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, 2, 6, 7, and 10-18 are pending and rejected. Claims 3, 8-9, and 19-20 are withdrawn. Claims 4 and 5 are cancelled.
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.
Claims 1, 2, 6, 7, 10, and 13-18 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Miyata, US 2022/0102137 A1 (provided on the IDS of 3/9/2026).
Regarding claim 1, Miyata teaches a method of processing a substrate (a substrate processing technique, abstract), comprising:
(a) supplying a non-reducing promoting agent that promotes adsorption of a modifying agent containing an organic ligand to the substrate, the organic ligand containing at least one selected from the group of a hydrocarbon group and an amino group (step A3 of supplying a O- and H-containing substance to a wafer, 0089, where the O- and H-containing gas react with a first applied modifier ligand to result in OH terminations that then react with a second modifier, 0091-0092, 0102 and Fig. 7C-D, indicating that it will promote adsorption of the second modifying agent, where the second modifying agent includes a first functional group such as a substituted amino group, where a substituent of the substituted amino group may be an alkyl group and a second functional group that may be a hydrocarbon group, 0112-0113, 0116, 0136-0137, such that the modifying agent will include an amino and a hydrocarbon group);
(b) supplying the modifying agent to the substrate such that a surface of the substrate is terminated by the at least one selected from the group of the hydrocarbon group and the amine group derived from the modifying agent (step A2 of supplying the second modifier so that it reacts with the OH terminations from step A3 to provide a third modified layer contains the second functional group, 0102 and Fig. 7D, such that the surface is terminated with the hydrocarbon group); and
(c) forming a film on the substrate after performing (a) and (b) (step B of selectively forming a film on the substrate after steps (a) and (b), 0170 and Fig. 6).
Regarding claim 2, Miyata teaches the process of claim 1. They further teach that the modifying agent is [R1]n2-(X)-[R2]m2 where R1 is the first functional group (amino group), R2 is the second functional group (hydrocarbon), n2 is 1 or 2, m2 is 2 or 3, and X is a C atom, a Si atom, a Ge atom, etc. (0143-0144). Therefore, when X is C or Si the modifying agent will not contain a metal element, where Si is a metalloid and C is a non-metal.
Regarding claim 6, Miyata teaches the process of claim 1. They further teach that the promoting agent is water vapor, hydrogen peroxide, hydrogen gas and oxygen gas, or hydrogen gas and ozone (0152). They teach that the O- and H-containing substance acts as an oxidizing agent (0046). Therefore, the promoting agent is oxidizing, which is further supported by the instant specification at paragraph 0045 which indicates that oxygen, ozone, water, hydrogen peroxide, and hydrogen gas with oxygen gas are oxidizing gases.
Regarding claim 7, Miyata teaches the process of claim 6. They teach supplying hydrogen and oxygen or ozone in step A3 (0152), such that oxygen or ozone is considered to be the promoting agent gas that does not contain a hydrogen element and hydrogen is considered to be an additional gas provided during the step since the process does not limit that gases provided during the step of supplying the promoting agent to those that consist of gases not containing a hydrogen element.
Regarding claim 10, Miyata teaches the process of claim 1. They further teach that in forming the film a gas containing a halogen element is used (0186-0187).
Regarding claim 13, Miyata teaches the process of claim 1. They further teach that Step A3 and Step A2 may be performed one or more times to increase the modification density of the surface of the first base (0169), such that step (a) will be performed a plurality of times.
Regarding claim 14, Miyata teaches the process of claim 1. They further teach annealing to remove the modified layer after performing step A and step B (0208-0211 and Fig. 8D). Therefore, they provide step (d) of removing the promoting agent after step (a), where step (a) and (d) are performed in this order a predetermined number of times, i.e., once.
Regarding claim 15, Miyata teaches the process of claim 1. They further teach performing step A1, step A3, and step A2 one or more times to increase the modification density (0169). Since they teach performing steps A1, A3, and A2 in this order (Fig. 6), the steps will be performed at least once in this order so as to provide performing (a) and (b) in this order a predetermined number of times, i.e., one or more times.
Regarding claim 16, Miyata teaches the process of claim 15. They further teach performing step B of forming the film a predetermined number of times (0204 and Fig. 6). Therefore, step (e) and (c) will be performed a predetermined number of times, i.e., performing steps A1, As, and A2 in order one or more times and then performing step (c) one or more times.
Regarding claim 17, Miyata teaches the process of claim 1. They further teach that in the step of forming the film, a reaction gas including a H-containing substance may be used for forming an oxide or a H-containing gas can be used for forming a nitride film (0201-0202).
Regarding claim 18, Miyata teaches the process of claim 1, where they further teach using the method to manufacture a semiconductor device (0002, 0057, and claim 1).
Claims 1, 2, 6, 7, 13, 15, 16, and 18 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Hashimoto, US 2021/0066073 A1.
Regarding claim 1, Hashimoto teaches a method of processing a substrate (a substrate processing sequence of forming an oxide film on a wafer, 0042), comprising:
(a) supplying a non-reducing promoting agent that promotes adsorption of a modifying agent containing an organic ligand to the substrate, the organic ligand containing at least one selected from the group of a hydrocarbon group and an amino group (pre-flowing an O2 gas to optimize OH termination on the surface of a wafer to promote the formation of a first layer in step A, 0090-0091, where in step A, TMDMAS adsorbs or reacts with OH termination, 0051, 0054, such that it will promote adsorption of a modifying agent containing an organic ligand including an amino group and a hydrocarbon group, i.e., the methyl group off of the methoxy group);
(b) supplying the modifying agent to the substrate such that a surface of the substrate is terminated by the at least one selected from the group of the hydrocarbon group and the amine group derived from the modifying agent (supplying TMDMAS to adsorb to the OH termination on the surface, 0051, 0054, where the adsorption result in the hydrocarbon group terminating the surface, i.e., having the methyl group on the surface, 0055-0056 and Fig. 6B); and
(c) forming a film on the substrate after performing (a) and (b) (supplying an oxygen gas and repeating the TMDMAS and oxygen supplying steps to form a film, 0060, 0064, and 0090-0091).
Regarding claim 2, Hashimoto teaches the process of claim 1. They teach using TMDMAS as the modifying agent (0051, 0054), such that it will not contain a metal element since Si is a metalloid.
Regarding claims 6 and 7, Hashimoto teaches the process of claim 1. They further teach pre-flowing oxygen to promote OH termination (0090-0091), such that the promoting agent is oxidizing and it is a gas that does not contain a hydrogen element. This is further supported by the instant specification at paragraph 0045 which indicates that oxygen is an oxidizing gas.
Regarding claim 13, Hashimoto teaches the process of claim 1. They further teach that a cycle which sequentially and non-simultaneously performs step A and step B after pre-flowing oxygen in advance may be implemented a predetermined number of times where n is one or more (0090). Therefore, step (a) of flowing oxygen will be repeated a plurality of times.
Regarding claims 15 and 16, Hashimoto teaches the process of claim 1. They further teach that a cycle which sequentially and non-simultaneously performs step A and step B after pre-flowing oxygen in advance may be implemented a predetermined number of times where the sequence if O2 -> (TMDMAS -> O2)xn (0090). Therefore, performing (a) and (b) in this order will be performed a predetermined number of times and (e) and (c) will be performed a predetermined number of times. Specifically, since the sequence is oxygen (promoting agent), TMDMAS (modifying agent), oxygen (reactant), TMDMAS (precursor), where the supply of oxygen and TMDMAS are sequentially repeated, the process will provide performing (a), (b), and (c) a predetermined number of times. Alternatively, performing (a) and (b) once and then forming the film in (c) would also provide a predetermined number of times.
Regarding claim 18, Hashimoto teaches the process of claim 1, where they also teach a method of manufacturing a semiconductor device using the claimed process (0002, 0042, and claim 1).
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claims 13 and 15-16 are alternatively rejected under 35 U.S.C. 103 as being unpatentable over Miyata, US 2022/0102137 A1 (provided on the IDS of 3/9/2026).
Regarding claim 13, Miyata teaches the process of claim 1. They further teach that Step A3 and Step A2 may be performed one or more times to increase the modification density of the surface of the first base (0169). 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 step (a) a plurality of times because Miyata teaches a range that includes performing it multiple times where it can increase the modification density such that it will be expected to improve the selectivity of the process. 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, Miyata teaches the process of claim 1. They further teach performing step A1, step A3, and step A2 one or more times to increase the modification density (0169). Since they teach performing steps A1, A3, and A2 in this order (Fig. 6), 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 them in this order one or more times with the expectation of successfully forming the modification layer. 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 16, Miyata suggests the process of claim 15. They further teach performing step B of forming the film a predetermined number of times (0204 and Fig. 6). Therefore, step (e) and (c) will be performed a predetermined number of times, i.e., performing steps A1, As, and A2 in order one or more times and then performing step (c) one or more times to provide a predetermined number of times.
Claim 7 is alternately rejected under 35 U.S.C. 103 as being unpatentable over Miyata as applied to claim 1 above, and further in view of Hashimoto, US 2021/0066073 A1.
Regarding claim 7, Miyata teaches the process of claim 1, as discussed in the 102(a)(1) rejection above, where in step A3 they teach supplying a hydrogen- and oxygen-containing gas. They further teach a step A1 of supplying a first modifier to react with OH termination on the substrate surface (0076). They teach that the first modifier includes an amino group that can be substituted with hydrocarbon groups and a hydrocarbon group (0112-0113 and 0116). They teach that supplying the first modifier provides a first modified layer that contains the first functional group and the second functional group (0076 and Fig. 7B). Therefore, they provide supplying a modifying agent to react with OH terminations resulting in the surface of the substrate being terminated by an amine group and a hydrocarbon group, where the film is formed after this step. They teach that the surface of the first base which is modified by the modifying agent is SiO, Ge, etc. (0244).
They do not teach that the promoting agent gas as a whole does not include hydrogen.
Hashimoto teaches forming an oxide film containing a central atom X of a precursor on a substrate by performing a cycle a predetermined number of times (abstract). They teach supplying a TMDMAS precursor to a wafer to react with OH termination on the wafer surface (0051, 0054, and Fig. 6A-B). They indicate that TMDMAS includes a methyl amino group that reacts with the OH terminations (0054 and Fig. 6B). They teach pre-flowing an oxygen gas to the wafer in advance to a wafer to optimize the adsorption site (OH termination) on the surface of the wafer before performing step A (0090-0091). They teach that by doing so it is possible to promote the formation of the first layer at step A and to shorten the incubation time when forming the film (0091).
From the teachings of Hashimoto, 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 pre-flowed oxygen prior to supplying the first modifier because Hashimoto teaches that by pre-flowing oxygen to a substrate it optimizes OH termination on the surface to promote the formation of a first layer that results from reaction of an amino-containing reactant such that it will be expected to also increase the OH termination on the surface for promoting reaction or adsorption with the first modifier prior to forming the film. Therefore, the promoting agent will be oxidizing in that it promotes the formation of hydroxyl group (and oxygen is indicated as being an oxidizing gas in paragraph 0045 of the instant specification) and since it is oxygen it is hydrogen-free.
Claims 11 and 12 are rejected under 35 U.S.C. 103 as being unpatentable over Miyata as applied to claim 1 above, and further in view of Waseda, US 2021/0035801 A1.
Regarding claims 11 and 12, Miyata teaches the process of claim 1, as discussed in the 102(a)(1) rejection above. They teach in step B of forming the film on the second base, a precursor containing silicon and a halogen-containing gas is provided (0170 and 0186). They teach that in growing the film, a gas containing a metal element such as Al, Ti, Hf, Zr, Ta, Mo, or W can be used as the precursor gas to form an oxide of the metal (0207). They teach that the second base may be a material such as SiN (0244 and 0250).
They do not teach that the metal-containing precursor includes a halogen element.
Waseda teaches forming a protective film on a surface of a third base by supplying a processing gas to a substrate in which a first base containing no oxygen, a second base containing oxygen, and a third base containing no oxygen and no nitrogen are exposed on the surface (abstract). They teach modifying a surface of the second base to be fluorine-terminated, and selectively forming a film on a surface of the first base by supplying a film-forming gas to the substrate after the surface of the second base is modified (abstract). They teach that the first base includes a SiN film (0042). They teach forming the film on the first base by supplying a gas containing a halogen element such as silicon tetrachloride (0043, 0095, and Fig. 4). They also teach that instead of using silicon tetrachloride, a metal halide gas such as titanium tetrachloride can be used with an oxygen-containing gas (0162).
From the teachings of Waseda, 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 Miyata to have used TiCl4 or a metal halide as the precursor gas in forming the film because Miyata teaches using different metal precursors, including Ti-based precursors, for forming films on a SiN base, where halogen-containing precursors can be used (as indicated by the silicon precursor) and Waseda teaches that metal halides and specifically TiCl4 are suitable for selective deposition of films on SiN bases such that it will be expected to provide a metal- or titanium-based film as desired. Therefore, the gas containing the halogen element will also contain a metal element while the modifying agent does not contain a metal element (as discussed more fully above for claim 2).
Response to Arguments
Applicant’s arguments dated 12/22/2025 have been fully considered and are persuasive in light of the amendments to the claims. Therefore, the rejection has been modified as indicated above.
In light of the amendment to Fig. 4, the previous drawing objection is 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
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