DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
As of the preliminary amendment filed on December 20, 2024, claims 1 – 10 are pending. Claim 7 has been amended.
Specification
The specification has not been checked to the extent necessary to determine the presence of all possible minor errors. Applicant’s cooperation is requested in correcting any errors of which applicant may become aware in the specification.
Claim Rejections - 35 USC § 103
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.
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 – 3, 5 – 10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Jordan WO2020185618 A1 (hereinafter “Jordan”).
Regarding claims 1, 2, 3, 5 and 9:
Jordan is directed to molybdenum-containing films, including pure molybdenum films (Abstract; page 2 lines 18 – 25). Jordan discloses a PEALD method for forming such films comprising (Fig. 4A, page 26 lines 15 – 32, page 29 line 21 – page 30 lline 11).):
Providing a semiconductor substrate to a process chamber; and then sequentially and repeatedly:
exposing the semiconductor substrate to substrate to a vaporized molybdenum precursor by introducing said precursor into the process chamber;
purging the processing chamber; and
exposing precursor-coated semiconductor substrate to a plasma generated from gaseous reducing agents such as hydrogen, ammonia, or alcohols, including introducing the plasma remotely (page 26 line 25 – page 27 line 15, page 28 line 24 – page 29 line 12).
While Jordan does not expressly teach that the substrate/reaction temperature is about 300°C or less, Jordan does disclose that the temperature may be e.g. between 100 – 400°C.
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d 1362, 1365-66(Fed. Cir. 1997). See MPEP 2144.05.
Regarding claim 6:
Jordan discloses that the molybdenum precursor may be a heteroleptic sulfur-containing compound, wherein the precursor is of the general form MoLn, wherein n may range from 2 to 6 and L is any sulfur-containing ligand (page 21 lines 1– 16; Fig. 1B). As a specific example, Jordan discloses molybdenum hexa-R-thiolate [Mo(L-R)6, where L is sulfur] (Mo(19)6 , Ligand 19 as depicted in Fig. 1B, R group being selected from H, alkyl or fluoroalkyl as described on page 17 lines 17 – 25 and page 19 lines 29 – 31).
Regarding claim 7:
Jordan discloses that the molybdenum precursor may be a heteroleptic halide-containing compound, wherein the molybdenum precursor is a compound having the general form Mo(X)m(L)n, wherein m is from 1–4, n is from 1-3, each X is a halide independently selected from F, Cl, Br, and I, and L is a bidentate ligand (page 17 lines 19 – 25). Examples include compounds of the form Mo(L)Cl4, wherein each ligand may be e.g. an amidinate molybdenum complex 27, a DAD complex 28, a beta-diketiminate complex 29, a pyrazolate complex 30, an amidate 30 complex 31, a beta-imino amide complex 32, a beta-ketoiminate complex 33, a betaamino alkoxide complex 34, an iminopyrrolidinate complex 35, an alpha-imino alkoxide complex 36, and a beta-diketonate complex 37 (page 17 lines 25 – 33; Fig. 2). Such compound meets the claimed formula wherein L is nitrogen or oxygen , X is chlorine, and R1 links between the two L groups as a cyclic group.
Regarding claim 8:
Jordan discloses that molybdenum pentachloride may be used as it is a conventioal precursor for depositing molybdenum (page 12 lines 1 – 11).
Claim(s) 10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Jordan and optionally in view of Wright Jr. US 2020011579 A1 (hereinafter “Wright”).
Regarding claim 10:
In addition to what is disclosed above in the rejection of claim 1, Jordan discloses an apparatus as depicted in Fig. 7, the apparatus comprising (page 33 line 4 – page 36 line 10): a process chamber body 702 [reaction chamber]; RF power supply 714 electrically connected to a pedestal 708 and showerhead 706 [direct plasma generator]; and one or more controllers (not shown). While Jordan does not expressly teach that the controller includes machine-readable instructions to perform the claimed steps, Jordan does disclose that the controllers require program instructions to enact a given process and the ability to define paramaters (page 32 lines 18 – 30, page 43 line 19 – 32). Jordan therefore implies the presence of instructions to enable performance of the methods disclosed within Jordan.
Jordan does not expressly teach that the controller has instructions to cause plasma from the plasma generator to form a metal thin film from a hydrogen-containing gas and from 0.01% to about 1% of an oxygen containing gas.
However, Jordan discloses that the reactants for forming molybdenum metal includes alcohols, which contain oxygen, and that the reactants may be used in combination (page 26 lines 29 – page 30 line 5). Absent a showing of unexpected results, an implicit range exists among constituents of a reactive gas. In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d 1362, 1365-66(Fed. Cir. 1997). See MPEP 2144.05. One of ordinary skill in the art would have the skill and motivation to write instruction sets to the extent to perform disclosed methods.
Optionally and additionally, Wright is directed to vapor deposition methods for depositing molybdenum films (Abstract). Wright discloses an ALD process comprising per cycle: providing a molybdenum precursor, purging, and introducing a hydrogen gas and oxygen gas purge; wherein the amount of oxygen is minimized to the extent necessary to clean away carbon residues, e.g. 0.01% by mass ([0043] – [0044], [0057] – [0060]; [0034]). Wright also discloses that the method may be controlled by a controller having programmable elements [instruction sets] ([0033] – [0034], [0051]).
Therefore, it would have also have been obvious to one of ordinary skill before the effective filing date of the claimed invention to include in the controller of Jordan instructions to introduce e.g. 0.01% oxygen because Wright teaches that the inclusion of oxygen in addition to hydrogen containing gases helps to further purify metal films of molybdenum.
Claims 4 is/are rejected under 35 U.S.C. 103 as being unpatentable over Jordan as applied to claims 1 – 3, 5 – 10 above, and further in view of Ailihumaer et al. US 2023/0323543 A1 (hereinafter “Ailihumaer”).
Regarding claim 4:
Jordan does not expressly teach a step of pre-treating the surface of the substrate with a remote plasma from the hydrogen-containing source.
Ailihumaer is directed to provide in situ selectively deposited molybdenum films having reduced resistivity and methods of reducing or eliminating lateral growth of a selectively deposited molybdenum layer (Abstract). As shown in Fig. 1, Ailihumaer discloses a step of cleaning substrates having vias with a plurality of chemical exposures before selectively depositing a molybdenum film ([0028]). One such exposure is an H2 plasma exposure ([0045]) by a remote plasma source ([0046]). The exposure helps clean the via to better deposit molybdenum films having such reduced resistivity ([0051]).
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the method of Jordan by pre-treating the surface of the substrate with a remote plasma from the hydrogen-containing source because Ailihumaer teaches that such cleaned substrate surfaces help in forming molybdenum films having reduced resistivity.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to JOSE I HERNANDEZ-KENNEY whose telephone number is (571)270-5979. The examiner can normally be reached M-F 6:30-3:30.
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/JOSE I HERNANDEZ-KENNEY/
Primary Examiner
Art Unit 1717
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