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 .
Status of the Claims
Claims 1-4, 6, 8-11, 13-19, and 21-23 are pending and rejected. Claim 20 is withdrawn. Claims 10, 11, and 14 are amended. Claims 5, 7, and 12 are cancelled.
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 6/23/2026 has been entered.
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 text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
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.
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.
Claims 1-4, 6, 8, 14-16, 18, 19, 21, and 23 are rejected under 35 U.S.C. 103 as being unpatentable over Kumar, US 2018/0323057 A1 in view of Koyama, US 7,851,318 B2 and alternatively further in view of Hausmann, US 2019/0057858 A1.
Regarding claims 1 and 8, Kumar teaches a method of film deposition (abstract), the method comprising:
providing a wafer including a patterned structure having a top, a bottom and a sidewall (providing a patterned substrate having one or more features, 0003, where the features include tops, bottoms, and sidewalls, 0034, 0042, and Fig. 4A, and where the substrate may be a wafer, 0024); and
forming a film on the wafer by a cyclical deposition (where the deposition process is repeated, 0009 and Fig. 3, so as to provide a cyclical process) process comprising a cycle of:
contacting the wafer with a first reactant comprising a silicon precursor to form an intermediate layer over the patterned structure of the wafer, wherein the silicon precursor comprises a silicon-nitrogen bond and includes no halogen (exposing the patterned substrate to a silicon-containing precursor to adsorb onto surfaces of the one or more features, thereby forming an adsorbed or intermediate layer, 0003, 0042, and Fig. 4B, where the precursor includes aminosilanes such as mono-, di-, tri, and tetra-aminosilane, t-butylaminosilane, methaylaminosilane, 0044 and 0047, so as to provide a silicon precursor comprising a silicon-nitrogen bond and no halogen);
generating a plasma from a gas consisting of H2, a hydrocarbon, or a combination thereof to modify the intermediate layer by delivering plasma anisotropically towards the top and the bottom of the patterned structure (performing a post-dose treatment operation to preferentially remove the adsorbed layer at tops of the one or more features, 0003, where the post-dose treatment is performed using a plasma generated from non-oxidizing gases such as any of nitrogen, argon, hydrogen, ammonia, helium, and CxHy, where x is an integer between and including 1-5 and y is an integer between and including 4-16, 0011, such that since any one of the gases can be used this indicates that the gas can consist or hydrogen and/or the hydrocarbon gas, and where the plasma is performed with a bias between 0 W and about 1000 W, where the bias is used to control the directionality of the plasma generated, 0050, such that the plasma will be delivered anisotropically to the substrate); and
contacting the wafer with a second reactant to form a material layer, the second reactant including at least one selected from the group consisting of a nitrogen precursor, an oxygen precursor and a carbon precursor (exposing the patterned substrate to a reactant and igniting a plasma to form a silicon-containing film over the patterned substrate, 0003, where the reactant is an oxygen-containing gas, a carbon-containing gas, or a nitrogen-containing gas, 0058-0059, and 0061-0062).
They teach that a carrier gas may flow continuously or it may flow only during one or more of the purge phases (0040, 0069, and Fig. 5). Therefore, when the carrier gas flows only during the purge phases, the post-dose treatment can generate excited species from a gas consisting of hydrogen and/or the hydrocarbon precursor. While they do not specifically teach that the plasma is directional towards the top and bottom of the patterned features, since they teach that the plasma is provided with a bias of between 0 W and about 1000 W, where the bias controls the directionality of the plasma generated, where the plasma removes precursor from the top surface or removes hydroxyl bonds on the surface of the substrate (0050), it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that the plasma will be provided anisotropically towards the substrate because it will direct the plasma to the surface where modification is desired.
They do not teach the ions in the plasma.
Koyama teaches irradiating a semiconductor substrate with accelerated hydrogen ions (abstract). They teach that in a hydrogen plasma, hydrogen ion species such as H+, H2+, and H3+ are present (Col. 16, lines 61 through Col. 17, line 19).
From the teachings of Koyama, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that H+, H2+ and H3+ ions will be present in the plasma because they teach that such ions are present in hydrogen plasmas. Therefore, the plasma will comprise H+, H2+, and H3+ ions as required by claims 1 and 8.
Alternatively:
They do not specifically teach that the plasma is anisotropic towards the top and bottom of the patterned structure.
Hausmann teaches modifying a conformal film deposited on a substrate by ALD by exposing the substrate to a directional plasma (abstract). They teach providing a directional plasma to areas of SiN film deposited on feature on the substrate such as the top and bottom (0037 and Fig. 5A and 6A). They teach tuning the plasma to modify the deposited film on the feature (0036). They teach that by appropriately biasing the substrate, ions in the plasma will preferentially modify the film deposited on the horizontal surfaces (0050). Therefore, Hausmann teaches that applying a bias to the substrate during plasma treatment provides a directional plasma towards the horizontal surfaces of a substrate having features.
From the teachings of Kumar and Hausmann, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have applied the directional plasma towards the substrate to as to be towards the top and bottom of the patterned structure due to the directionality and patterns because Hausmann teaches that applying a bias to the substrate during plasma treatment provides a directional plasma towards the horizontal surfaces of a substrate having features and Kumar teaches applying a bias for forming a directional plasma for modifying top surfaces of a substrate having features such that it will be expected to direct the plasma to the top surfaces for removing the precursor at the top surfaces while also providing plasma in a direction towards the bottom features since they are parallel.
Regarding claims 2-4, Kumar in view of Koyama and alternatively further in view of Hausmann suggest the process of claim 1. Kumar further teaches that the aminosilane is BTBAS or trisilylamine (TSA) (0047), so as to meet the requirements of claims 2-4. They also teach using mono-, di-, tri-, and tetra-aminosilane, t-butylaminosilane, methylaminosilane (0047), meeting the requirements of claim 3.
Regarding claim 6, Kumar in view of Koyama and alternatively further in view of Hausmann suggest the process of claim 1. Kumar further teaches that the gas for the post-dose treatment includes gases such as hydrogen and CxHy, where x is an integer between and including 1-5 and y is an integer between and including 4-16 (0011). As noted above the post-dose treatment gas can comprise one or more gases such that it can consist of hydrogen and/or the hydrocarbon. Therefore, the gas consists of hydrogen and/or an alkane having 1-5 carbon atoms so as to be within the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.”
Regarding claim 14, Kumar in view of Koyama and alternatively further in view of Hausmann suggest the process of claim 1. As noted above, the plasma is generated before the wafer is contacted with the second reactant (Fig. 3).
According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.”
Regarding claim 15, Kumar in view of Koyama and alternatively further in view of Hausmann suggest the process of claim 1. Kumar further teaches that the film is deposited and the post-dose treatment operation is performed at a pedestal temperature between about 25°C and about 650°C (0007) or such as about 200°C (0041). Therefore, the temperature will overlap or be within the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.”
Regarding claim 16, Kumar in view of Koyama and alternatively further in view of Hausmann suggest the process of claim 1. Kumar further teaches that the cyclical deposition process comprises ALD (abstract).
Regarding claims 18 and 19, Kumar in view of Koyama and alternatively further in view of Hausmann suggest the process of claim 1. Kumar further teaches that the material layer is any of a silicon oxide, silicon nitride, and silicon carbide (0008). They teach that when the film is a nitride, the second reactant is a nitrogen precursor (0062).
Regarding claims 21 and 23, Kumar in view of Koyama and alternatively further in view of Hausmann provide the shared steps of claims 1 and 21. Kumar further teaches that chamber is optionally purged after exposing the substrate to the precursor (0048 and Fig. 3). They teach that the chamber is optionally purged after the post-dose treatment process (0057 and Fig. 3). They teach that the chamber is optionally purged to remove any residual byproducts after exposure to the second reactant (0064 and Fig. 3). Therefore, the cyclic process can consist of claimed step (a), (b), (c), (d), and (e), since the purging after the post-dose treatment is optional, where the cycle can consist of (a), then optionally (b), then (c), then (d), and then optionally (e).
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Kumar in view of Koyama and alternatively further in view of Hausmann as applied to claim 1 above, and further in view of Kubota, US 2022/0108881 A1.
Regarding claim 9, Kumar in view of Koyama and alternatively further in view of Hausmann suggest the process of claim 1.
They do not teach the frequency of the hydrogen plasma.
Kubota teaches methods of forming silicon nitride by depositing a silicon oxide layer overlying a sidewall of a surface using a cyclical deposition process, depositing a silicon nitride layer overlaying the silicon oxide layer, and exposing the silicon nitride layer to activated species generated from a hydrogen-containing gas (abstract). They teach that the hydrogen-containing gas can include hydrogen and an inert gas, where the volumetric ratio of the hydrogen to inert gas can range from about 10 to about 0 (0045), indicating that the gas does not require inert gas. They teach that the activated species can be generated by a direct plasma where the activated species are directional and can preferentially interact with the silicon nitride layer on horizontal surfaces (0046). They teach that a plasma frequency can be between about 10 MHz and about 2.5 GHz (0046).
From the teachings of Kubota, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Kumar in view of Koyama and alternatively further in view of Hausmann to have used a frequency of about 10 MHz to about 2.5 GHz because Kubota teaches that such a frequency can be used to generate a directional plasma from hydrogen gas such that it will be expected to generate the plasma as desired. Therefore, the plasma frequency will overlap the claimed range. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.”
Claims 1-4, 6, 8, 9, 11, 13-15, 18, 19, 21, and 23 are rejected under 35 U.S.C. 103 as being unpatentable over Asrani, US 2023/0386829 A1 in view of Chatterjee, US 2014/0073144 A1 and Koyama, US 7,851,318 B2.
Regarding claims 1 and 8, Asrani teaches a method of film deposition (abstract), the method comprising:
providing a wafer including a patterned structure having a top, a bottom and a sidewall (where the substrate has at least one feature having an opening width, one or more sidewall, and extends a depth from a top surface of the substrate to a bottom, 0006 and Fig. 3A-C, where the substrates include semiconductor wafers, 0016); and
forming a film on the wafer by a cyclical deposition (where the process of deposition, modification, and conversion is cyclic, 0039 and Fig. 2) process comprising a cycle of:
contacting the wafer with a first reactant comprising a silicon precursor to form an intermediate layer over the patterned structure of the wafer, wherein the silicon precursor includes no halogen (delivering one or more precursors to a processing region of the chamber housing the structure, where the precursors include one or more silicon-containing precursors such as silane, 0043, 0061, and Fig. 2, such that the precursor includes one with no halogen, and where a silicon-containing material deposits on the substrate, 0043-0044 and Fig. 2);
generating a plasma from a gas consisting of H2, a hydrocarbon, or a combination thereof to modify the intermediate layer by delivering plasma anisotropically towards the top and the bottom of the patterned structure (where an etching or modifying process is performed using a plasma containing diatomic hydrogen, where in the modifying process the silicon-containing precursor flow may be halted, the processing region may be purged, the flow of inert gases may also be halted, 0051, indicating that the modification process includes generating a plasma from a gas consisting of hydrogen, where the plasma is delivered with a bias to provide directionality so as to draw plasma effluents to the substrate which may bombard the film, 0052, 0054-0055, and claim 7, indicating that the plasma will be delivered anisotropically towards the top and the bottom of the patterned structure since it is directional towards the substrate and because it is indicated at modifying the top and bottom of the feature and providing plasma effluents that penetrate the bottom of the feature, 0052 and 0055); and
contacting the wafer with a second reactant to form a material layer, the second reactant including at least one selected from the group consisting of a nitrogen precursor, an oxygen precursor and a carbon precursor (where the formed silicon material is converted by contacting with a nitrogen-containing precursor, an oxygen-containing precursor, and/or a carbon-containing precursor, 0059 and Fig. 2).
They teaches that the silicon-containing precursors that may be used include silane, disilane, or other organosilanes, TEOS, higher order silanes as well as any other silicon-containing precursor may be used in silicon-containing film formation (0061). They teach forming a flowable silicon film in the features (abstract).
They do not teach using a precursor having a Si-N bond.
Chatterjee teaches a method of forming a dielectric layer by depositing a silicon-containing film by CVD using a local plasma (abstract). They teach that the silicon-containing film is flowable during deposition at low substrate temperature (abstract). They teach that a silicon precursor (e.g. a silylamine, higher order silane, or halogenated silane) is delivered to the substrate processing region and excited in a local plasma (abstract). They teach that a second plasma gas vapor is combined with the silicon precursor in the substrate processing region and may include ammonia, nitrogen, argon, hydrogen, and/or oxygen (abstract). They teach that silicon precursors may include silylamines such as H2N(SiH3), HN(SiH3)2, and N(SiH3)3, a higher order silane such as SinH2n+2, where n>=3 (0019).
From the teachings of Chatterjee, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Asrani to have used a silylamine such as H2N(SiH3), HN(SiH3)2, or N(SiH3)3 as the precursor because Chatterjee teaches that such precursors are suitable for forming a flowable film as an alternative to those taught by Asrani and because Asrani teaches that any other silicon-containing precursor can be used such that it will be expected to provide the flowable silicon-containing material during the deposition phase. Therefore, the precursor will include a Si-N bond and no halogen.
They do not teach the ions in the plasma.
Koyama teaches irradiating a semiconductor substrate with accelerated hydrogen ions (abstract). They teach that in a hydrogen plasma, hydrogen ion species such as H+, H2+, and H3+ are present (Col. 16, lines 61 through Col. 17, line 19).
From the teachings of Koyama, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that H+, H2+ and H3+ ions will be present in the plasma because they teach that such ions are present in hydrogen plasmas. Therefore, the plasma will comprise H+, H2+, and H3+ ions as required by claims 1 and 8.
Regarding claims 2-4, Asrani in view of Chatterjee and Koyama suggest the process of claim 1, where it is suggested to use H2N(SiH3), HN(SiH3)2, or N(SiH3)3 as the precursor such that it will include TSA and meet the requirements of claims 2-4.
Regarding claim 6, Asrani in view of Chatterjee and Koyama suggest the process of claim 1, where Asrani teaches that the gas consists of diatomic hydrogen since flow of the other gases is halted (0051).
Regarding claim 9, Asrani in view of Chatterjee and Koyama suggest the process of claim 1. Asrani teaches using plasma power having frequencies of greater than or about 20 MHz when generating the source plasma (0046).
They do not teach the frequency for forming the hydrogen plasma.
Chatterjee teaches forming a plasma gas from gases including H2 (0020). They teach that the plasma may be ignited using radio frequencies near 13.56 MHz but that higher frequencies such as 2.4 GHz can be used (0021).
From the teachings of Chatterjee, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used a frequency of 2.4 GHz to generate the hydrogen plasma because they teach that such a frequency can be used to generate a plasma from a hydrogen gas such that it will be expected to generate the plasma as desired. Therefore, the plasma frequency will be within the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.”
Regarding claim 11, Asrani in view of Chatterjee and Koyama suggest the process of claim 10. Asrani teaches that the film has a greater thickness on the bottom and top surfaces than the sidewall surface (abstract). While they do not teach that the ions have monotonic energy, since they suggest forming the ions at a frequency within the claimed range, using H2 gas, and that the growth is thicker on the top and bottom of the features, the resulting ions are also expected to have a substantially monotonic energy distribution. According to MPEP 2112.01 I, “Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977)”.
Regarding claim 13, Asrani in view of Chatterjee and Koyama suggest the process of claim 1. Asrani teaches that the film has a greater thickness on the bottom and top surfaces than the sidewall surface (abstract).
Regarding claim 14, Asrani in view of Chatterjee and Koyama suggest the process of claim 1. Asrani further teaches that the plasma is generated before the wafer is contacted with the second reactant (Fig. 2).
Regarding claim 15, Asrani in view of Chatterjee and Koyama suggest the process of claim 1. Asrani further teaches that the process is performed at a temperature below or about 20°C (0062), so as to be within the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.”
Regarding claims 18 and 19, Asrani in view of Chatterjee and Koyama suggest the process of claim 1. Asrani further teaches that the material is converted to a silicon nitride, silicon oxide, silicon carbon nitride, or silicon oxycarbonitride (0059). They teach using nitrogen-containing precursors such as N2, N2O, NH3, N2H2, as well as any other nitrogen-containing precursors to form silicon nitride (0061), such that when forming silicon nitride, a nitrogen-containing precursor is used.
Regarding claims 21 and 23, Asrani in view of Chatterjee and Koyama suggest the shared process steps of claims 1 and 21. Asrani teaches that the processing region may be purged after flow of the silicon-containing precursor (0051). They teach that a densifying step is provided simultaneously with the modifying step (0055). Therefore, the process will consist of claimed steps (a), (b), (c), and (d) in this order (Fig. 2).
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over Asrani in view of Chatterjee and Koyama as applied to claim 1 above, and further in view of Cheng, US 2023/0340661 A1.
Regarding claim 10, Asrani in view of Chatterjee and Koyama suggest the process of claim 1. Asrani teaches that beneficially, plasma effluents delivered more directionally may penetrate the remaining film formed at the bottom of the feature and may reduce hydrogen incorporation to densify the film, where densifying the top region is also desirable to protect the underlying material from damage (0055). They teach drawing plasma effluents to the substrate to bombard the film and cause densification of the deposited materials (0052). They teach that the plasma treatment modifies the film at the top and bottom of the features (0051). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed the hydrogen ions to be substantially unidirectional so that they are delivered substantially toward the top and bottom of the patterned structure relative to the sidewall because Asrani indicates that it is desirable to have a directional plasma to densify/modify the top and bottom of the film on the substrate such that by directing the plasma substantially to the top and bottom it will be expected to densify the desired regions. Therefore, the portions at the top and bottom of the intermediate layer are modified.
As to the material on the sidewall, Asrani teaches that the material on the sidewall is selectively etched over the top material and the bottom material (0006). They teach that the process may limit of prevent sidewall coverage during trench fill (0024). They teach that by adjusting the source power and the bias power during plasma, an etching operation may be performed, which may reduce sidewall coverage of the deposited material while limiting any effect on the previously treated materials (0052). They teach adjusting the plasma to increase etching of the deposited material along the sidewalls (0056).
Therefore, they indicate that it is desirable to remove and reduce sidewall coverage, but they do not indicate if any material remains.
Cheng teaches depositing a film on a substrate by PECVD or PEALD where the film is deposited to fill a gap (0031). They teach that the film comprises silicon (0033). They teach that during deposition, the substrate is exposed to one or more process gases and/or conditions that form the film (0038 and Fig. 3A-D). They teach determining whether the gap has been completely filled and if not, the method moves to an etching treatment (0049 and Fig. 2). They teach that the etching treatment etches the non-conformal film, where it etches a greater thickness of the film on the sidewall than at the top or bottom (0051 and Fig. 3A-D). They teach that the directional plasma treatment preferentially modifies the top film and bottom film with respect to the sidewall film so that the modified film is more etch resistant (0052). They teach that the etching process removes substantially all of the sidewall film from the feature and leaving some of the top and bottom film (0053 and Fig. 3C). They teach that removing substantially all of the sidewall film means that at least about 95% of the surface area of the sidewalls has been etched (0053 and Fig. 3C). They teach that removing substantially all of the sidewall film comprises a nucleation delay for a subsequent deposition process (0053). They teach that the gas for etching consists essentially of H2 (0054). Therefore, Cheng provides a method similar to that of Asrani of depositing a material for gapfilling and then treating with a directional hydrogen plasma to modify the film on the top and bottom of the features while etching the material on the sidewall, where etching at least 95% of the material is desirable for the gapfilling process.
From the teachings of Cheng, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Asrani to have etched at least 95% of the film during the directional plasma treatment because Cheng teaches that such a range is suitable for removing sidewall material in a gapfilling process such that it will be expected to provide an acceptable etching amount for the process. Therefore, in the process of Asrani in view of Chatterjee, Koyama, and Cheng, the etching will be done so that 5% or less material remains on the sidewalls of the structure, such that the range includes leaving portion of the intermediate layer on the sidewall of the patterned structure. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.”
Claim 16 is rejected under 35 U.S.C. 103 as being unpatentable over Asrani in view of Chatterjee and Koyama as applied to claim 1 above, and further in view of Kang, US 2014/0106574 A1.
Regarding claim 16, Asrani in view of Chatterjee and Koyama suggest the process of claim 1. Asrani teaches depositing a flowable silicon film for gapfilling, where the film is converted to a nitride, oxide, carbide, oxynitride, oxycarbide, carbon nitride, oxycarbonitride, etc. by reaction with a conversion precursor (abstract and 0059).
They do not teach that the gapfilling process is an ALD process.
Kang teaches method for filling one or more gaps on a substrate using PEALD (abstract). They teach introducing a first reactant in vapor phase into a reaction chamber so that is adsorbs on the substrate surface, introducing a second reactant in vapor phase into the chamber to adsorb onto the substrate surface, and expose the surface to plasma to drive a reaction between the first and second reactants (0005). They teach that the process is repeated to form additional layers to fill the gap (0005). They teach that the first reactant is a silicon-containing reactant and the second reactant is an oxidizing reactant (0006). They teach that the gap is filled as a bottom-up mechanism (0006). They teach that the gap-filling material may be silicon oxide (0010).
From the teachings of Kang, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Asrani in view of Chatterjee and Koyama to have deposited the film using a PEALD process by supplying the silicon precursor, etching, and then converting and repeating because Kang teaches that such a process is suitable for bottom-up gapfilling using a silicon precursor and converting it to an oxide for filling with silicon oxide such that it will be expected to provide a suitable cyclic method for filling the gap while also providing the modification plasma for modifying the films on the top and bottom of the features.
Claim 17 is rejected under 35 U.S.C. 103 as being unpatentable over Asrani in view of Chatterjee and Koyama as applied to claim 1 above, and further in view of Chen, US 2019/0259598 A1.
Regarding claim 17, Asrani in view of Chatterjee and Koyama suggest the process of claim 1. Asrani teaches using nitrogen-containing precursors such as N2, N2O, NH3, N2H2, as well as any other nitrogen-containing precursors to form silicon nitride during the conversion process (0061). Chatterjee teaches that silylamines or halogenated silanes such chlorinated silanes can be used, suggesting that they have similar reactivities (0019).
They do not teach forming -NH2 groups on the structure.
Chen teaches methods for forming a silicon nitride film on a substrate in a deposition chamber (abstract). They teach forming the silicon nitride film on a substrate by sequentially exposing the substrate to a sequence of processing gases that includes, a first silicon halide precursor that absorbs onto a surface of the substrate to form an absorbed layer of the silicon halide; a first reacting gas comprising N2 and a hydrogen-containing gas and one or both of Ar and He (0005). They teach that the hydrogen-containing gas may include at least one of H2, etc. (0005). They teach that PEALD chambers currently use RF plasm and VHF plasma, but that these sources do not allow for the production of high-quality SiN films (0020). They teach using microwave plasma sources, e.g., 2.45 GHz, for the reaction gas to form high quality SiN films because the plasma sources provide stronger molecule excitation capability and lower plasma sheath potential (0020). They teach that the ions in microwave plasma have lower energy (0020). They teach that the lower ion energy and lower plasma sheath potential result in less damage to the substrate and less metal contamination during processing (0021). They teach that the inclusion of hydrogen-containing gas in the microwave results in H* radicals which react with N* radicals formed from N2 dissociation to form NH*/NH2* radicals which absorb on the substrate surface and provide absorbing sites where the silicon precursor sticks and reacts in a subsequent ALD cycle (0032). They teach that the presence of hydrogen-containing gas in microwave plasma results in improved GPC and improved throughput (0032).
From the teachings of Chen, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used a H2/N2 plasma during the conversion step because Chen teaches depositing silicon nitride where N2 and H2 gases will result in forming absorbed NH and NH2 sites that can provide absorbing sites for the silicon-containing precursor, where since Chatterjee teaches that the silicon-containing precursor can be an silylamines or halosilane, the precursors are considered to have similar reactivity, such that it will be expected to provide the benefit of adding absorbing sites of the precursor to facilitate growth on the horizontal surfaces resulting from the conversion process. Therefore, conversion plasma will provide -NH2 surface groups on the patterned structure of the wafer.
Claims 21 and 22 are rejected under 35 U.S.C. 103 as being unpatentable over Hausmann, US 2019/0057858 A1 in view of Koyama, US 7,851,318 B2.
Regarding claims 21 and 22, Hausmann teaches a method of film deposition (0013), the method comprising:
providing a wafer including a patterned structure having a top, a bottom and a sidewall (where the substrate has a feature recessed from a surface of the substrate so as to have a bottom and sidewall, 0013, where the feature is also depicted as having a top, Fig. 6A); and
forming a film on the wafer by a cyclical deposition process consisting of a cycle of:
(a) contacting the wafer with a first reactant comprising a silicon precursor to form an intermediate layer over the patterned structure of the wafer, wherein the silicon precursor comprises a silicon-nitrogen bond and includes no halogen (where the conformal film is deposited by exposing the substrate to a silicon-containing reactant such as aminosilanes that do not include a halide, 0059-0060 and Fig. 1C, so as to provide a silicon precursor comprising a silicon-nitrogen bond, where the silicon precursor adsorbs to the substrate, 0003 and 0063, so as to form an intermediate layer, where the feature is formed in a wafer, 0095);
optionally (b) purging the chamber (where in embodiments, a purge may be used to remove vapor phase silicon-containing reactant, 0063);
(c) generating a plasma comprising hydrogen ions to modify the intermediate layer by delivering the plasma anisotropically towards the top and the bottom of the patterned structure (forming the conformal film includes N2, where reactive species such as hydrogen can be included, 0035 and 0062, where the plasma is directional, 0003, 0037, 0080, 0095, Fig. 3, and Fig. 6A-D, indicating that the plasma is anisotropic, where since the plasma will include hydrogen gas it is also expected to include hydrogen ions); and
(d) contacting the wafer with a second reactant to form a material layer, the second reactant including at least one selected from the group consisting of a nitrogen precursor, an oxygen precursor and a carbon precursor (where the reaction gas includes N2 and it is provided with the hydrogen, 0035 and 0062, where the process is repeated so as to provide a cyclical process, 0063).
Hausmann teaches that the N2-derived plasma is ion-heavy and directionally applied to create active sites on exposed horizontal surfaces to accommodate additional deposition of SiN thereon (0095). Therefore, when adding hydron into the gaseous mixture it will also be expected to provide hydrogen ions in the plasma because the plasma is indicated as being ion-heavy with nitrogen ions, indicating that the plasma generates ions.
Further, Hausmann indicates that the plasma power and nitrogen exposure can occur simultaneously (Fig. 4), such that the step of exposing the substrate to the nitrogen-containing reactant and the plasma ignition are understood to occur at the same time. Therefore, in the process of Hausmann, the steps will include claimed step (a), then optionally claimed step (b), and then claimed steps (c) and (d) together simultaneously since the hydrogen and nitrogen are provided together in the anisotropic plasma.
They do not teach the ions in the plasma.
Koyama teaches irradiating a semiconductor substrate with accelerated hydrogen ions (abstract). They teach that in a hydrogen plasma, hydrogen ion species such as H+, H2+, and H3+ are present (Col. 16, lines 61 through Col. 17, line 19).
From the teachings of Koyama, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that H+, H2+ and H3+ ions will be present in the plasma because they teach that such ions are present in hydrogen plasmas.
Response to Arguments
Applicant’s arguments dated 5/26/2026 have been fully considered.
In light of the amendment to claim 14, the previous 112(b) rejection is withdrawn.
Regarding Applicant’s argument over the directionality of Kumar, it is noted that Kumar teaches that the plasma is provided with a bias to control the directionality, where the plasma removes precursor from the top surface, providing the suggestion that the directionality of the plasma will be towards the substrate such that it is expected to be towards the top and bottom of the patterned structure because it is directed down to the substrate. Note Fig. 6 of Kumar which indicates that the process gases are provided from above the substrate such that when the plasma is directed to the top of the substrate the plasma gases will be directed towards the top and bottom of the substrate. While Applicant argues that delivering the plasma towards the top and bottom of the structure would remove molecules from both the top and bottom, the modification of the film on the top and bottom of the features will depend on various factors other than only the directionality, such as the power of the plasma, pressure, distance from the electrode, etc. Therefore, the teachings of Kumar that the plasma is biased to provide directionality of the plasma, where the plasma removed precursor from the top surface, are considered to provide the suggestion that the directionality is towards the substrate. It is noted that Hausmann also indicates that providing a bias provides a directional plasma towards the substrate.
Regarding Applicant’s argument that combining Kumar with Hausmann would remove molecules from the top and bottom of the structure, as noted above, the removal of material using plasma would be dependent on various factors other than only directionality, such as plasma power, pressure, distance from the electrode, etc. Therefore, simply providing the plasma having a directionality by applying bias as taught by Kumar, where Hausmann indicates that biasing provides directionality towards the substrate is not considered to be sufficient to indicate that the material will necessarily be removed from the bottom of the structure.
Regarding Applicant’s arguments over Asrani, Asrani specifically teaches that the plasma is delivered with a bias to provide directionality so as to draw plasma effluents to the substrate (0052, 0054-0055, and claim 7), indicating that the plasma is directed towards the substrate to as to be towards the top and bottom surfaces of the substrate. Also note Fig. 1 of Asrani which indicates that the gases are provided from the top of the substrate, further indicating that the gases will be provided from above the substrate and directed down to the substrate so as to be towards the top and bottom surfaces. They also indicate that the plasma penetrates the bottom of the features (0055), indicating that the plasm will be directed towards the bottom of the features. Specifically, since the plasma is provided from above the substrate (Fig. 1) and is directed towards the substrate, the direction of the plasma is understood to be towards the substrate so as to be towards the horizontal surfaces, i.e., downwards. Additionally, as to removing material from the bottom of the features using the directional plasma, as discussed above, the removal of the material will be dependent on other factors than only the directionality of the plasma, such as the power, pressure, spacing, etc. This is further supported by Asrani indicating that increasing the plasma power during modification increases the amount of material etched from the bottom of the structure, indicating that plasma power and bias power may be adjusted to control the etching (0053).
Applicant’s arguments over claim 10 are persuasive and therefore the rejection has been modified as indicated above.
Conclusion
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718
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