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 .
Status of the Claims
Claims 1-12 and 14-20 are pending and rejected. Claim 13 is withdrawn. Claims 1, 5-7, 9, 10, 12, and 15 are amended.
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.
Claims 1-7, 9-12 and 14-20 are rejected under 35 U.S.C. 103 as being unpatentable over van Druenen, US 2022/0189775 A1 (provided on the IDS of 10/29/2024) in view of Blasco, US 2009/0311879 A1.
Regarding claim 1, van Druenen teaches a method for forming a rare-earth-containing layer (methods for depositing rare earth metal carbide containing layers, abstract), the method comprising:
providing a substrate within a process chamber (providing a substrate to a reaction chamber, 0181 and Fig. 11); and
depositing the rare-earth-containing layer over the substrate (depositing a rare earth metal carbide containing layer, 0181 and Fig. 11), the method of depositing the rare-earth-containing layer comprising:
providing a rare-earth precursor comprising a rare earth element into the process chamber (providing a first precursor pulse in which a rare earth metal precursor is provided to the reaction chamber, 0181 and Fig. 11, where the rare earth precursor includes a rare earth metal, 0010),
providing a metal precursor comprising a metal element selected from groups 4-13 metals into the process chamber (providing a second precursor pulse in which a transition metal precursor is provided to the reaction chamber, 0181 and Fig. 11, where the transition metal is iron, titanium, and vanadium, 0103), and
providing one or more non-metal element reactants comprising a first non-metal element and a second non-metal element different from the first non-metal element into the process chamber (where after the first precursor pulse, a first reactant pulse is provided in which a carbon reactant is provided to the reaction chamber, where the carbon reactant can be a halogenated C1 to C6 alkane or alkene, 0017, 0181, and Fig. 11, and after the second precursor pulse a second reactant pulse is performed to supply a nitrogen reactant such as N-2 or NH3, 0181 and Fig. 11),
wherein the rare-earth-containing layer comprises the rare-earth element, the metal element, the first non-metal element, and the second non-metal element (where since the process provides the rare-earth element precursor, the metal precursor, a carbon precursor, and a nitrogen precursor, the resulting film is expected to include the rare-earth metal, the transition metal, carbon, and nitrogen, further they indicate that the first sub-cycle provides a rare-earth carbide sublayer, 0181).
Alternatively, while they do not specifically teach that the film includes the transition metal and nitrogen, 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 film will include the rare-earth element, the metal element, carbon, and nitrogen, since such precursors and reactants are provided and further they indicate that the film can include nitrogen, 0139).
They do not teach providing the non-metal element reactants after providing the rare-earth precursor and the metal precursor.
Blasco teaches a method of forming on at least one support at least one metal containing dielectric films having the formula (M11-aM2a)ObNc, where 0≤a<1, M1 and M2 are metals using precursors with pentadienyl ligands and/or cyclopentadienyl ligands (abstract and 0027). They teach that M1 is Hf, Zr, and/or Ti and M2 is Mg, Ca, Zn, B, Al, In, lanthanides (Sc, Y, La, and rare earths), Si, Ge, Sn, Ti, Zr, Hf, V, Nb, and Ta (0045). They provide the steps of the process as (b) providing the metal precursor, (c) providing the rare-earth precursor, (d) providing the at least one oxygen containing and/or nitrogen containing fluid, (e) reacting the precursors with the oxygen containing and/or nitrogen containing fluid, and (f) depositing the film onto the substrate (0030 and 0045-0048). Blasco teaches that the reactants can be introduced into the reactor either simultaneously (CVD), sequentially (ALD), or different combinations thereof (one example is to introduce e.g., the two metal sources together in one pulse and the oxygen gas in a separate pulse (0052).
From the teachings of Blasco, 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 van Druenen to have sequentially provided the metal precursor, the rare earth precursor, and then the carbon and nitrogen precursors because Blasco teaches that the reactants can be provided sequentially and they outline the step in this order, where the metal precursors are reacted with the oxygen and nitrogen reactants suggesting it is a suitable sequence for forming a film including multiple metals and non-metal elements, where the carbon and nitrogen reactants will be able to react with both the rare earth metal precursor and the metal precursor on the substrate. 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 provided the metal precursors together and then provide the carbon and nitrogen sources because Blasco indicates that metal precursors can be provided together and then a non-metal source can be provided suggesting that such a sequence will also desirably provide a mixed metal film including carbon and nitrogen on the substrate. Therefore, in the process of van Druenen in view of Blasco, the non-metal precursors will be provided after providing the rare-earth precursor and the metal precursor. Further, according to MPEP 2144.04(IV)(C): See also In re Burhans, 154 F.2d 690, 69 USPQ 330 (CCPA 1946) (selection of any order of performing process steps is prima facie obvious in the absence of new or unexpected results). Therefore, the order of providing the gases is considered to be obvious in the absence of new or unexpected results.
Regarding claims 2 and 3, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that any rare-earth metal precursor mentioned can be used in the first precursor pulse (0181). They teach that the rare-earth precursor is selected from precursors of lanthanum, yttrium, erbium, samarium, europium, ytterbium, gadolinium, neodymium, and cerium (0103), such that the rare earth element will be and the rare-earth precursor will comprise lanthanum, yttrium, erbium, samarium, europium, ytterbium, gadolinium, neodymium, or cerium.
Regarding claim 4, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that any rare-earth metal precursor mentioned can be used in the first precursor pulse (0181). They teach that the rare-earth precursor comprises a rare-earth element in an oxidation state of +3 or +4 (0010).
Regarding claim 5, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that any rare-earth metal precursor mentioned can be used in the first precursor pulse (0181). They teach that the rare-earth precursor comprises a substituted or unsubstituted cyclopentadienyl ligand (0012).
Regarding claims 6 and 7, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that any transition metal precursor mentioned can be used in the second precursor pulse (0181). They teach using transition metal precursors such as precursors of iron, titanium, and vanadium (0103). Therefore, the metal precursor comprises titanium, vanadium, or iron.
Regarding claim 9, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that titanium, iron, vanadium precursors are further precursors that are provided in the process where the further precursor comprises a substituted or unsubstituted cyclopentadienyl ligand (0103). Therefore, when using a transition metal precursor such as titanium, iron, or vanadium, the precursor will include a cyclopentadienyl or unsubstituted cyclopentadienyl ligand.
Regarding claim 10, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that the first non-metal element and/or the second non-metal element is selected from a group 14 non-metal (carbon) or a group 15 non-metal (nitrogen) (0181). Therefore, the first non-metal element and/ or the second non-metal element is taught or suggested to be a group 14 non-metal (carbon) or a group 15 non-metal (nitrogen).
Regarding claims 11 and 12, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches providing a first reactant pulse using a carbon reactant and a second reactant pulse including a nitrogen reactant (0181), such that a first non-metal element reactant is provided and a second non-metal element reactant is provided, where the first comprises a group 14 non-metal (carbon) and the second comprises a group 15 non-metal (nitrogen). They teach that the carbon reactant is a halogenated alkane or alkene and the nitrogen reactant is N2 or NH3 (0017 and 0181), such that the first and second non-metal reactants are different.
Regarding claim 14, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that the substrate has a gate dielectric 420 on the surface (0167 and Fig. 4). They teach that the gate electrode 430 has a first conductive layer 431, a rare-earth metal carbide containing layer 432, and a second conductive layer 433 (0167 and Fig. 4). They teach depositing the first conductive layer on the gate dielectric (0008). Therefore, prior to depositing the first conductive layer, the substrate will have an outer surface comprising a dielectric layer extending along the outer surface (Fig. 4).
Regarding claim 15, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that the dielectric layer comprises a high-k material such as hafnium oxide, tantalum oxide, zirconium oxide, etc. (0167).
Regarding claim 16, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches depositing a first conductive layer prior to forming the rare-earth-containing layer (0008).
Regarding claim 17, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that the first conductive layer comprises a first transition metal compound (0021).
Regarding claims 18-20, van Druenen in view of Blasco suggests the process of claim 1. van Druenen further teaches that the first conductive layer comprises a first transition metal carbide or nitride such as titanium nitride or titanium carbide (0021-0022 and 0025-0026). They teach that the first conductive layer can be TiN, ZrN, HfN, VN, NbN, TaN, ScN, CrN, MoN, WN, TiC, VC, HfC, TaC, ZrC, ScC, or NbC (0132 and 0134). Therefore, the first transition metal compound comprises a first non-metal constituent element that is different from the first non-metal element or the second non-metal element and a metal element that can be different from the rare-earth element and/or the metal element.
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over van Druenen in view of Blasco as applied to claim 1 above, and further in view of Chen, US 2022/0285147 A1.
Regarding claim 8, van Druenen in view of Blasco suggest the process of claim 1. As noted above for claims 6 and 7, they teach using iron, titanium, or vanadium as the transition metals.
They do not teach the oxidation state of the metal precursor.
Chen teaches methods for depositing layers comprising a titanium, aluminum, and carbon (abstract). They teach that the process is cyclical (abstract). They teach that a deposition cycle comprises an aluminum precursor pulse and a transition metal precursor pulse (0057). They teach that the transition metal precursor comprises at least one of vanadium, titanium, etc. (0083). They teach that the transition metal precursor can comprise a transition metal in any suitable oxidation state, where the oxidation state can be +2, +3, +4, or +5 (0086). They teach that the transition metal precursor comprises a metal in an oxidation state of +4 (0086). They teach that the transition metal can be titanium in a +4-oxidation state (0086).
From the teachings of Chen, 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 van Druenen in view of Blasco to have used vanadium or titanium in an oxidation state of +2, +3, +4, or +5 and to specifically have used titanium in a +4 oxidation state because Chen teaches that such oxidation states are suitable for titanium and vanadium precursors for the deposition of a vanadium or titanium containing layer by a cyclical process such that it will be expected to provide desirable oxidation states for the precursors. Therefore, the oxidation state will overlap or be within the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” 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.”
Claims 1-7 and 9-12 are rejected under 35 U.S.C. 103 as being unpatentable over Blasco, US 2009/0311879 A1, and for claim 4, as evidenced by van Druenen, US 2022/0189775 A1.
Regarding claim 1, Blasco teaches a method for forming a rare-earth-containing layer (a method of forming on at least one support at least one metal containing dielectric films having the formula (M11-aM2a)ObNc, where 0≤a<1, M1 and M2, where M1 is Hf, Zr, and/or Ti and M2 is selected from a group including lanthanides such as Sc, Y, La, and rare earths, abstract, 0031, and 0045, such that when M2 is a rare earth element the film will be a rare-earth-containing layer), the method comprising:
providing a substrate within a process chamber (providing a substrate to a reactor, 0029); and
depositing the rare-earth-containing layer over the substrate (forming the layer on the substrate, 0048), the method of depositing the rare-earth-containing layer comprising:
providing a rare-earth precursor comprising a rare earth element into the process chamber (introducing into the reactor at least one M2 containing precursor, where M2 is selected from the group including lanthanides, Sc, Y, and rare earths, 0045),
providing a metal precursor comprising a metal element selected from groups 4-13 metals into the process chamber (introducing into the reactor at least one metal containing precursor having the formula (RyOp)x(RtCp)zM1R’4-x-z, where M1 is Hf, Zr, and/or Ti, 0030-0031), and
providing one or more non-metal element reactants comprising a first non-metal element and a second non-metal element different from the first non-metal element into the process chamber (providing at least one oxygen containing and/or nitrogen containing fluid into the reactor, 0046, where the oxygen fluid is oxygen, ozone, water, hydrogen peroxide, or oxygen-containing radials and the nitrogen-containing fluid is nitrogen, ammonia, hydrazine and its alkyl or aryl derivatives, nitrogen-containing radicals, and mixtures thereof, 0049, or where when both nitrogen and oxygen are needed the fluid may be selected from NO, NO2, etc., 0050),
wherein the rare-earth-containing layer comprises the rare-earth element, the metal element, the first non-metal element, and the second non-metal element (where the film has the formula (M11-aM2a)ObNc, where 0≤a<1, M1 and M2, where M1 is Hf, Zr, and/or Ti and M2 is selected from a group including lanthanides such as Sc, Y, La, and rare earths, abstract, 0031, 0045, and 0048).
As to providing the non-metallic reactants after the metal and rare-earth metal precursors, Blasco teaches that the reactants can be introduced into the reactor either simultaneously (CVD), sequentially (ALD), or different combinations thereof (one example is to introduce e.g., the two metal sources together in one pulse and the oxygen gas in a separate pulse (0052). They provide the steps of the process as (b) providing the metal precursor, (c) providing the rare-earth precursor, (d) providing the at least one oxygen containing and/or nitrogen containing fluid, (e) reacting the precursors with the oxygen containing and/or nitrogen containing fluid, and (f) depositing the film onto the substrate (0030 and 0045-0048). 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 sequentially provided the metal precursor, the rare earth precursor, and then the oxygen and/or nitrogen precursor because Blasco teaches that the reactants can be provided sequentially and they outline the step in this order suggesting it is a suitable sequence for the process. 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 provided the metal precursors together and then provide the oxygen and nitrogen source because they indicate that the metals can be provided together and then the oxygen source can be provided, where the oxygen source can be mixed with a nitrogen source. Therefore, in the process of Blasco, the non-metal precursor(s) will be provided after providing the rare-earth precursor and the metal precursor.
Regarding claims 2 and 3, Blasco suggests the process of claim 1. They further teach that M2 is selected from lanthanides (Sc, Y, La, and rare earths) (0045). Therefore, the rare earth element is selected from lanthanum, yttrium, and scandium and the rare earth precursor will also contain these elements.
Regarding claims 4 and 5, Blasco suggests the process of claim 1. They further teach that the M2 precursor is in the form of a cyclopentadienyl lanthanide Ln(R1Cp)(R2Cp)(R3Cp), where each Ri is independently H or a C1-C6 carbon chain, either linear, branched, or cyclic (0065). Therefore, the rare-earth precursor will include a cyclopentadienyl ligand. Further, 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 selected La(Cp)3, Y(Cp)3, or Sc(Cp)3 as the precursor because Blasco teaches using Sc, Y, and La as lanthanides (0045), where the R groups can be H so as to provide Ln(Cp)3 precursors. Therefore, they provide rare earth metal precursors having a +3 oxidation state as evidenced by van Druenen (0109).
Regarding claims 6 and 7, Blasco suggests the process of claim 1. They further teach that M1 is Hf, Zr, and/or Ti, where the precursor includes M1 (0030-0031).
Regarding claim 9, Blasco suggests the process of claim 1. They further teach that the metal precursor comprises a cyclopentadienyl ligand (0030).
Regarding claims 10-12, Blasco suggests the process of claim 1. They further teach providing at least one oxygen containing and/or nitrogen containing fluid to the reactor (0046). They teach that the oxygen fluid is oxygen, ozone, water, hydrogen peroxide, or oxygen-containing radials and the nitrogen-containing fluid is nitrogen, ammonia, hydrazine and its alkyl or aryl derivatives, nitrogen-containing radicals, and mixtures thereof (0049). They teach that when both nitrogen and oxygen are needed, the fluid may be selected from NO, NO2, etc. (0050). They teach that selecting an oxygen and nitrogen containing fluid automatically generates an oxynitride with a certain ratio of N/O molecules and that if the ratio is not appropriate, then another nitrogen and/or oxygen containing fluid is needed (0050). Therefore, the first non-metal element is oxygen or nitrogen and the second non-metal element is the other of nitrogen or oxygen, where a first non-metal element reactant and a second non-metal element reactant different from the first non-metal element reactant are provided.
Response to Arguments
Applicant’s arguments, filed 7/6/2026, have been fully considered and are persuasive in light of the amendments. The rejection over Clark has been withdrawn and the rejection over van Druenen has been modified as indicated above. Further a new rejection using Blasco has been added. Additionally, the previous drawing objection and 112(b) rejections have been withdrawn.
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 nonprovisional extension fee (37 CFR 1.17(a)) 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 mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CHRISTINA D MCCLURE whose telephone number is (571)272-9761. The examiner can normally be reached Monday-Friday, 8:30-5:00 EST.
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718 /GORDON BALDWIN/Supervisory Patent Examiner, Art Unit 1718
