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 Claim 20 is withdrawn.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 1, 6, 8, and 13 are amended. Claims 5, 7, and 12 are cancelled. Claims 21-23 are newly added.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 14 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 14, the claim requires that the plasma is generated before or while the wafer is contacted with the second reactant, however, claim 1 has been amended so that the plasma is generated from a gas consisting of H2, a hydrocarbon, or a combination thereof, where the second reactant can be a nitrogen precursor, an oxygen precursor, or a carbon precursor. Therefore, it is unclear how the plasma can be generated while the wafer is contacted with the second reactant when the second reactant can comprise gases other than hydrogen, a hydrocarbon, or a combination thereof. For the purposes of examination, the claim is being interpreted as though the plasma consists of hydrogen, a hydrocarbon, or a combination thereof, where if the plasma is done while exposing to the second reactant, the second reactant must be a hydrocarbon. Appropriate action is required without adding new matter.
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).
Claims 9 and 10 are 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.”
Regarding claim 10, Kumar in view of Koyama and Kubota and alternatively further in view of Hausmann suggest the process of claim 9. As discussed above, they suggest forming a directional plasma towards the substrate such that 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 plasma so that the ions and plasma effluents are delivered substantially towards the top and the bottom of the patterned structure because Kumar teaches forming a directional plasma to modify the top surface by applying a bias and Hausmann indicates that applying a directional plasma towards the substrate modifies a top surface such that it will be expected to provide the directional plasma as desired.
Claims 1-4, 6, 8-11, 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 10, Asrani in view of Chatterjee and Koyama suggest the process of claim 9. 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). 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 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.
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 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 10/21/2025 have been fully considered.
In light of the amendment to the specification, the previous drawing objection is withdrawn.
In light of the amendments to the claims, a new 112(b) rejection has been made over claim 14 as discussed above.
In light of the amendments to claim 1, Applicant’s arguments are considered persuasive, therefore, new rejections have been made as discussed above.
Regarding Applicant’s arguments over claim 21, it is noted that Hausmann in view of Koyama is still considered to suggest claim 21 and 22 for the reasons discussed above, where the hydrogen plasma and the nitrogen exposure occur simultaneously.
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 CHRISTINA D MCCLURE whose telephone number is (571)272-9761. The examiner can normally be reached Monday-Friday, 8:30-5:00 EST.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Gordon Baldwin can be reached at 571-272-5166. 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.
/CHRISTINA D MCCLURE/Examiner, Art Unit 1718 /GORDON BALDWIN/Supervisory Patent Examiner, Art Unit 1718