DETAILED ACTION
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on January 7, 2026 has been entered.
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 102/103
The rejections of claims 1, 5, 7, 8 under 35 USC §102 as being anticipated by Stoffelback et al. “Half-sandwich molybdenum(III) compounds containing diazadiene ligands and their use in the controlled radical polymerization of styrene”. Journal of Organometallic Chemistry 663 (2002). Pages 269 – 276 in the previous Office Action are withdrawn due to Applicant amendment.
The rejections of claims 1, 3, 5, 6, 7, 8 under 35 USC §102 or, in alternative, 35 U.S.C. §103 as being anticipated/obvious over Stoffelbach et al. “A Bis(diazadiene) Adduct of MoCl2: Mononuclear, Octahedral, Undistorted and Diamagnetic”. Eur. J. Inorg. Chem. 2004, 726_731 in the previous Office Action are withdrawn due to Applicant amendment.
Claim(s) 9, 12, 14 remain rejected under 35 U.S.C. 103 as being unpatentable over Vaarstra et al. US 2006/0046521 A1 (hereafter “Vaarstra”) in view of Milligan US 2008/0274617 A1 (hereafter “Milligan”).
Regarding claims 9, 12, 14:
Vaarstra is directed to an atomic layer deposition (ALD) method for deposition of molybdenum-containing films (Abstract; [0039] Claim 7). Vaarstra discloses that their method comprises:
providing a first molybdenum-containing precursor, wherein the first precursor may comprise a halogen, an organic ligand such as diketoiminate [containing nitrogen] and combinations thereof ([0037] – [0038]);
providing a bulk semiconductor wafer as a substrate and placing the substrate in a deposition chamber ([0023], [0040], [0060]; claim 7, claim 18);
Introducing the first precursor into the deposition chamber and chemisorbing the precursor onto the substrate [surface reaction] (Claim 7);
purging non-chemisorbed first precursors from the chamber [removing unabsorbed molybdenum-containing precursor] ([0018]); and
reacting the first precursor with a reactant with a second precursor such as e.g. H2O [water] and/or dihydrogen sulfide [thiol] ([0042], Claim 17).
While Vaarstra does not expressly teach specific embodiments of first precursors having a halogen and diketoiminate, Vaarstra does teach that combinations of ligands can comprise the first precursor. It would have then been obvious to one of ordinary skill in the art before the effective filing date of the present invention have chosen first precursors with desired ligands (including combinations of specific halides and beta-diketoiminates, meeting claim 14) from the list of Vaarstra for suitable molybdenum deposition. The deposited film may consist essentially of a metal film, in addition to oxides, nitrides, silicides, sulfides or selenides of the metal.
Vaarstra does not expressly teach that their method forms a molybdenum metal layer by treating the surface of the semiconductor surface with hydrogen gas after reaction of the first precursor with the second precursor.
Milligan is directed to the periodic plasma annealing of deposited metal thin film or metal nitride thin films that were produced using an ALD technique (Abstract). As depicted in Fig. 1, Milligan disclose a method comprising: alternately providing a pulse of transition metal source and a plasma pulse of reducing agent to form films of transition metal on a substrate; performing plasma annealing [plasma treatment] onto deposited films; and repeating both the formation of transition metal films and plasma annealing until a desired thickness is deposited ([0037] – [0045], particularly [0043] – [0045]). The deposited films are annealed by exposing the films to a plasma activated reducing agent in order to remove any oxygen and/or halide impurities that are present in the metal film ([0044]). The reducing agent may be a plasma species generated from excitation of supplied hydrogen gas (0027]).
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 Vaarstra by including a step of treating the surface of the semiconductor surface with hydrogen gas after reaction of the first precursor with the second precursor to purify [form] the molybdenum-containing film to a more pure molybdenum film because Vaarstra teaches that their method intends to allow the formation of molybdenum metal films and Milligan teaches that such a treatment step allows for the removal of e.g. oxygen and/or halide impurities that would be present on the surfaces of deposited films.
Claim(s) 18 remains rejected under 35 U.S.C. 103 as being unpatentable over Vaarstra in view of Milligan and Thombare et al (US 2018/0294187).
Regarding claim 18:
Vaarstra discloses a processing chamber having a substrate holder and one or more inlets for reactants ([0057]). Vaarstra in view of Milligan also render obvious a set of instructions comprising the recited steps as discussed above in the rejection of claims 9, 12 and 14 mutatis mutandis.
Vaarstra does not expressly teach a system controller that comprises such a set of instructions as program instructions.
Thombare discloses a process system ([0089]) for deposition of molybdenum [0004] comprising a controller employed to control process conditions during deposition ([0091]).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the present invention to have combined the system of Vaarstra in view of Milligan with a system controller containing the method of Vaarstra in view of Milligan as program instructions because Thombare teaches that such an inclusion allows for control of process conditions during deposition.
Claim(s) 9, 12, 14, 19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Vaarstra in view of Wright, Jr et al. US20200115798A1 (hereinafter “Wright”, of record).
Regarding claims 9, 12, 14 and 19:
The disclosure of Vaarstra discussed above in the rejections of claims 9, 12, 14 under 35 USC 103 over Vaarstra in view of Milligan also apply to the present rejection, mutatis mutandis.
Vaarstra does not expressly teach that their method forms a molybdenum metal layer by treating the surface of the semiconductor surface with hydrogen gas without plasma after reaction of the first precursor with the second precursor.
Wright is directed to vapor deposition methods for depositing elemental tungsten or molybdenum films. Wright discloses that their method comprises: providing an organometallic precursor containing molybdenum and ligands, wherein the ligands may be e.g. alkyl groups having carbonyl groups or alkyl imide groups ([0024]); providing a reducing co-reactant to deposit an impure molybdenum film ([0005], [0031], [0035], [0037], [0038]); and treating the impure molybdenum with an oxidizer in combination of hydrogen or sequentially with oxidizer followed by hydrogen ([0035] – [0036], [0041], Claims 7, 9). Wright discloses that the post treatment with hydrogen aids in removing contaminants that are present on the deposited molybdenum film, such as oxygen contaminants ([0041]).
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 Vaarstra by including a step of treating the surface of the semiconductor surface with hydrogen gas without plasma after reaction of the first precursor with the second precursor to purify [form] the molybdenum-containing film to a more pure molybdenum film because Vaarstra teaches that their method intends to allow the formation of molybdenum metal films and Wright teaches that such a treatment step allows for the removal of e.g. oxygen and/or other impurities that would be present on the surfaces of deposited films.
Response to Arguments
Applicant's arguments filed on January 7, 2026 have been fully considered but they are not persuasive.
Applicant’s principal arguments are:
a.) There is no reasonable expectation of success in combining an ALD process designed for heteroleptic precursors with the process designed for homoleptic precursors. Vaarstra further highlights potential issues with applying the ALD process for homoleptic precursors to heteroleptic precursors, e.g., it could introduce undesired deposited material defects.
In response to the applicant's arguments, please consider the following comments.
a.) In response to applicant’s argument that there is no teaching, suggestion, or motivation to combine the references, the examiner recognizes that obviousness may be established by combining or modifying the teachings of the prior art to produce the claimed invention where there is some teaching, suggestion, or motivation to do so found either in the references themselves or in the knowledge generally available to one of ordinary skill in the art. See In re Fine, 837 F.2d 1071, 5 USPQ2d 1596 (Fed. Cir. 1988), In re Jones, 958 F.2d 347, 21 USPQ2d 1941 (Fed. Cir. 1992), and KSR International Co. v. Teleflex, Inc., 550 U.S. 398, 82 USPQ2d 1385 (2007).
In this case, Vaarstra indicates an intention and desire to form pure molybdenum films and Milligan provides motivation to modify the method of Vaarstra by indicating that their treatment step, allows for the removal of impurities such as halogen impurities. One of ordinary skill in the art would have welcomed such a modification in view of Vaarstra’s intention and the use of precursors that can have halogen ligands and films with potential oxide impurities in embodiments where a pure metal film is desired (e.g. [0049] indicating higher halogen content in films deposited by HfCl4 versus [0050] of Vaarstra indicating lower halogen content in films deposited with trichloro(dimethylamino)hafnium, thus implying a concern for the amount of halogen impurity). "The test for obviousness is not whether the features of a secondary reference may be bodily incorporated into the structure of the primary reference.... Rather, the test is what the combined teachings of those references would have suggested to those of ordinary skill in the art." In re Keller, 642 F.2d 413, 425, 208 USPQ 871, 881 (CCPA 1981). Absent a teaching away from the modification proposed, the precursors of Milligan do not affect the motivation for treatment in this case.
With regards to reasonable expectation of success, the reasonable expectation of success requirement refers to "the likelihood of success" in combining or modifying prior art disclosures to meet the limitations of the claimed invention. See Elekta Ltd. v. ZAP Surgical Sys., Inc., 81 F.4th 1368, 1375, 2023 USPQ2d 1100 (Fed. Cir. 2023) and Intelligent Bio-Sys., Inc. v. Illumina Cambridge Ltd., 821 F.3d 1359, 1367, 119 USPQ2d 1171, 1176 (Fed. Cir. 2016). Applicant cites paragraph [0003] of Vaarstra to argue that ALD processes of Vaarstra using heteroleptic precursors would require different considerations compared to Milligan’s ALD processes using homoleptic precursors. However, the modification to the method Vaarstra does not concern deposition itself, but a treatment after deposition [of a given monolayer or overall film] (“after the reaction [to form molybdenum metal], treating the surface …”). As explained above, even films deposited with heteroleptic precursors can lead to undesired impurities that Milligan’s teachings can address. No evidence has been presented that Vaarstra would criticize, discredit, or otherwise discourage the modification proposed. The arguments of counsel cannot take the place of evidence in the record. In re Schulze, 346 F.2d 600, 602, 145 USPQ 716, 718 (CCPA 1965); In re Geisler, 116 F.3d 1465, 43 USPQ2d 1362 (Fed. Cir. 1997).
Reasons for Allowance
Claims 1, 3 and 5 – 8 are allowed.
The following is a statement of reasons for the indication of allowable subject matter:
PNG
media_image1.png
200
400
media_image1.png
Greyscale
Regarding claim 1 and claims dependent on claim 1, the prior art of record does not teach and does not reasonably suggest the recited precursor for deposition of molybdenum-containing films, wherein the precursor is a compound including molybdenum and a DAD ligand, wherein the DAD ligand is selected from the group of:
PNG
media_image2.png
200
400
media_image2.png
Greyscale
PNG
media_image3.png
200
400
media_image3.png
Greyscale
and wherein the compound is Mo(DAD)m(L)n(X)p, wherein each L is the neutral ligand
independently selected from the group consisting of CO, an amine, a phosphine, a nitrile, an isonitrile, and a thioether, each X is the anionic ligand independently selected from the group consisting of a halide, an alkyl, an allyl, a cyclopentadienyl, an alkoxide, an amide, and an imide, m is 1-3, n is 1, and p is 0-4, wherein the precursor is heteroleptic in the context of present claim 1.
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.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Dah-Wei Yuan can be reached on (571) 272-1295. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/JOSE I HERNANDEZ-KENNEY/
Primary Examiner
Art Unit 1717