DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Election/Restrictions
Applicant’s election without traverse of Claims 1-29 in the reply filed on 08 DEC 2025 is acknowledged.
Claims 30-32 withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 08 DEC 2025.
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 8, 10, 12, 14, 15, and 18 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.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, claim 8 recites the broad recitation “between 0.50 and 8.0%”, and the claim also recites “more particularly between 1.0 and 5.0%” which is the narrower statement of the range/limitation. A further even narrower recitation of “even more particularly between 2.0 and 4.50%” is also present. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, claim 18 recites the broad recitation “between 150 and 450 degrees Celsius”, and the claim also recites “preferably between 250 and 350 degrees Celsius” which is the narrower statement of the range/limitation. A further even narrower recitation of “more preferably around 300 degrees Celsius” is also present. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims.
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c). In the present instance, claims 10, 12, and 14 separately recite the broad recitation “wherein said dopant precursor is a low-reactivity precursor”, and the claims also separately recite “said dopant precursor preferably being a low-reactivity [element] precursor…” with a corresponding list of compounds, which is the narrower statement of the range/limitation. The claim(s) are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims.
Claim 15 recites the limitation "”Hf(OR)4" in Line 4 thereof. There is insufficient antecedent basis for this limitation in the claim, as there is no definition of what R comprises in either Claim 1 or Claim 15.
Claim Rejections - 35 USC § 102
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claim(s) 1-12, 15-16, 19-22, 26, and 28-29 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Clark ‘288 (U.S. PGPub 2008/0233288).
Claim 1 – Clark ‘288 teaches a method for forming a doped hafnium zirconium oxide (HZO) layer on a substrate (Abstract, PG 0091), the method comprising (PG 0096-0103, Figure 3A):
providing said substrate in a reaction chamber (PG 0096);
executing one or more cycles (PG 0098), a cycle comprising
a hafnium precursor pulse, wherein at least a part of the substrate is contacted with one or more hafnium precursor by introducing said one or more hafnium precursor in the reaction chamber 9PG 0096);
a zirconium precursor pulse, wherein at least a part of the substrate is contacted with one or more zirconium precursor by introducing said one or more zirconium precursor in the reaction chamber 9PG 0096);
an oxygen precursor pulse, wherein at least a part of the substrate is contacted with one or more oxygen precursor by introducing said one or more oxygen precursor in the reaction chamber (PG 0096);
a dopant precursor pulse, wherein at least a part of the substrate is contacted with one or more dopant precursor by introducing said one or more dopant precursor in the reaction chamber (PG 0096);
thereby forming a doped HZO layer (PG 0096);
wherein said dopant precursor comprises a dopant element characterized by having three or four valence electrons and an atomic radius which is less than the atomic radius of an Hf or Zr element of the HZO layer (PG 0034, e.g. silicon).
Claim 2 – Clark ‘288 teaches the method according to claim 1, wherein an oxygen reactant pulse is carried out after each hafnium precursor pulse and/or after each zirconium precursor pulse (PG 0096).
Claim 3 – Clark ‘288 teaches the method according to claim 2, wherein said dopant precursor pulse is carried out after said hafnium precursor pulse without any intervening oxygen reactant pulse (PG 0099, order of sequential and alternating deposition steps may be chosen to obtain desired film growth and film composition).
Claim 4 – Clark ‘288 teaches the method according to claim 2, wherein said dopant precursor pulse is carried out after said zirconium precursor pulse without any intervening oxygen reactant pulse (PG 0099, order of sequential and alternating deposition steps may be chosen to obtain desired film growth and film composition).
Claim 5 – Clark ‘288 teaches the method according to claim 1, wherein each pulse is followed by a purge with an inert gas chosen from at least one of N2 and a noble gas (PG 0102, purge gas; PG 0069, noble gases or nitrogen).
Claim 6 – Clark ‘288 teaches the method according to claim 1, wherein said hafnium precursor pulse, said zirconium precursor pulse, said oxygen reactant pulse and/or said dopant precursor pulse comprises a plurality of micropulses (PG 0101, e.g. ABCCX has multiple sequential C pulses).
Claim 7 – Clark ‘288 teaches the method according to claim 1, wherein said dopant element is selected from the list consisting of Aluminium, Gallium [both PG 0034 Group XIII], and Silicon (PG 0034, expressly listed).
Claim 8 – Clark ‘288 teaches the method according to claim 1, wherein the concentration of said dopant element in said HZO layer ranges between 0.50 and 8.0 of the relative dopant element concentration, more particularly between 1.0 and 5.0 % of the relative dopant element concentration, and even more particularly between 2.0 and 4.50 % of the relative dopant element concentration (PG 0032, 0.1-20 atomic percent encompasses all claimed ranges)
Claim 9 – Clark ‘288 teaches the method according to claim 1, wherein said dopant element is Al (PG 0034, aluminum is a Group XIII element).
Claim 10 – Clark ‘288 teaches the method according to claim 9, wherein said dopant precursor is a low-reactivity precursor, said dopant precursor preferably being a low-reactivity Aluminium precursor represented by the general formula Al(R1)3, wherein each R1 is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, N(R2)2, and alkoxy, and wherein each R2 is chosen from hydrogen or alkenyl (PG 0065-0066, all ligand types disclosed across combinations of disclosed compounds).
Claim 11 – Clark ‘288 teaches the method according to claim 1, wherein said dopant element is Si (PG 0034).
Claim 12 – Clark ‘288 teaches the method according to claim 11, wherein said dopant precursor is a low-reactivity precursor, said dopant precursor preferably being a low-reactivity Silicon precursor selected from the list consisting of Si(R3)4, wherein each R3 is independently selected from the group consisting of hydrogen, halogen, alkyl, and N(R4)2, and wherein each R4 is chosen from hydrogen or alkyl (PG 0068, all cited ligands disclosed across listed compounds).
Claim 15 – Clark ‘288 teaches the method according to claim 1, wherein said hafnium precursor is chosen from the list consisting of HfCl4, Tetrakis(dimethylamido)hafnium (Hf(N(CH3)2)4), Tetrakis(ethylmethylamino)hafnium (Hf(N(C2H5)(CH3))4), Tetrakis(diethylamido)hafnium (Hf(N(C2H5)2)4), and Hf(OR)4. (PG 0033, hafnium tert-butoxide held to read on Hf(OR)4).
Claim 16 – Clark ‘288 teaches the method according to claim 1, wherein said zirconium precursor is chosen from the list consisting of tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium, and tetrakis(ethylmethylamino)zirconium (PG 0033).
Claim 19 – Clark ‘288 teaches the method hod according to claim 1, wherein the method is an Atomic Layer Deposition (ALD) method (PG 0070, PG 0095).
Claim 20 – Clark ‘288 teaches the method according to claim 1, wherein the method further comprising the step of providing a seed layer prior to forming said doped HZO layer, said seed layer being a ZrO2 seed layer (PG 0096, PG 0099; starting the deposition process with a zirconium pulse and an oxygen pulse forms a zirconia seed layer prior to further deposition steps).
Claim 21 – Clark ‘288 teaches the method according to claim 1, wherein said substrate comprises a Metal Oxide (MO) surface layer, and/or wherein said method further comprises the step of forming a Metal Oxide (MO) top layer on said doped HZO layer, thereby forming a layered doped HZO structure (PG 0096, PG 0099; starting the deposition process with a metal precursor and an oxygen pulse forms a metal oxide seed layer layer prior to further deposition steps; at least hafnium and zirconium are metals; similarly, ending with a metal precursor and an oxygen pulse forms a metal oxide layer on top of the doped HZO layer; the claim as presented does not require that the metal oxide layer be a discrete metal from the doped HZO materials)
Claim 22 – Clark ‘288 teaches the method according to claim 21, wherein the MO surface layer and/or the MO top layer is in direct contact with the doped HZO layer (inherent from the proposed deposition profiles in the rejection of Claim 21).
Claim 26 – Clark ‘288 teaches the method according to claim 1, wherein said doped HZO layer increases the dielectric constant value (κ) of said HZO layer (PG 0019, benefits of doped HZO films include increased dielectric constant)
Claim 28 – Clark ‘288 teaches the method according to claim 1, wherein said doped HZO layer is formed without any intervening vacuum break (PG 0072, the chamber may be held at constant vacuum throughout deposition).
Claim 29 – Clark ‘288 teaches the method according to claim 21, wherein said layered doped HZO structure is formed without any intervening vacuum break (PG 0072, the chamber may be held at constant vacuum throughout deposition).
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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim(s) 17-18, 24-25, and 27 are rejected under 35 U.S.C. 103 as being unpatentable over Clark ‘288 as applied to claims 1 and 26 above
Claim 17 – Clark ‘288 teaches the method according to claim 1, but does not expressly teach or suggest wherein the decomposition temperature of the dopant precursor is higher compared to the operating temperature to form the doped hafnium zirconium oxide (HZO) layer. 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. Therefore, selection of particular precursor deposition temperatures is held as prima facie obvious in the absence of unexpected results accruing from the selection. See further MPEP 2144.05.
Claim 18 – Clark ‘288 teaches the method according to claim 17, wherein the operating temperature to form the doped HZO layer is between 150°C and 450°C, preferably between 250°C and 350°C, more preferably around 300°C (PG 0070, room temperature to 550 degrees Celsius encompasses all claimed values).
Claim 24 – Clark ‘288 teaches the method according to claim 1, but does not expressly teach or suggest wherein said doped HZO layer stabilises the tetragonal phase of said HZO layer such that a Morphotropic Phase Boundary (MPB) is reached between the orthorhombic and tetragonal phases of said HZO layer to allow a change in the polarization switching voltage of said HZO layer. However, PG 0023 expressly teaches that the doped compound disclosed in Clark ‘288 allows for stable desired crystallographic forms. Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. Therefore, Examiner asserts a prima facie case of obviousness given the substantially identical process disclosed in Clark ‘288 to arrive at the claimed product. See further MPEP 2112.01.
Claim 25 – Clark ‘288 teaches the method according to claim 24, but does not expressly teach or suggest wherein changing the polarization switching voltage of said HZO layer changes the Capacitance Voltage (CV) linearity of said HZO layer. Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. Therefore, Examiner asserts a prima facie case of obviousness given the substantially identical process disclosed in Clark ‘288 to arrive at the claimed product. See further MPEP 2112.01.
Claim 27 – Clark ‘288 teaches the method according to claim 26, but does not expressly teach or suggest wherein the dielectric constant value (κ) of said doped HZO layer is above 35 at about -2 and -3MV/cm. Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. Therefore, Examiner asserts a prima facie case of obviousness given the substantially identical process disclosed in Clark ‘288 to arrive at the claimed product. See further MPEP 2112.01.
Claim(s) 13 is rejected under 35 U.S.C. 103 as being unpatentable over Clark ‘288 as applied to claim 1 above, and further in view of Wu ‘937 (U.S. PGPub 2021/0375937).
Claim 13 – Clark ‘288 teaches the method according to claim 1, but does not expressly teach or suggest wherein said dopant element is Ge. Wu ‘937 is drawn generally to semiconductor structures (PG 0022) and in particular embodiments thereof discloses structures comprising doped HZO, where the dopants may be silicon, germanium, or certain rare earths generally commensurate with those taught in Clark ‘288 as discussed above. Therefore, it would have been obvious to a person having ordinary skill in the art at the time the invention was made or filed to have modified the invention of Clark ‘288 to use germanium as a dopant for HZO as suggested by Wu ‘937, as Clark ‘288 wants to make doped HZO semiconductor devices and Wu ‘937 discloses germanium as a suitable alternative dopant to several other materials disclosed in Clark ‘288.
Claim(s) 14 is rejected under 35 U.S.C. 103 as being unpatentable over Clark ‘288 / Wu ‘937 as applied to claim 13 above, and further in view of Matero ‘841 (U.S. PGPub 2014/0065841).
Claim 14 – Clark ‘288 / Wu ‘937 renders obvious the method according to claim 13, but does not expressly teach or suggest wherein said dopant precursor is a low-reactivity precursor, said dopant precursor preferably being a low-reactivity Germanium precursor represented by the general formula Ge(R5)4, wherein each R5 is independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, N(R6)2, cycloalkyl, and alkoxy, and wherein each R6 is chosen from hydrogen, alkyl, or alkenyl. As disclosed above, Clark ‘288 introduces dopants as oxide layers thereof. Matero ‘841 is drawn to ALD processes for forming germania (Abstract); this is commensurate with the formation of dopant oxide layers in Clark ‘288 if the dopant is chosen to be germanium as suggested by Wu ‘937. Matero ‘841 discloses a wide selection of precursors for germanium ALD processes at PG 0077-0113. Therefore, it would have been obvious to a person having ordinary skill in the art at the time the invention was made or filed to have modified the invention of Clark ‘288 / Wu ‘937 to use germanium precursors as suggested by Matero ‘841, as Clark ‘288 / Wu ‘937 want to form germania-doped HZO films and Matero ‘841 teaches suitable ALD precursors for forming germania. The disclosed formulas as cited in Matero ‘841 render obvious all R5 ligands except cycloalkyl and render obvious all R6 ligands.
Claim(s) 23 is rejected under 35 U.S.C. 103 as being unpatentable over Clark ‘288 as applied to claim 21 above, and further in view of Pesic ‘146 (U.S. PGPub 2022/0140146).
Claim 23 – Clark ‘288 teaches the method according to claim 21, but does not expressly teach or suggest wherein said metal oxide is TiO2. Pesic ‘146 is drawn to CMOS devices and analogues (PG 0002) and discloses structures comprising doped HZO layers integrated with titanium oxide layers in semiconductor technology (PG 0055). Therefore, it would have been obvious to a person having ordinary skill in the art at the time the invention was made or filed to have modified the invention of Clark ‘288 to overlay the doped HZO layer therein with titanium oxide as suggested by Pesic ‘146, as Clark ‘288 wants to make doped HZO semiconductors and Pesic ‘146 shows examples of desirable titanium oxide / doped HZO materials in semiconductors.
Double Patenting
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the conflicting claims are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on nonstatutory double patenting provided the reference application or patent either is shown to be commonly owned with the examined application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. See MPEP § 717.02 for applications subject to examination under the first inventor to file provisions of the AIA as explained in MPEP § 2159. See MPEP § 2146 et seq. for applications not subject to examination under the first inventor to file provisions of the AIA . A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The filing of a terminal disclaimer by itself is not a complete reply to a nonstatutory double patenting (NSDP) rejection. A complete reply requires that the terminal disclaimer be accompanied by a reply requesting reconsideration of the prior Office action. Even where the NSDP rejection is provisional the reply must be complete. See MPEP § 804, subsection I.B.1. For a reply to a non-final Office action, see 37 CFR 1.111(a). For a reply to final Office action, see 37 CFR 1.113(c). A request for reconsideration while not provided for in 37 CFR 1.113(c) may be filed after final for consideration. See MPEP §§ 706.07(e) and 714.13.
The USPTO Internet website contains terminal disclaimer forms which may be used. Please visit www.uspto.gov/patent/patents-forms. The actual filing date of the application in which the form is filed determines what form (e.g., PTO/SB/25, PTO/SB/26, PTO/AIA /25, or PTO/AIA /26) should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to www.uspto.gov/patents/apply/applying-online/eterminal-disclaimer.
Claims 1, 3, and 4 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claim 1 of copending Application No. 18/319333 (reference application). Although the claims at issue are not identical, they are not patentably distinct from each other because the subject matter between the claims is present in both sets of claims.
This is a provisional nonstatutory double patenting rejection because the patentably indistinct claims have not in fact been patented.
Claims 1, 5, 7 and 20-23 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1, 7, and 8 of copending Application No. 19/251984 (reference application). Although the claims at issue are not identical, they are not patentably distinct from each other because the subject matter between the claims is present in both sets of claims.
This is a provisional nonstatutory double patenting rejection because the patentably indistinct claims have not in fact been patented.
Conclusion
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/MICHAEL G MILLER/ Primary Examiner, Art Unit 1712