluoride layer:
However, Shanbhag discloses forming an aluminum oxide layer onto a showerhead and pedestal in an embodiment of their method [meeting claim 18] ([0155]). Furthermore, Shanbhag discloses that yttrium fluoride is as suitable a coating as yttrium oxide in a bilayer of protective coatings as discussed above.
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have envisioned an embodiment of Shanbhag or otherwise have modified an embodiment of Shanbhag wherein a first layer comprising aluminum oxide and a second layer of yttrium oxide are independently deposited as a bilayer because Shanbhag discloses that their method of deposition can apply to the formation of both materials, and because as taught by Shanbhag, the use of yttrium fluoride is known to be suitable for the purpose of being a protective coating, alongside yttrium oxide. The courts have held that the selection of a known material/device/product based for its intended use supports a prima facie case of obviousness. Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945), Ryco, Inc. v. Ag-Bag Corp., 857 F.2d 1418, 8 USPQ2d 1323 (Fed. Cir. 1988).
With regards to the deposition of the first layer and then the deposition of the second layer are subsequent to the performance of the recited wet clean process.
Shanbhag discloses that in the course of fabricating semiconductor devices, a cleaning process tends to be required in order to restore the repeatability and precision of semiconductor fabrication ([0037]). Shanbhag further discloses that cleaning processes can alter the surface conditions of underlying reaction chamber components, including components (e.g. showerheads) that are “coated with an in situ formed undercoat” ([0037]). Shanbhag further discloses that the disclosed protective coating may end up flaked off due to exposure to cleaning plasma or other plasma depending on the deposited thickness ([0059]). Shanbhag also discloses that after a period use, the coated chamber component and their coatings may begin to degrade ([0062]).
West is directed to methods of fabricating substrate processing chamber components and the refurbishment of substrate processing chamber components (Abstract; [0019]). West discloses that in both the manufacturing and the refurbishment contexts, particles can be generated or retained from their respective processes that act as contamination of chamber component surfaces ([0019]).
West discloses embodiments of a cleaning and manufacturing/refurbishing method comprising: grit-blasting a chamber component to roughen/texture the surface of the component, especially performing grit-blasting after the processing of a number of substrates ([0024], [0026], [0028]); before/after grit-blasting, rinsing or [bath] immersing a chamber component with/into a solution comprising aqueous HF and HNO3 [meeting claims 15, 17] in a concentration from about 3% to about 80% by volume as a chemical cleaning ([0024], [0028], [0032], [0037]); and after the grit-blasting and cleaning step, subsequently applying a fresh coating onto the cleaned chamber component surfaces ([0028], [0033], [0037]). The fresh coatings are those intended to be formed of materials that are corrosion resistant such as aluminum oxide ([0032]).
In view of the prior art as a whole, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the method of Shanbhag by performing deposition of the first layer and then the deposition of the second layer are subsequent to the performance of the recited wet clean process because as taught by both Shanbhag and West: substrate processing chamber components accumulate process residue and otherwise degrade over use, West teaches and Shanbhag suggests that substrate processing chamber components can be refurbished and thus naturally reduce the cost of replacing used processing chamber components; and because West teaches that processing chamber components – whether coated or not – should be textured and/or cleaned to allow for better adhesion of freshly applied protective coatings.
Regarding claim 16:
West discloses that the cleaning solution may have at least one of HF and HNO3 in a concentration from about 3% to about 80% by volume (%v/v) ([0024], [0028], [0032], [0037]), which overlaps with the claimed range.
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d 1362, 1365-66(Fed. Cir. 1997). See MPEP 2144.05.
Regarding claim 20:
Shanbhag does not expressly teach the repetition of the steps of depositing the first and second layers.
However, Shanbhag does disclose that there may be two or more protective coatings and that they may be arranged as a bilayer, trilayer and so forth ([0064] – [0065]). The repetition of deposition steps to lead to a repetition of formed protective coatings amount to a duplication of steps and parts. Absent a showing of unexpected results, a prima facie case of obviousness exists where steps and their resultant products are merely duplicates. In re Harza, 274 F.2d 669, 124 USPQ 378 (CCPA 1960).
Claim(s) 19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Shanbhag in view of West as applied to claims 13 – 18, 20 above, and further in view of Wang.
Regarding claim 19:
Shanbhag in view of West does not expressly teach that the method further comprising removing surface oxidation on the rare earth fluoride using an additional wet clean process.
The disclosure of Wang discussed above in the rejection of claims 1 – 12 under 35 USC 103 over Shanbhag in view of Wang applies to the present rejection, mutatis mutandis.
It would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the method of Shanbhag by including a step of removing surface oxidation on the rare earth fluoride using an additional wet clean process because Wang teaches that such a cleaning step helps reduce potential contaminants from being reintroduced into process chambers and would include the removal of surface oxidation by re-fluorination, as taught by Wang.
Response to Arguments
Applicant’s arguments, filed July 14, 2026, with respect to the rejection(s) of the claim(s) under USC §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 Shih and West.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any extension fee pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the date of this final action.
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/JOSE I HERNANDEZ-KENNEY/
Primary Examiner
Art Unit 1717
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