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 .
Applicant’s election without traverse of Group I, claims 1-11, in the reply filed on 4/8/26 is acknowledged. Claims 12-18 have been withdrawn as being directed toward a non-elected invention as elected in paper filed 4/8/26. Claims 1-11 remain in the application for prosecution thereof.
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Considering the amendment filed 7/22/26, the 35 USC 112 rejection over claim 3 has been withdrawn, however, the rejection over claim 8 is maintained for the reasons provided below.
Claim Rejections - 35 USC § 112
Claim 8 is 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.
Regarding claim 8, the term “second plasma generated” is confusing as no “first plasma generated” is recited? Clarification is requested.
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.
Claim 1 is rejected under 35 U.S.C. 103 as being unpatentable over Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701).
Chang et al. (7,404,985) teaches a noble metal layer formation for copper film deposition whereby the noble metal formation is applied by a cyclical deposition process (claimed ALD) and can include cobalt (abstract). Chang et al. (7,404,985) teaches the substrate can be heated to a desired temperature prior to deposition (claimed preprocessing step) and a silicon substrate (claimed three-dimensional substrate) is placed into a process chamber (Fig. 2), supplying a carrier gas flow to the chamber, including argon or helium (step 104), after the carrier gas stream pulsing a noble metal precursor is added to the carrier gas stream (step 106) with the noble metal including cobalt precursors, then supplying a reducing gas to form the cobalt film (step 108) (col. 4, line 6 – col. 5, line 60). Subsequent deposition cycles can be performed to achieve a desired thickness, and the steps 104-108 are repeated (col. 7, lines 8-16).
Marsh (7,078,326) teaches a nucleation method of atomic layer deposition of cobalt on bare silicon during the formation of a semiconductor device. Marsh (7,078,326) teaches treatment of the silicon substrate to one or more exposures of titanium nitride and tantalum nitride followed by optional exposure to ammonia (claimed preprocessing step) and after this treatment the silicon surface is exposed to a metal organic cobalt precursor and then exposed to hydrogen or ammonia (claimed reaction gas) to reduce the precursor to an ALD cobalt metal layer. Additional layers may be completed to form the cobalt metal layer of desired thickness (abstract). Marsh (7,078,326) also teaches cleaning the after with hydrofluoric acid to remove native oxides to form clean bare silicon (also claimed preprocessing step). The first layer of cobalt can be utilized as a seed layer and additional cobalt formation may be performed to the nucleation or base layer to form a thicker cobalt layer by ALD (col. 2, lines 25-55).
Chang et al. (7,404,985) or Marsh (7,078,326) fails to teach the cobalt buffer layer to be formed at a lower temperature than the cobalt layer and the claimed temperature ranges.
Mattinen et al. (2022/0251701) teaches deposition of transition metal comprising material on a substrate by a cyclic deposition (abstract). Mattinen et al. (2022/0251701) teaches a forming cobalt sulfide layer on a silicon substrate whereby a cobalt seed or barrier layer can be formed at lower temperatures and at higher temperatures the cobalt sulfide is gradually changed to cobalt oxide and finally cobalt [0095].
Therefore it would have been obvious for one skilled in the art before the effective filing date of the claimed invention to have modified Chang et al. (7,404,985) or Marsh (7,078,326) process to include forming a seed/barrier layer for cobalt with lower temperatures and elemental cobalt at higher temperatures as evidenced by Mattinen et al. (2022/0251701) with the expectation of forming the desired cobalt layer.
Regarding the temperatures, the Examiner acknowledges the fact that the temperatures are not specifically those claimed, however, the Examiner takes the position that Mattinen et al. (2022/0251701) teaches forming cobalt seed/barrier layers at lower temperatures and cobalt layer at higher temperatures and one skilled in the art would have been suggested to utilize the claimed temperatures absent a showing of criticality thereof as these temperatures are taught to form the cobalt layers and teaches increasing the temperature of deposition changes the layered structure as desired.
Claims 2,3 and 6 are rejected under 35 U.S.C. 103 as being unpatentable over Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) in combination with Wang et al. (2014/0273489).
Features detailed above concerning the teachings of Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) are incorporated here.
Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) fails to teach the preprocessing includes a wet processing including the water and dihydrofuran with the claimed ratio and duration time.
Wang et al. (2014/0273489) teaches a processing system for processing silicon wafers for coating whereby the silicon wafer can be exposed to a wet etching (claimed wet processing) using deionized water and hydrofluoric acid such as DHF [0172]. Wang et al. (2014/0273489) teaches treatment times of 1 second to 30 minutes [0179]. Wang et al. (2014/0273489) teaches the ratio of water to DHF of 200:1 to 50:1 [0027].
Therefore, it would have been obvious for one skilled in the art before the effective filing date of the claimed invention to have modified Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) process to include a preprocessing step of wet etching with water and DHF as evidenced by Wang et al. (2014/0273489) with the expectation of similar success, i.e. cleaning surface of silicon substrate.
Regarding claim 3, Wang et al. (2014/0273489) teaches several preprocessing treatments and hence would be suggestive of utilizing a combination including the four claimed, wet processing (wet etching), degassing, pre-cleaning or etching and thermal processing [0024]-[0037]. The Examiner takes the position that the additional preprocessing steps would be expected to effectively remove the oxide layer and produce a cleaner surface and hence would be within the skill of one in the art to utilize one or more preprocessing treatments with the expectation of success.
Regarding claim 6, Wang et al. (2014/0273489) teaches thermal treatment to remove silicon oxides including heating up to 800C as well as to about 150C for greater than or about 2 min [0029]-[0030].
Claim 4 is rejected under 35 U.S.C. 103 as being unpatentable over Chang et al. (7,404,985) in combination with Mattinen et al. (2022/0251701).
Features detailed above concerning the teachings of Chang et al. (7,404,985) in combination with Mattinen et al. (2022/0251701) are incorporated here.
Chang et al. (7,404,985) teaches heating the substrate prior to or during deposition and may be heated by heating the support pedestal (claimed heating base) or heating with a lamp (col. 3, lines 12-21) and at temperatures of up to 300C (col. 4, lines 29-32).
Regarding the heating duration time of 25-35 seconds, the Examiner takes the position that the heating times would be a matter of design choice of a practitioner in the art based upon the substrate, temperature utilized and amount desired to remove of the oxide layer absent a showing of criticality thereof.
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701).
Features detailed above concerning the teachings of Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) are incorporated here.
Marsh (7,078,326) teaches the reducer to include hydrogen or ammonia and the pulses are 0.01-50 seconds to form a thickness of the cobalt layer of 5A-1,000A which is 80-300 nm (col. 5, lines 25 – col. 6, lines 60).
Regarding the claimed duration of discharging, the Examiner takes the position that this is understood as the process includes purging steps after the hydrogen/ammonia and cobalt precursors are introduced to form the cobalt layer.
Claim 5 is rejected under 35 U.S.C. 103 as being unpatentable over Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) in combination with Lu et al. (2007/0015360).
Features detailed above concerning the teachings of Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) are incorporated here.
Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) fails to teach the preprocessing include a pre-cleaning processing.
Lu et al. (2007/0015360) teaches removing oxides from a surface including a remote plasma process including a NF3/NH3 cleaning gas at a RF power from 5-600 Watts at a frequency of 50-90 KHZ and a ratio of the cleaning materials being 1:1 [0021]-[0022].
Therefore, it would have been obvious for one skilled in the art to have modified Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) process to include a precleaning process as evidenced by Lu et al. (2007/0015360) with the expectation of producing a clean surface after removal of the oxide layer for subsequent deposition thereto.
Claims 7-10 are rejected under 35 U.S.C. 103 as being unpatentable over Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) in combination with Vayrynen et al. (2021/0317578).
Features detailed above concerning the teachings of Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) are incorporated here.
Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) fails to teach the claimed cobalt precursor being bis (N’N’-diisopropylacetamidinato cobalt).
Vayrynen et al. (2021/0317578) teaches a cyclical deposition method of forming metal containing materials whereby a cobalt precursor includes bis (N’N’-diisopropylacetamidinato cobalt) [0068].
Therefore, it would have bene obvious for one skilled in the art to have modified Chang et al. (7,404,985) or Marsh (7,078,326) in combination with Mattinen et al. (2022/0251701) process to include the cobalt precursor of bis (N’N’-diisopropylacetamidinato cobalt) as evidenced by Vayrynen et al. (2021/0317578) with the expectation of forming the cobalt film.
Regarding the temperatures [0039],[0090], cobalt precursor [0068], pulses, discharging(purging steps), carrier/purge gas include argon [0030],[0094] are taught by Vayrynen et al. (2021/0317578). Regarding the duration of the pulses and discharging/purging, the Examiner takes the position that these parameters would be optimized by one skilled in the art absent a showing of criticality thereof the claimed times.
Response to Amendment
Applicant’s arguments with respect to claims 1-11 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
Applicant argued the “first plasma” is recited in claim 5 thus the “second plasma” in claim 8 is clearly distinguished from the first plasma in claim 5 which obviates the rejection.
The Examiner disagrees. First off, claim 8 does not depend from or upon claim 5 and hence no recited “first plasma” is found in claims 7 or 1 from which claim 8 depends upon. Hence the rejection is maintained. Secondly, the rejection is not about the first plasma being “distinguished” from the “second plasma” but that there is a recitation of a first plasma when reciting a “second plasma”.
Applicant argued the prior art fails to teach depositing the cobalt buffer layer at a first temperature range and depositing a cobalt film at a second temperature range.
First off, it is noted that eventhough temperature ranges are recited does not require “separate” first and second chambers but would be applicable to forming a cobalt buffer layer at a temperature and then raising that temperature to a second and higher temperature to form the cobalt film on the cobalt buffer layer. Secondly, Mattinen et al. (2022/0251701) teaches this as detailed above.
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 BRIAN K TALBOT whose telephone number is (571)272-1428. The examiner can normally be reached Monday -Friday 7-4PM.
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/BRIAN K TALBOT/ Primary Examiner, Art Unit 1712
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