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
Applicant’s election without traverse of Group I, claims 1-23 in the reply filed on 6/8/2026 is acknowledged.
Claims 24-30 have been cancelled.
Drawings
The drawings are objected to as failing to comply with 37 CFR 1.84(p)(5) because they do not include the following reference sign(s) mentioned in the description: 1150A and 1150C in paragraph 0045. Corrected drawing sheets in compliance with 37 CFR 1.121(d) are required in reply to the Office action to avoid abandonment of the application. Any amended replacement drawing sheet should include all of the figures appearing on the immediate prior version of the sheet, even if only one figure is being amended. Each drawing sheet submitted after the filing date of an application must be labeled in the top margin as either “Replacement Sheet” or “New Sheet” pursuant to 37 CFR 1.121(d). If the changes are not accepted by the examiner, the applicant will be notified and informed of any required corrective action in the next Office action. The objection to the drawings will not be held in abeyance.
Claim Rejections - 35 USC § 112
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.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 2, 3, 5, and 6 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Regarding claim 2, the term “short duration” is a relative term which renders the claim indefinite. The term “short” is not defined by the claim, the specification does not provide a standard for ascertaining the requisite degree, and one of ordinary skill in the art would not be reasonably apprised of the scope of the invention. For the purposes of examination, any duration is considered to be short. Since claims 2, 5, and 6 depend from claim 2 and do not remedy the clarity of the claim, they are also rendered indefinite. It is noted that claim 4 defines what a short duration is and is therefore clear. Appropriate action is required without adding new matter.
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.
Claims 1-6, 9-11, 15, 16, 19, 20, and 22 are rejected under 35 U.S.C. 103 as being unpatentable over Fenwick, US 2017/0323772 A1 in view of Song, US 2006/0124455 A1, Lange, US 2024/0035163 A1, and as evidenced by GPB, “Table of Electronegativities”, 2004.
Regarding claim 1, Fenwick teaches a method of forming a thin film (abstract and 0002), the method comprising:
providing a substrate to be coated (depositing a source material on an article, 0006, so as to provide a substrate to be coated);
(a) exposing the substrate to a metal deposition, resulting in some of the metal depositing on the substrate as a deposited metal (providing and depositing a source material that is a metal that is to be deposited on the article, 0006, 0069, and Fig. 5A); and
(b) exposing the substrate to a plasma generated from a mixture of process gases comprising one or more gaseous oxygen-containing compounds and one or more gaseous fluorine-containing compounds, resulting in at least some of the deposited metal reacting with the plasma to form a metal-fluoride-containing product (providing oxygen and fluorine ions or radicals to the substrate by high-energy plasma to form an MOF thin film, 0069 and Fig. 5A, such that the metal will react with the fluorine and oxygen plasma to form the MOF layer).
They do not teach providing a cyclic process.
Song teaches a thin film deposition apparatus and film forming method (abstract and 0061). They provide an example of forming silicon oxide where an incomplete silicon oxide SiOx1 (x1<2) is formed on a substrate by sputtering and then a thin film of SiOx2 (x1<x2≤2) is formed having a more advanced oxidation than the incomplete silicon oxide (0061). They teach that substrates are held on magnetron sputter electrodes and silicon is used as the target material (0062 and Fig. 1). They teach providing oxygen and argon gas for sputtering so as to form the incomplete silica film on the substrate (0064-0066). They teach that after the incomplete silica film is formed, the substrate is moved from the deposition zone to a reaction process zone (0067 and Fig. 1). They teach that oxygen gas as a reactive gas and argon gas as an inert gas are introduced into the reaction process zone to form a plasma that oxidizes the incomplete silicon oxide to the oxidized film (0068-0069). They teach that by carrying out the process, a thin film having the desired composition can be formed, where the thin films are formed in layers and a thin film having a desired thickness can be formed (0070). They teach that the process imparts high density, good quality, and high functional performance to a deposited thin film (0078). They teach that the reactive gas in the reaction zone can be an oxidizing gas such as ozone or dinitrogen monoxide, a nitriding gas such as nitrogen, a carbonizing gas such as methane, or a fluorinating gas such as fluorine or carbon tetrafluoride (0092). They teach that the target can be a material other than silicon, where examples include niobium, aluminum, titanium, zirconium, tin, magnesium, etc. (0093). They teach that various films can be formed such as MgF2, alumina, etc. (0094). They teach that the apparatus repeats a cycle of depositing a thin film on a substrate by sputtering and performing plasma processing so as to form a thin film having a target thickness (0035).
From the teachings of Song, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Fenwick to have formed the MOF film by repeatedly performing a cycle comprising the sequential steps of exposing the substrate to metal deposition or a deposited metal-containing compound and then exposing the deposited material to a plasma of oxygen and fluorine-containing species and to repeat the process for several cycles using the apparatus of Song because Song teaches that such a process imparts high density, good quality, and high functional performance to a deposited thin film such that it will be expected to provide a desirable MOF film.
As to the film forming an ionic bond as opposed to a covalent bond, Fenwick teaches forming the MOF films where suitable metals include yttrium, gadolinium, aluminum, cerium, dysprosium, zirconium, calcium, magnesium, erbium, lanthanum, neodymium, ytterbium, and strontium (0044).
Lange teaches that when a difference in electronegativity is 1.7 or more, the type of bond is called an ionic bond, where examples of ionically bonded solids are oxides and fluorides, including the alkali metal halides and alkaline earth metal halides (0003).
GPB provides the electronegativities for the various elements (pg. 1).
From the teachings of Lange as evidenced by GPB, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that the MOF materials of Fenwick in view of Song will also be expected to form an ionic bond with fluorine to provide an ionic metal-fluoride-containing product because Fenwick in view of Song provides MOF films having metals such as aluminum, calcium, magnesium etc., which have a difference in electronegativity with fluorine greater than 1.7 such that they are expected to also provide an ionic bond between the materials. Further, since they provide the process of claim 1, using metals meeting the requirements of claim 18, the resulting product is also expected to preferentially form an ionic bond over a covalent bond and to form an ionic metal-fluoride-containing product.
Regarding claims 2-4, Fenwick in view of Song, Lange, and as evidenced by GPB suggest the process of claim 1. Fenwick further teaches sputtering the metal material where an oxygen and fluorine-containing material are provided as a plasma (0055-0056, 0069, Fig. 3B, and Fig. 5A).
As discussed above, Song teaches providing a Si target and sputtering in oxygen to provide an incomplete silica film and then plasma treating in oxygen to oxidize the film to the desired stoichiometry, where other metal targets can be used and other reactive gases can be provided during plasma treatment.
From the teachings of Song, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have deposited the film by reactive sputtering in an oxygen-containing atmosphere or an oxygen and fluorine-containing atmosphere to provide an incomplete metal oxide or incomplete metal oxyfluoride and then to have exposed the incomplete film to the plasma of oxygen and fluorine so as to provide the desired stoichiometry because Song teaches sputtering in a reactive gas that is incorporated in the film and then plasma treating to tune the stoichiometry is desirable and Fenwick teach that the film can be deposited by reactive sputtering in an oxygen and fluorine-containing atmosphere such that it will be expected to provide the film as desired with a desirable stoichiometry. Therefore, the reactive sputtering will comprise sputtering in an oxygen-containing atmosphere to provide a metal-containing compound comprising a metal oxide on the substrate which will then be exposed to the plasma to result in at least some of the metal oxide to form the ionic metal-fluoride-containing product so as to form the final film.
As to the time of sputtering, Song teaches depositing thin films in each cycle having an average thickness of 0.01 nm to 1.5 nm and repeating to form films having a target thickness or several nanometers to several hundreds of nanometers (0035). They provide an example of depositing silica and Nb2O5 at rates of 0.3 nm/s and 0.2 nm/s, respectively, or at 0.5 nm/s and 0.4 nm./s, respectively (0080-0081). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have performed the reactive sputtering for a time of about 0.02 to 7.5 seconds because Song teaches that it is desirable to form each film with a thickness of 0.01 nm to 1.5 nm per cycle, where deposition rates are in the range of 0.2 to 5 nm/s, suggesting that such a deposition rate is suitable for the process, such that it will be expected to provide a suitable time for forming a film having a desirable thickness per cycle. Alternatively, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the sputtering time to be within the claimed range so as to form a film having a desired thickness depending on the deposition rate of the materials. Therefore, the sputtering time will overlap the claimed range or be optimized to be within the claimed range. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claims 5 and 6, Fenwick in view of Song, Lange, and as evidenced by GPB suggest the process of claim 3. Song further teaches that at a certain point in time, the target 29a becomes a cathode, whereas the target 29b becomes an anode (0064 and Fig. 1). They teach that the targets 29a and 29b are held on the magnetron sputter electrodes (0045 and Fig. 1), such that one of the targets is or is proximal to a cathode and the other is or is proximal to an anode. They teach that the substrate faces the magnetron sputter electrodes (0045 and Fig. 1), such that the substrate is considered to be proximal to an anode when it moves by the sputter electrode acting as an anode.
They teach that the substrate holder is rotated about the Z-axis where, as the holder is rotated, the substrates on the outer surface of the substrate are transported between a position where they face the film deposition process zone and a position where the substrates face the reaction process zone (0038, 0041, and Fig. 1). They teach controlling the speed of the holder to provide the film on the substrate and after the film is formed, the holder is rotated to transport the substrate to the reaction zone (0066 and 0067).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have moved the substrate from a deposition zone where the substrate is proximal to an anode and the target is proximate or is a cathode and then to a plasma zone and to have controlled the substrate speed to control the amount of time in the deposition zone (so as to control the duration of the plasma) because Song teaches controlling the speed of a holder to provide the film on the substrate, where magnetron sputtering electrodes provide a cathode and anode, where the substrate is proximal to the anode, and then moving the substrate to a plasma zone such that it will be expected to provide desirable movement of the substrate between the desired zones and deposition of the film as desired. Therefore, the cathode will comprise a magnetron sputtering cathode as required by claim 6.
Regarding claim 9, Fenwick in view of Song, Lange, and as evidenced by GPB suggest the process of claim 1. Song teaches using a fluorinating gas such as CF4 (0092). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used CF4 as the source of the fluorine ions or radicals because Song teaches that such a gas is suitable for fluorinating. Therefore, the fluorine-containing gas will be a fluorocarbon.
Regarding claims 10 and 11, Fenwick in view of Song, Lange, and as evidenced by GPB suggest the process of claim 1. As discussed above for claim 5, Song provides the suggestion of moving the substrate through different zones of a reaction chamber, including transporting through a sputter zone and a plasma zone as in Fig. 1.
Regarding claim 15, Fenwick in view of Song, Lange, and as evidenced by GPB suggest the process of claim 1. Fenwick further teaches introducing oxygen ions or radicals (0006). Song teaches using oxygen or ozone as the oxidizing gas (0092). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used ozone or oxygen as the source of the oxygen ions or radicals because Song teaches that such a gas is suitable for oxidizing.
Regarding claim 16, Fenwick in view of Song, Lange, and as evidenced by GPB suggest the process of claim 1. As discussed above, Song suggests providing the plasma gas to achieve the desired stoichiometry. Fenwick teaches that the MOF has the formula MxOyFz, where M is the metallic element, y has a value of 0.1 to 1.9 times a value of x, and z has a value of 0.1 to 3.9 times the value of x (0004). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the volume percent of oxygen and fluorine in the plasma gases to be within the claimed range because Song suggests providing the gases to achieve a desired stoichiometry such that it will be expected to provide the gases at a suitable amount for achieving the desired MOF material. According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claim 19, Fenwick in view of Song, Lange, and as evidenced by GPB suggest the process of claim 1. Fenwick teaches that that plasmas may include non-reactive species such as Ar (0056). Song teaches providing argon gas as an inert gas in the reaction process zone so that the density of radicals of the reactive gas in a plasma can be increased (0068 and 0071). It would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have included argon gas in the process gas as an inert gas because Song teaches that it is desirably included for increasing the density of radicals of the reactive gas. Therefore, it will provide a background gas the is substantially non-reactive with the other gases because it is inert.
Regarding claim 20, Fenwick in view of Song, Lange, and as evidenced by GPB suggest the process of claim 1. Song teaches providing the plasma in the reaction zone 60 using generator 61 (0036, 0041, and Fig. 1). They teach that the plasma is generated in the reaction process zone 60 to perform plasma processing on the substrates arranged on the substrate holder 13 (0055 and Fig. 1). Therefore, since the plasma is generated in the reaction zone where the substrate is located, it is considered to be generated proximal to an exposed surface of the substrate.
Regarding claim 22, Fenwick in view of Song, Lange, and as evidenced by GPB suggest the process of claim 1. Fenwick teaches forming the protective coating on a surface of a chamber component (0004), therefore, the coating will be formed on at least a portion of the substrate or an entire surface of the substrate.
Claims 1, 14, 15, 18, 19, and 20-22 are rejected under 35 U.S.C. 103 as being unpatentable over Deepak, US 2024/0347336 A1 in view of Lange, US 2024/0035163 A1 and as evidenced by GPB, “Table of Electronegativities”, 2004.
Regarding claim 1, Deepak teaches a method of forming a thin film (methods of depositing a layer on a component, abstract), the method comprising:
providing a substrate to be coated (providing a component for semiconductor processing to a processing region of a processing chamber, 0004);
repeatedly performing a cycle (repeating the deposition process, where the process is an ALD process, 0034, 0040, 0048, and Fig. 2), comprising the sequential steps of:
(a) exposing the substrate to a metal-containing precursor resulting in some of the metal-containing precursor adsorbing on the substrate as an adsorbed metal-containing precursor (providing to the substrate plasma effluents of a first precursor which adsorb onto the surface of the component, 0006 and 0035, where the first precursor can be a metal-containing precursor, 0037, so as to provide an adsorbed metal-containing precursor); and
(b) exposing the substrate to a plasma generated from a mixture of process gases comprising one or more gaseous oxygen-containing compounds and one or more gaseous fluorine-containing compounds, wherein the metal of the adsorbed metal-containing precursor, resulting in at least some of the metal of the adsorbed metal-containing precursor reacting with the plasma to form a metal-fluoride-containing product (providing a second precursor decomposed into second plasma effluents so it generates species that react with the monolayer adsorbed on the component to form the material layer, 0036, where the second precursor may be a fluorine-containing precursor and a co-reactant can be provided with the fluorine-containing precursor, the co-reactant being an oxygen-containing precursor, 0037-0038, such that the substrate will be exposed to a plasma generated from a mixture of process gases comprising gaseous oxygen-containing compounds and one or more fluorine-containing compounds);
whereby after multiple cycles a thin film of the metal-fluoride-containing product is formed on the substrate (where the process is repeated to form multiple monolayers, 0040, and the resulting material is AlF3, AlOxFy, CaF2, CaOxFy, YF3, etc., 0038).
They do not teach that the film has ionic bonds.
Lange teaches that when a difference in electronegativity is 1.7 or more, the type of bond is called an ionic bond, where examples of ionically bonded solids are oxides and fluorides, including the alkali metal halides and alkaline earth metal halides (0003).
GPB provides the electronegativities for the various elements (pg. 1).
From the teachings of Lange as evidenced by GPB, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that the materials of Deepak will also be expected to form an ionic bond with fluorine to provide an ionic metal-fluoride-containing product because Deepak provides metal fluoride and metal oxyfluoride films having metals such as aluminum, calcium, yttrium etc., which have a difference in electronegativity with fluorine greater than 1.7 such that they are expected to also provide an ionic bond between the materials. Further, since they provide the process of claim 1, using metals meeting the requirements of claim 18, the resulting product is also expected to preferentially form an ionic bond over a covalent bond and to form an ionic metal-fluoride-containing product.
Regarding claim 14, Deepak in view of Lange and as evidenced by GPB suggest the process of claim 1. Deepak teaches that the pulse size of the first precursor or of the second precursor may be less than or about 75 minutes, less than or about 20 seconds, or less than or about 10 seconds (0042). Therefore, the step (b) of exposing the substrate to the plasma and step (a) of exposing the substrate to the metal-containing precursor will overlap the claimed range. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.”
Regarding claim 15, Deepak in view of Lange and as evidenced by GPB suggest the process of claim 1. Deepak teaches that he gaseous oxygen-containing compound is water, oxygen, ozone, hydrogen peroxide, an oxygen-containing plasma, or an alcohol-based plasma (0038).
Regarding claim 18, Deepak in view of Lange and as evidenced by GPB suggest the process of claim 1. Deepak teaches that the layer of material may comprise AlF3, CaF2, YF3, ScF3, etc. (0038).
Regarding claim 19, Deepak in view of Lange and as evidenced by GPB suggest the process of claim 1. Deepak teaches that the precursor may include an inert carrier gas and a reaction precursor that may be or include a vapor or a gas (0024 and 0035). Therefore, the process gases will further comprise a background gas that is substantially non-reactive with the one or more gaseous oxygen-containing compound, the one or more gaseous fluorine-containing compounds, and the metal-containing precursor because it is an inert gas that carries the precursor.
Regarding claim 20, Deepak in view of Lange and as evidenced by GPB suggest the process of claim 1. Deepak teaches generating the plasma within the plasma system to provide a direct plasma (0023 and Fig. 1), such that the plasma is considered to be generated proximal to an exposed surface of the substrate since it is generated in the chamber.
Regarding claim 21, Deepak in view of Lange and as evidenced by GPB suggest the process of claim 1. Deepak teaches purging the plasma effluents of the first precursor prior to supplying the second (0006 and 0036). Therefore, unabsorbed metal-containing precursor will be purged from proximal the substrate prior to exposing the substrate to the plasma (second precursor).
Regarding claim 22, Deepak in view of Lange and as evidenced by GPB suggest the process of claim 1. Deepak teaches forming a layer of material on the component (0024, 0048, and Fig. 3), such that the thin film will be formed on a portion or an entire surface of the substrate.
Claims 7, 8, and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Deepak in view of Lange and as evidenced by GPB as applied to claim 1 above, and further in view of Allen, US 2023/0123796 A1.
Regarding claim 7, Deepak in view of Lange and as evidenced by GPB suggest the process of claim 1. Deepak teaches that an oxygen-containing co-reactant can be provided with the metal precursor and/or the fluorine precursor (0038).
They do not teach sequentially providing the metal precursor, the oxygen-containing precursor, and then the fluorine plasma.
Allen teaches a coated optical component having an ALD coating that includes a metal fluoride ALD coating (abstract). They teach that after stopping a pulse of a metal-containing precursor and before providing a pulse of the fluorine-containing source, the surface is exposed to a pulse containing an oxygen source such as water plasma, oxygen plasma, ozone plasma, water, oxygen, ozone, etc. (0030). They teach that the oxygen source may cause oxidation of the ligated metal to form a metal oxide which is then reduced upon exposure to fluorine to provide the metal fluoride (0030). They teach that the concentration of carbon deposits in the metal fluoride ALD coating can be reduced or eliminated by conducting an oxide formation step between the metal precursor pulse and the fluorine source pulse (0107). They teach that the ligated metal deposited on the surface is exposed to an oxygen source for a pulse duration sufficient to oxidize or convert the ligated metal to the pulse containing the oxygen source to cause the ligand of the ligated metal to react with oxygen of the oxygen source to replace the ligand with oxygen (0107). They teach that exposure to fluorine may convert the metal oxide to the metal fluoride containing coating (0107).
From the teachings of Allen, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have first exposed the substrate to the metal precursor and then an oxygen precursor to form an oxide prior to exposure to the plasma because Allen teaches that such a process reduces the amount of carbon in the final film such that it will also be expected to reduce the carbon content in the films of Deepak in view of Lange and as evidenced by GPB. Therefore, step (a) will comprise exposing the substrate to the metal-containing precursor and then exposing to an oxygen-containing atmosphere so that at least a portion of the adsorbed metal-containing precursor is converted to a metal oxide, wherein in step (b) at least some of the metal oxide will be formed into the ionic metal-fluoride-containing product.
Regarding claim 8, Deepak in view of Lange and Allen and as evidenced by GPB suggest the process of claim 7. Deepak teaches using ALD (0034 and 0048). As noted above, Allen teaches performing an ALD process, where the oxygen source is selected from water, water plasma, ozone, ozone plasma, oxygen, oxygen plasma, etc. (0107). Therefore, exposing the adsorbed metal-containing precursor to an oxygen-containing atmosphere will be a thermal ALD or a plasma ALD process.
Regarding claim 17, Deepak in view of Lange and Allen and as evidenced by GPB suggest the process of claim 1. Deepak teaches using ALD (0034 and 0048). They teach using fluoride precursors such as HF, NF3, etc. (0038). They teach forming films such as AlF3, CaF2, AlOxFy, CaOxFy, etc. (0038).
They do not teach using one of the listed precursors.
As discussed above, Allen teaches depositing a metal fluoride film by ALD. They teach using precursors such as bis(ethylcyclopentadienyl)magnesium, bis(cyclopentadienyl)magnesium(II), bis(N,N’-di-sec-butylacetamidinato) magnesium, Bis(N,N’-diisopropylformamidinato)calcium(II), Ca(1,2,4-triisopropylcyclopentadienyl)2, trimethylaluminum, triethylaluminum, etc. (0101-0102). They teaches using fluorine sources such as HF, NF3, CF3I, SF6, etc. (0104).
From the teachings of Allen, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Deepak in view of Lange and as evidenced by GPB to have used metal amidinates, metal alkyls, or metal cyclopentadienyls as the metal precursor such as those taught by Allen because Allen indicates that such precursors are suitable for forming metal fluoride films by ALD using the same fluoride precursors as Deepak such that it will be expected to provide suitable precursors for forming the desired films.
Claim 23 is rejected under 35 U.S.C. 103 as being unpatentable over Deepak in view of Lange and as evidenced by GPB as applied to claim 1 above, and further in view of Sun, US 2022/0037126 A1.
Regarding claim 23, Deepak in view of Lange and as evidenced by GPB suggest the process of claim 1. Deepak teaches applying the film to chamber components (abstract).
They do not teach providing a mixed metal fluoride material.
Sun teaches coated chamber components having a protective coating that includes at least one metal fluoride having a formula selected from the group consisting of M1xM2yFw, M1xM2yM3zFw, etc. ,where at least one of M1, M2, or M3 is magnesium or lanthanum (abstract). They teach depositing the layer by ALD or PVD (abstract). They teach that M1, M2, and M3 each represent a different metal, where suitable metals include magnesium, yttrium, lanthanum, or aluminum (0056). They teach providing one or more precursors 490A and 490B, where the precursors may be one or more metal precursors of M1, M2, M3, or a combination thereof (0089 and Fig. 4A). They teach that when the coating is M1xM2yFw, a precursor of M1 and a precursor of M2 is provided to the chamber and when three metals are in the coating, a single precursor of each metal is provided (0090). They teach that the precursors can be provided at the same time as in co-dosing or one after the other as in co-deposition (0091). They teach removing excess precursor and then providing the reactant for fluorination (0091). They teach that a recant for fluorination can be provided or an oxygen containing reactant can be provided to form an oxide that is subsequently fluorinated (0091). They teach that the coatings have a lower rate of evaporation compared to common reaction products of substrate with fluorine containing species and they are expected to be more fluorine resistant than the underlying substrate (0045).
From the teachings of Sun, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Deepak in view of Lange and as evidenced by GPB to have supplied a first and second metal-containing precursor during step (a), where the metals are selected from magnesium, yttrium, lanthanum, and aluminum to provide a fluoride coating having a mixed metal because Sun teaches that such a coating is desirable for protecting chamber components where the coatings have a lower rate of evaporation compared to common reaction products of substrate with fluorine containing species and they are expected to be more fluorine resistant than the underlying substrate such that it will be expected to provide a desirable protective coating for the components. Further, the metals are also expected to from ionic bonds with fluorine due to the different in electronegativity as discussed above.
Claims 1, 7, 8, 10, 12, 13, 15-19, and 21-23 are rejected under 35 U.S.C. 103 as being unpatentable over Enman, US 2022/0351960 A1 in view of Lange, US 2024/0035163 A1 and as evidenced by GPB, “Table of Electronegativities”, 2004.
Regarding claim 1, Enman teaches a method of forming a thin film (methods of depositing metal fluoride films on a substrate, abstract), the method comprising:
providing a substrate to be coated (where the process is performed to deposit the metal fluoride film on the substrate surface in a processing chamber, 0026 and Fig. 1, indicating that the substrate is provided);
repeatedly performing a cycle (where the process is an ALD process that is repeated until the desired thickness is deposited, 0029, 0068, and Fig. 1), comprising the sequential steps of:
(a) exposing the substrate to a metal-containing precursor resulting in some of the metal-containing precursor adsorbing on the substrate as an adsorbed metal-containing precursor (exposing the substrate surface to a metal precursor, 0026 and Fig. 1, where the metal precursor reacts with the surface to adsorb or chemisorb onto the substrate, 0034, such that it will provide an adsorbed metal-containing precursor); and
(b) exposing the substrate to a plasma generated from a mixture of process gases comprising one or more gaseous oxygen-containing compounds and one or more gaseous fluorine-containing compounds, wherein the metal of the adsorbed metal-containing precursor, resulting in at least some of the metal of the adsorbed metal-containing precursor reacting with the plasma to form a metal-fluoride-containing product (exposing the substrate surface to the fluoride precursor, where the fluoride precursor is selected from various plasma precursors and can also include an oxidant such as oxygen plasma, 0061, 0065-0066, and Fig. 1, such that the substrate will be exposed to a plasma generated from a gas comprising oxygen-containing and fluorine-containing compounds, and where the process results in forming the metal fluoride film, 0007 and 0057, such that the gas will react with the adsorbed metal precursor to provide the film);
whereby after multiple cycles a thin film of the metal-fluoride-containing product is formed on the substrate (where the process is repeated to form the metal fluoride, 0068 and Fig. 1, where examples of the film formed include yttrium fluoride, calcium fluoride, magnesium fluoride, 0092-0102, and where the metal precursors include aluminum, strontium, scandium, zirconium, lanthanum, lanthanides, etc., 0034, so as to provide aluminum fluoride, strontium fluoride, lanthanum fluoride, etc. films).
They do not teach that the film has ionic bonds.
Lange teaches that when a difference in electronegativity is 1.7 or more, the type of bond is called an ionic bond, where examples of ionically bonded solids are oxides and fluorides, including the alkali metal halides and alkaline earth metal halides (0003).
GPB provides the electronegativities for the various elements (pg. 1).
From the teachings of Lange as evidenced by GPB, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that the materials of Enman will also be expected to form an ionic bond with fluorine to provide an ionic metal-fluoride-containing product because Enman provides metal fluoride and metal oxyfluoride films having metals such as aluminum, calcium, yttrium etc., which have a difference in electronegativity with fluorine greater than 1.7 such that they are expected to also provide an ionic bond between the materials. Further, since they provide the process of claim 1, using metals meeting the requirements of claim 18, the resulting product is also expected to preferentially form an ionic bond over a covalent bond and to form an ionic metal-fluoride-containing product.
Regarding claim 7, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman further teaches that the surface is exposed to an oxidizing agent between the metal precursor and the fluoride exposure (0072 and Fig. 2). They teach that the exposure to the oxidizing agent forms a metal oxide film, where upon exposure to the fluoride precursor the metal fluoride is formed (0072 and 0074). They teach that the oxidizing agent is peroxide, water, oxygen, ozone, oxygen plasma, or combinations thereof (0074). Therefore, step (a) will comprise exposing the substrate to the metal precursor and subsequently exposing to an oxygen-containing atmosphere such that the adsorbed metal-containing precursor is converted to a metal oxide and then in step (b) is exposed to the plasma to result in at least some of the metal oxide forming the ionic metal-fluoride-containing product.
Regarding claim 8, Enman in view of Lange and as evidenced by GPB suggest the process of claim 7. Enman further teaches that the process is an ALD process, where the oxygen reactant is peroxide, water, oxygen, ozone, oxygen plasma, or combinations thereof (0027 and 0074). Therefore, the process will be a thermal or plasma-enabled ALD process.
Regarding claims 10 and 12, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman further teaches that ALD refers to the sequential exposure of two or more reactive compounds to deposit a layer of material on a substrate surface, where in spatial ALD, different portions of the substrate surface are exposed simultaneously to the two or more reactive compounds so that any given point on the substrate is substantially not exposure to more than one reactive compound simultaneously (0030). They teach that in spatial ALD, a first reactive gas and second reactive gas are delivered simultaneously to the reaction zone but are separated by an inert gas curtain and/or a vacuum curtain (0032). They teach that the substrate is moved relative to the gas delivery apparatus so that any given point on the substrate is exposed to the gases (0032). Therefore, the ALD process is understood to also include spatial ALD, where the substrate is moved relative to the gas delivery apparatus so as to be exposed to the different gases such that the substrate will be moved in each cycle so as to be transported through different zones (reactive gas areas), including transporting the substrate through a metal-containing precursor zone and a plasma zone (so as to provide exposure to the different gases with spatial distinction).
Regarding claim 13, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman teaches that in time domain ALD the reactants are pulsed into the chamber (0031). Therefore, since the fluorine and oxygen-containing gases are generated into a plasma in a pulse, the resulting plasma is considered to be a pulse plasma because it will be turned on and off during the process so as to provide the reactant as needed.
Regarding claim 15, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman further teaches that the oxygen-containing compounds are selected from water, peroxide, oxygen, ozone, oxygen plasma, or combinations thereof (0066).
Regarding claim 16, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. While they do not teach the concentration of fluorine and oxygen in the plasma gas, according to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). Therefore, Enman in view of Lange and as evidenced by GPB are considered to render the claimed ranges obvious in the absence of evidence that the range is critical.
Regarding claim 17, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman further teaches using metal alkyl compounds, metal cyclopentadienyl compounds, metal amide compounds, metal amidine compounds, metal alkoxide compounds, etc. (0035).
Regarding claim 18, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman further teaches forming calcium fluoride, magnesium fluoride, and yttrium fluoride (0092-0102). They teach using metals such as aluminum, strontium, scandium, and lanthanum (0034), so as to provide fluorides thereof.
Regarding claim 19, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman further teaches that the metal precursor is flowed in an inert carrier gas (0058). They teach that the fluoride precursor is also carried in an inert carrier gas (0066). Therefore, the process gases further comprise a background gras that is substantially non-reactive with the one or more gaseous oxygen-containing compounds, fluorine-containing compounds, and the metal-containing precursor since it is inert.
Regarding claim 21, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman further teaches purging the metal-containing precursor prior to exposure to the fluorine precursor (0060 and Fig. 1). Therefore, unabsorbed precursor will be purged.
Regarding claim 22, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman further teaches forming the metal fluoride film on a substrate surface (abstract), such that the metal-fluoride-containing product is formed on a portion of the substrate or an entire surface of the substrate.
Regarding claim 23, Enman in view of Lange and as evidenced by GPB suggest the process of claim 1. Enman further teaches that the metal precursor comprises a combination of metals and comprises one or more compounds (0034). Therefore, since they provide a mixture of precursor compounds, where the precursors can include one or more metals, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have provided a mixture of precursor having different metals so as to provide a metal fluoride material having multiple metals because they indicate that more than one metal and more than one metal precursor can be provided. They teach using metals such as aluminum, strontium, magnesium, scandium, and lanthanum (0034), so as to provide fluorides thereof.
Further, the metals are also expected to form ionic bonds with fluorine due to the difference in electronegativity as discussed above.
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable over Deepak or Enman in view of Lange and as evidenced by GPB as applied to claim 1 above, and further in view of Shanbhag, US 2019/0185999 A1.
Regarding claim 13, Deepak or Enman in view of Lange and as evidenced by GPB suggest the process of claim 1.
They do not teach generating the plasma using a pulse plasma or DC.
Shanbhag teaches forming a protective coating ex situ in an ALD process to coat one or more chamber components (abstract). They teach and apparatus including a showerhead and pedestal that electrically communicate with an RF power supply (0140 and Fig. 7). They teach that the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, and RF source frequency, and a plasma power pulse timing (0140). They teach that the plasma power may be intermittently pulsed to reduce ion bombardment with the substrate surface relative to continuously powered plasma (0140).
From the teachings of Shanbhag, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have generated the plasma from a pulsed plasma because Shanbhag teaches that a pulsed plasmas reduces ion bombardment compared to a continuously supplied plasma such that it will be expected to reduce damage to the substrate and the deposited film.
Conclusion
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718
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