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 .
Election/Restrictions
Applicant’s election without traverse of Species A in the reply filed on 6/23/26 is acknowledged.
Claim 18 is withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected species, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 6/23/26. Claims 1-17 and 19-20 are pending examination.
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.
Claim(s) 1-2, 4-5, 10-11, 13-17, and 19-20 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Suzuki (US 2009/0065939; hereafter Suzuki).
Claim 1: Suzuki teaches a method for area selective deposition, (see, for example, abstract, Fig 2) the method comprising:
providing a substrate (patterned substrate (25)) in a process chamber (10), the substrate containing a growth surface (such as exposed area at bottom of trench of 302) and a non-growth surface (such as 314 or 316) (see, for example, Fig 2-4, [0025], [0030]);
and selectively depositing a metal-containing film on the growth surface relative to the non-grown surface (see, for example Fig 2B, [0025]) by:
exposing the substrate to a first gas flow containing carbon monoxide (CO) gas to form adsorbed CO on the substrate (see, for example, Fig 2B, [0021-25]),
and exposing the substrate to a second gas flow containing a metal carbonyl precursor (such as Ru3Co12), wherein the adsorbed CO reduces decomposition rate of the metal carbonyl precursor on the non-growth surface (see, for example, Fig 2B, [0021-0025], [0035], [0047-0048]).
Claim 2: Suzuki has taught wherein the first and second flows are comprised of a shared CO source and wherein the system comprises a gas supply system with one or more control valves, filters, and mass flow controllers; as the flow of CO taught to be mixed with metal carbonyl stems from the same CO source, one could interpret the contribution of the CO flow from the shared source as inclusive of the first gas flow temporally overlapping with the second as the flow of the common CO occurs during both steps. (See, for example, Fig 3-4, [0035-37], [0048-54]).
Claims 4-5: Suzuki further teaches wherein a first material containing the non-growth surface contains a dielectric material (304) and a second material containing the growth surface contains a metal / metal containing material (metallization layer 302), and wherein the non-growth surface has a different chemical composition than the growth surface (see, for example, [0024], Fig 2A).
Claims 10-11, and 13: Suzuki further teaches wherein the second flow metal carbonyl precursor includes Ru3Co12 (see, for example, abstract). Claim 11 only conditionally limits the second metal carbonyl precursor of claim 10, the teaching in Suzuki of the first metal carbonyl precursor thus meets the full scope of claim 11.
Claim 14: wherein the metal-containing film contains Ru (see, for example, [0025]).
Claim 15: Suzuki further teaches heating the substrate to a temperature between about 170-190 degrees Celsius (see, for example, [0019]).
Claim 16: Suzuki further teaches maintaining a gas pressure below about 15 Torr in the process chamber (such as between 1mTorr and 1000m Torr, such as 100mTorr) (see, for example, [0019], [0044]).
Claim 17: Suzuki further teaches the selectively depositing the metal-containing film is a chemical vapor deposition (CVD) process (TCVD) (see, for example, [0025]).
Claim 19: refer to the rejection of claims 1, 10-11, 13-14, above wherein Suzuki further teaches the second gas flow is formed by vaporizing triruthenium dodecacarbonyl (Ru.sub.3(CO).sub.12) in the presence of CO carrier gas (see, for example, [0025], [0037], and [0048]), and wherein the first gas flow at least precedes the second gas flow (see, for example, [0025] as it at least pretreats the surface prior to second gas flow).
Claim 20: refer to rejections of claims 5 and 19 above.
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.
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.
Claim(s) 2-3 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki.
Claim 2-3: Suzuki teaches the method of claim 1 (above). And further teaches wherein the first flow is used to pretreat the surface, thus teaching that the flow at least is initiated prior to the second flow, but is silent as to whether it is ceased before the second flow is initiated. But it is asserted that with respect to claims 2-3, the disclosure of Suzuki would inherently teach one of the two alternative scenarios presented in claim 1-2 as the first flow either is shut off before the second is started (reading on claim 2) or at some point thereafter (reading on claim 3). Alternatively Suzuki has taught wherein the first and second flows are comprised of a shared CO source and wherein the system comprises a gas supply system with one or more control valves, filters, and mass flow controllers; and wherein such a system readily controls the relative amount of metal precursor and CO over the duration of the process (See, for example, Fig 3-4, [0035-37], [0048-54]). Alternatively although no explicit embodiment is taught with respect to the timing of the stopping of the first CO flow relative to the initiation of the second flow, it would have been obvious to one of ordinary skill in the art at the time before the effective filing date of the claimed invention to have incorporated stopping either before or after the start of the second flow since the retention of CO flow would predictably serve as means to modulate overall precursor concentration, and/ or since the selection of any order of performing process steps is prima facie obvious in the absence of new of unexpected results (In re Burhans, 154 F.2d 690, 69 USPQ 330 (CCPA 1946)).
Claim(s) 2 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki as applied to claim 1 above, and further in view of Ishizaka (US2016/0343817; hereafter Ishizaka’817).
Claim 2: Suzuki teaches the method of claim 1 above, wherein the first flow is used to pretreat the surface, thus teaching that the flow at least is initiated prior to the second flow, but is silent as to specifically whether it is ceased before the second flow is initiated. Ishizaka’817 is directed to a method of metal (further Ru) deposition onto metallic surfaces from metal carbonyl (further Ru3(CO)12)/CO mixes, and further with CO pretreatment (See, for example, abstract, Fig 4-8, [0029]). Ishizaka’817 teaches wherein CO flow both pretreats and mixes with the metal carbonyl to provide controllable periods of pretreatment, deposition, and post-treatment; and wherein the first gas flow temporally overlaps with the second gas flow resulting in greater controlled relative CO ratios to yield greater control of film morphology (See, for example, abstract, Fig 4-8, [0080-0085]). Therefore it would have been obvious to one of ordinary skill in the art at the time before the effective filing date of the claimed invention to have incorporated first flow temporally overlapping the second gas flow as it has been demonstrated as a predictable sequence in the art to achieve deposition of Ru metal films, and further as it provides for greater control of film morphology.
Claim(s) 3 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki as applied to claim 1 above, and further in view of Yu et al (US2017/0241014; hereafter Yu’014).
Claim 3: Suzuki teaches the method of claim 1 above, wherein the first flow is used to pretreat the surface, thus teaching that the flow at least is initiated prior to the second flow, but is silent as to specifically whether it is ceased before the second flow is initiated. Yu’014 is directed to a method of ruthenium metal deposition onto metallic surfaces from Ru carbonyl (further Ru3(CO)12)/CO mixes, and further with CO pretreatment (See, for example, abstract, Fig 2, [0029]). Yu’014 teaches wherein stoppage of the CO pretreatment prior to initiation of the Ru3(CO)12)/CO mix achieves predictable deposition of Ru metal, and further provides for more uniform and continuous Ru metal films onto metallic surfaces with improved electrical properties (See, for example, [0033]). Therefore it would have been obvious to one of ordinary skill in the art at the time before the effective filing date of the claimed invention to have incorporated stopping the CO pretreat first flow before the start of the second flow since the stopping of CO flow prior to Ru3(CO)12)/CO flow has been demonstrated as a predictable sequence in the art to achieve deposition of Ru metal films, and further as it provides for more uniform and continuous Ru metal films on metallic areas with improved electrical properties.
Claim(s) 6-7 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki as applied to claim 1 above, and further in view of Ishizaka et al (US 2010/0248473; hereafter Ishizaka).
Claims 6-7: Suzuki teaches the method of claim 1 (above), but does not explicitly teach the selectively depositing further comprises: exposing the substrate to a third gas flow prior to exposing the substrate to the second gas flow, the third gas flow containing a small molecule inhibitor (SMI) or a self-assembled monolayer precursor. Ishizaka is similarly directed to a method of selective deposition of metal films, further like Suzuki specifically to selective deposition to bottom trench surfaces relative to sidewalls, and further utilizing metal precursors comprising metal carbonyl precursors, further still a mixture of Ru3CO12 and CO (See, for example, abstract, [0008-0009], [0090], Fig 4A-D). Ishizaka teaches wherein incorporating exposing the pattern substrate to a gas flow containing a small molecule inhibitor / self assembly monolayer precursor, such as including silane, prior to exposure with the metal depositing second flow results in the generation of enhanced selectivity by generation of a hydrophobically modified surface which limits / blocks metal deposition thereon (see, for example, Fig [0066-0069], Fig 4A-C). Therefore it would have been obvious to one of ordinary skill in the art at the time before the effective filing date of the claimed invention to have incorporated exposing the substrate to a third gas flow prior to exposing the substrate to the second gas flow, the third gas flow containing a small molecule inhibitor (SMI) or a self-assembled monolayer precursor, further a silane, since such an incorporation would predictably achieve the intended desire to enhance the selectivity of metal deposition to bottom of trench metallic features vs dielectric sidewalls by introducing hydrophobic modification.
Claim(s) 6-9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki as applied to claim 1 above, and further in view of Yu et al (US 2020/0343136; hereafter Yu).
Claims 6 and 8: Suzuki teaches the method of claim 1 (above), but does not explicitly teach the selectively depositing further comprises: exposing the substrate to a halogen-containing catalyst that promotes the deposition of metal-containing film on the growth surface, nor exposing the substrate to a third gas flow prior to exposing the substrate to the second gas flow, the third gas flow containing a small molecule inhibitor (SMI) or a self-assembled monolayer precursor. Yu is similarly directed to a method of selective deposition of metal films, further like Suzuki, it is specifically to selective deposition to trench surfaces relative to upper fields, and further utilizing metal precursors comprising metal carbonyl precursors, further including Ru (See, for example, abstract, [0005-0007], [0034], Fig 2-4). Suzuki further teaches wherein initial metallic surfaces can be modified by a exposure to a halogen- containing compound which serves as a catalyst for ruthenium formation thereon [0025], [0068]). The halogen exposure can further be used in combination with deactivating means comprising subsequent flow of hydrogen or ammonia to enhance the selectivity of ruthenium formation achieved from subsequent ruthenium precursor flow deposition (See, for example, Fig 4, [0010-11], [0045-0046] [0065], [0069]). Therefore it would have been obvious to one of ordinary skill in the art at the time before the effective filing date of the claimed invention to have incorporated exposing the substrate to a halogen-containing species since it serves predictably as a catalyst that promotes the deposition of metal-containing film on desired surfaces, and / or it would have been obvious to one of ordinary skill in the art at the time before the effective filing date of the claimed invention to have incorporated exposure to such halogen-containing species in combination with exposure to a third flow of SMI (such as hydrogen / ammonia) since the combination of these extra flows would further predictably enhance the selectivity of the metal film deposition process.
Claim 7: Yu further teaches wherein the SMI includes hydrogen, or ammonia (See, for example, [0010-11], [0045-0046] [0065], [0069]).
Claim 9: Yu further teaches wherein the halogen-containing catalyst includes I2, CH3I, or C2H5I. (see, for example, [0036]).
Claim(s) 12 is/are rejected under 35 U.S.C. 103 as being unpatentable over Suzuki as applied to claim 1 above, and further in view of McFeely et al (US 2008/0315429; hereafter McFeely)
Claim 12: Suzuki teaches the method of claim 1 (above), wherein a noble metal carbonyl (Ru3(CO)12) is used as a precursor for the CVD deposition of Ru metal films, but it does not explicitly teach wherein the second gas flow containing the metal-carbonyl precursor includes Ru(CO)5. McFeely similarly teaches method wherein a noble metal carbonyl is used as a precursor for the CVD deposition of Ru metal films (see, for example, abstract, [0002]). McFeely further teaches wherein either or both of (Ru3(CO)12) or Ru(CO)5 perform predictably / suitably as the ruthenium carbonyl precursor compound to facilitate Ru metal cap deposition (see, for example, [0002], [0022], [0049], claim 6). Therefore it would have been obvious to one of ordinary skill in the art at the time before the effective filing date of the claimed invention to have incorporated the second gas flow containing the metal-carbonyl precursor includes Ru(CO)5 as such a material is known in the art as a predictable and suitable ruthenium carbonyl precursor compound to facilitate Ru metal cap deposition via CVD, and since where two known alternatives are interchangeable for a desired function, an express suggestion to substitute one for the other is not needed to render a substitution obvious. In re Fout, 675 F.2d 297,301 (CCPA 1982); In re Siebentritt, 372 F.2d 566, 568 (CCPA 1967).
Conclusion
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/NATHAN H EMPIE/ Primary Examiner, Art Unit 1712
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