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 .
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.
Claims 13-17, and 19 are rejected under 35 U.S.C. 103 as being unpatentable over Adam Jandi et al U.S. Patent Application: 2018/0053660, here after Jandi), further
in view of (U. S. Phillip S.H. Chen et al (U. S. Patent Application: 2021/0062331, here
after Chen), Miika Leinikka et al (U. S. Patent Application: 2005/0212139, here
after Leinikka).
Claim 13 is rejected. Jandi teaches a process of deposition (ALD or CVD) for
forming a thin film comprising metal(elemental) tungsten on a substrate comprising a
gap in a reaction space (e.g. chamber), the process comprising a plurality of deposition
cycles (CVD, or ALD process comprising a plurality of deposition cycles) [0078] which in fact require providing substrate in reaction space, and performing plurality of deposition cycle until the gap is filled with elemental tungsten (bulk tungsten) [0091]. Jandi teaches each deposition cycle comprising:
contacting the substrate (comprising a gap) with a first reactant comprising a
tungsten precursor comprising W(CO)6[0091]; contacting the substrate with a reducing
gas(H2) to form elemental(metal), and repeating the cycle to filling the gap with elemental metal tungsten [0091]. Jandi does not teach oxidation of tungsten and then reducing it. Chen teaches depositing elemental metal tungsten comprising depositing tungsten oxide and then reducing tungsten oxide to metal by hydrogen or carbon monoxide, where pulsing oxidant (H2O) helps reducing carbon content of film [abstract]. Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention was made to have a process of forming a thin film comprising tungsten that Jandi teaches by method of Chen, because it helps reducing carbon content of the film. Chen teaches a process of ALD/CVD for forming a thin film comprising each cycle of: contacting the substrate with a first reactant comprising a tungsten precursor comprising W(CO)6[abstract, 0011]; tungsten from the tungsten oxide [0013, 0015, 0018], contacting the substrate with a second reactant such as water vapor H2O which in fact, form tungsten oxide [0012, 0015], and contacting the substrate with a reducing gas(H2) to form elemental(metal) tungsten from the tungsten oxide [0013, 0015, 0018]. Chen does not clearly teach contacting the substrate with carbon monoxide. Leinikka teaches reducing tungsten oxide to metal by hydrogen or carbon monoxide [0052]. Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention was made to have a process of forming a thin film comprising tungsten where the reducing gas (third reactant) is (additional flow of) carbon monoxide, because it can also reduce tungsten oxide to elemental tungsten metal.
Claim 14 is rejected as in ALD process, after exposing substrate to each
reactant, an inert gas purges in chamber and therefor the deposition cycle comprises
removing excess tungsten precursor and reaction byproducts, from the reaction space
after contacting the substrate with the tungsten precursor and prior to contacting the
substrate with the second (H20) and the third reactants (CO) [also look at Chen 0039,
0041].
Claim 15 is rejected for the same reason claim 13 is rejected. Jandi teaches
filling gap with elemental tungsten, and the rejection of claim 13 is based on only
reactants that are used in the deposition cycle are the first reactant (tungsten
precursor), second reactant (water vapor) and third reactant (carbon monoxide).
Leinikka teaches reactant are hydrogen or carbon monoxide [0052]. Chen teaches the
process can be CVD, therefore the first and the second process can overlap.
Claim 16 is rejected. Chen teaches the substrate is contacted with the first
reactant (tungsten precursor), and the second (water vapor) or the third reactant
(hydrogen or carbon monoxide) [See claim 13 rejections above]. Chen teaches the
process can be CVD, therefore the second and the third process can overlap.
Claim 17 is rejected for the same reason claim 13 is rejected and the fact that the
process is ALD process. The deposition cycle comprises, in order: contacting the
substrate with the vapor phase tungsten precursor, and simultaneously with second
(HO) and third (CO) reactants.
Claim 19 is rejected as Chen teaches deposition temperature is 250C [claim 4].
Claims 1-2, 5, 7-8, 21-22, and 24 are rejected under 35 U.S.C. 103 as being
unpatentable over Xinyu Fu et al (U. S. Patent Application: 2017/0062224, here after
Fu), further in view of Masayuki Kitamura et al (U.S. Patent Application: 2020/0294793,
here after Kitamura-2), and Hanit Fisher et al (U. S. Patent Application: 2021/0384035,
here after Fisher).
Claim 1 is rejected. Fu teaches a deposition process for forming a thin film
comprising metal(elemental) tungsten on a substrate in a reaction space, the process
comprising a plurality of deposition cycles wherein each deposition cycle comprises:
contacting the substrate with a first reactant comprising a tungsten oxyhalide,
wherein the oxyhalide adsorbs on the substrate [0006, 0013, 0016, 0026, 0027 last 3
lines] which in fact forms adsorbed tungsten oxyhalide;
contacting the substrate with a third reactant comprising hydrogen, wherein the
deposition cycle is repeated to form the elemental tungsten thin film [0026, 0029, 0054,
0057]. Fu does not teach contacting with carbon monoxide gas. Kitamura-2 teaches a
method of deposition of a film comprising elemental tungsten were reducing gas is
hydrogen [0028-0030], and teaches to easily remove by products due to reaction of
tungsten precursor, introducing carbon monoxide to the chamber prior to introducing
hydrogen gas [0034-0036, 0038]. Therefore, it would have been obvious to one of
ordinary skill in the art at the time of the invention was made to have a
process of forming a thin film comprising tungsten on a substrate as Fu teaches where
a gas comprising CO is introduced to chamber prior to hydrogen reducing gas, because
it helps removing by product better. Kitamura-2 also teaches after
contacting the substrate with process gas (metal precursor), contacting it with carbon
monoxide [0038], which in fact reacts and removing oxygen from the adsorbed
metal(tungsten) precursor, and producing a tungsten halide remaining(adsorbed) on the substrate and carbon dioxide; Kitamura-2 teaches CO is added in purging gas [0036] and therefore, the produced CO from the reaction space will be removed with purge gas as well. Kitamura-2 teaches contacting the substrate (including the tungsten halide) with
a third reactant comprising H2(reducing gas) after the contacting the substrate with the
second reactant [fig. 3], which in fact removing a halide from the tungsten halide,
producing hydrogen chloride and the elemental tungsten thin film (formation of
elemental tungsten and when the precursor is tungsten oxychloride, then the hydrogen
halide is HCI), which in fact is removed by purging from the reaction space. Fu does not
teach annealing process. Fisher teaches forming tungsten film and also teaches
annealing the film to modify the film properties [0071]. Therefore, it would have been
obvious to one of ordinary skill in the art at the time of the invention was made to have a
process of forming a thin film comprising tungsten on a substrate as Fu and Kitamura-2
teach where the tungsten film in annealed after deposition because it helps to improve
the film properties.
Claim 2 is rejected as Fu teaches deposition is via CVD using gas phase
reactions of two or more chemical species. [0016], therefore two or more of contacting
the substrate with the first reactant, contacting the substrate including the adsorbed
tungsten oxyhalide with a second reactant, and contacting the substrate including the
tungsten halide with a third reactant comprising H2-overlap
Claim 5 is rejected as Fu teaches the tungsten precursor comprises WOCI4 [Fu
0054].
Claim 7 is rejected as Fu teaches the resulting film would have too much oxygen
incorporation [0059], therefore substrate have to be contacted with an oxygen
reactant (due to dissociation of precursor).
Claims 7-8 are rejected. Kitamura-2 teaches contacting the substrate with an
oxygen reactant comprising ozone (O3), N2O, NO2 [0021]. Therefore, it would have
been obvious to one of ordinary skill in the art at the time of the invention was made to
have a process of forming a thin film comprising tungsten on a substrate as Fu, and
Kitamura-2 teach where the substrate exposes to(O3), N2O, NO2, because they are
also reducing gases.
Claim 21 is rejected. Fu teaches film resistivity is less than 50 umΩcm [0044],
which includes less than 30 umΩcm the claimed range.
Claim 22 is rejected for the same reason claim 1 is rejected. Fu teaches
deposition is via CVD using gas phase reactions of two or more chemical species.
[0016], therefore two or more of contacting the substrate with the first reactant,
contacting the substrate including the adsorbed tungsten oxyhalide with a second
reactant, and contacting the substrate including the tungsten halide with a third reactant
comprising H2-overlap. Fu also comprising following inert gas through the
reaction space between pulses of reactants (purging the reaction space of produced
carbon dioxide and hydrogen chloride from reaction) [e.g., Fu 0040, 0053]. Fisher
teaches annealing is done in oxygen environment [0071].
Claim 24 is rejected as Fisher teaches annealing is done at high
temperature(1000C) under hydrogen peroxide gas and oxygen and hydrogen gas
[0071] which obviously results in decomposition of hydrogen peroxide to form water.
Response to Arguments
Applicant's arguments filed 04/01/26 have been fully considered but they are not
persuasive. The applicant argues the references do not teach filling a gap with tungsten,
however, Jandi teaches filling the gap with bulk tungsten with sequential CVD or ALD (see claim rejection above, 0078), where in each sequential CVD or ALD cycles CO gas is used.
The applicant argues Kitamura does not teach adsorbed tungsten oxyhalide, however Fu teaches the precursor is oxyhalide and therefor after adsorption of oxyhalide on surface of substrate carbon monoxide inherently remove oxygen from it and leave tungsten halide on surface.
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 TABASSOM TADAYYON ESLAMI whose telephone number is (571)270-1885. The examiner can normally be reached M-F 9:30-6.
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/TABASSOM TADAYYON ESLAMI/Primary Examiner, Art Unit 1718
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