DETAILED ACTION
In the amendment filed on June 11, 2025, claims 1 – 20 are pending. Claims 1, 7, 8, 10, 11, 13, 14 have been amended. Claims 19, 20 have been added. Claim 18 has been withdrawn from consideration.
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 present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Specification
The disclosure is objected to because of the following informalities: Paragraph [0036] of the instant specification recites the word “harosilane”. This appears to be a misspelling of “halosilane” . Furthermore, the specification appears to use different words to inconsistently describe the same objects: “halogensilane” and “halosilane” both appearing in paragraph [0036].
Appropriate correction is required.
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.
Claims 13, 14 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 claims 13, 14:
As a preliminary matter, the Examiner notes that claim 14 recites “harosilane”, which appears to be a misspelling of “halosilane”.
Parent claim 1 has been amended to require that the silicon precursor comprises one or more of a silane, organosilane, or a silazane. However, claims 13 and 14 continues to recite “wherein the silicon precursor comprises …”. As written, it becomes unclear whether the silicon precursor requires an additional chemical compound among the recited chemical compounds (i.e. the silicon precursor further comprises), or if the recited chemical compounds are the required specific compounds that would satisfy the requirement of the silicon precursor being one or more of the recited “silane, organosilane, or a silazane”; rendering the claim indefinite.
Additionally, regarding claim 14:
Additionally in view of the amendment to the claims, the phrase "such as" renders the claim indefinite because it is unclear whether the limitations following the phrase are part of the claimed invention. See MPEP § 2173.05(d).
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA 35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA 35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claim 14 is rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.
Parent claim 1 has been amended to require that the silicon precursor comprises one or more of a silane, organosilane, or a silazane. However, in the interpretation of claim 14 where the recited silicon precursor is claim 14 recites that the silicon precursor can be a “harosilane”, “SiI4 and other silicon-compound species that contain at most only a halogen and hydrogen. In view of the distinction the instant specification places between silanes and halogensilanes/halosilanes, halogensilanes are not silanes under the broadest reasonable interpretation consistent with the specification. Furthermore, while halosilanes as a genus may overlap with organosilanes and/or silazanes (e.g. an organosilane with a halogen-substituted ethyl moiety, or an organosilane with a halogen also bonded to the silicon atom), the claim recites specific species that cannot be interpreted as organosilanes or silazanes (e.g. SiI4). Accordingly, claim 14 fails to include all the limitations of the claim upon which it depends.
Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
Claim Rejections - 35 USC § 102
The rejections of the claims under 35 USC § 102 in the previous Office Action are withdrawn due to Applicant amendment.
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.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claim(s) 14 and 17 is/are newly rejected under 35 U.S.C. 102(a)(1) and (a)(2) as being anticipated by Ueda et al. US 2019/0333753 A1 (hereafter “Ueda”).
Regarding claim 14:
In light of the indefiniteness of claim 14 and its improper dependent form, Ueda is directed to methods of forming silicon nitride films (Abstract). Ueda discloses that their methods comprise (Fig. 2, 5):
placing a substrate or workpiece in a reaction chamber ([0035]);
continuously flowing nitrogen gas [N2, nitrogen reactant pulse] in the reaction chamber [meeting claim 9] ([0039], [0042]);
supplying a pulse of silicon precursor into the reaction chamber ([0032], [0038], [0044]);
forming a nitrogen plasma in a pulse to convert the silicon precursor into a deposited silicon nitride film, wherein the formation of a nitrogen plasma necessarily involves applying a plasma power ([0039] – [0040], [0077], [0103]);
providing a pulse of hydrogen gas [hydrogen reactant] concurrent with the flow of nitrogen [overlapping], wherein a first plasma power is applied during the pulse of hydrogen gas ([0034], [0047] – [0048]); and
stopping the flow of hydrogen gas while maintaining the flow of nitrogen gas [preventing overlap], wherein a second plasma power is applied to generate a nitrogen-containing plasma without hydrogen in order to further treat the deposited silicon nitride film ([0047] – [0050]).
Ueda discloses that the silicon precursor may be e.g. SiI4 or HSiI3 ([0038]).
Regarding claim 17:
Ueda discloses a substrate having trenches with a silicon nitride film deposited thereon, meeting the structural requirements implied by the use of the method disclosed by Ueda (Abstract; Fig. 1) as substantially the same as the claimed structure. While Ueda does not expressly teach that the silicon precursor comprises one or more of the recited species, claim 17 is a product-by-process claim. "[E]ven though product-by-process claims are limited by and defined by the process, determination of patentability is based on the product itself. The patentability of a product does not depend on its method of production. If the product in the product-by-process claim is the same as or obvious from a product of the prior art, the claim is unpatentable even though the prior product was made by a different process." In re Thorpe, 777 F.2d 695, 698, 227 USPQ 964, 966 (Fed. Cir. 1985). Once the examiner provides a rationale tending to show that the claimed product appears to be the same or similar to that of the prior art, although produced by a different process, the burden shifts to applicant to come forward with evidence establishing an nonobvious difference between the claimed product and the prior art product. In re Marosi, 710 F.2d 799, 803, 218 USPQ 289, 292-33 (Fed. Cir. 1983).
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
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.
Claim(s) 1 – 6, 8 – 9, 11 – 13, 15 – 17, 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Ueda et al. US 2019/0333753 A1 (hereafter “Ueda”) in view of Iijima et al. US 2020/0075325A1 (hereafter “Iijima”).
Regarding claims 1, 8, 9, 13, 17, 20:
Ueda is directed to methods of forming silicon nitride films (Abstract). Ueda discloses that their methods comprise (Fig. 2, 5):
placing a substrate or workpiece in a reaction chamber ([0035]);
continuously flowing nitrogen gas [N2, nitrogen reactant pulse] in the reaction chamber [meeting claims 7, 8, 9] ([0039], [0042]);
supplying a pulse of silicon precursor, e.g. SiI4 or HSiI3 ([0038]) into the reaction chamber ([0032], [0038], [0044]);
forming a nitrogen plasma in a pulse to convert the silicon precursor into a deposited silicon nitride film, wherein the formation of a nitrogen plasma necessarily involves applying a plasma power ([0039] – [0040], [0077], [0103]);
providing a pulse of hydrogen gas or NH3 [hydrogen reactant, meeting claims 8 and 20] concurrent with the flow of nitrogen [overlapping], wherein a first plasma power is applied during the pulse of hydrogen gas ([0034], [0047] – [0048], [0093]); and
stopping the flow of hydrogen gas while maintaining the flow of nitrogen gas [preventing overlap], wherein a second plasma power is applied to generate a nitrogen-containing plasma without hydrogen in order to further treat the deposited silicon nitride film ([0047] – [0050]).
Ueda does not expressly teach that the silicon precursor comprises one or more of a silane, an organosilane, or a silazane.
Iijima is directed to a silicon nitride film forming method (Abstract; [0003] – [0005]). Iijima discloses reacting a deposited silicon precursor with a plasma of reactant gas and hydrogen containing gas (Fig. 2; [0028] – [0031]). Ijima further discloses that alongside silicon precursors only containing iodine and optionally hydrogen ([0020]), suitable precursors for forming silicon nitride films include organosilanes having an iodine group, such as Et2MeSiI ([0021]).
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the method of Ueda by having an organosilane as the silicon precursor because as taught by Iijima, the use of organosilanes having iodine groups is known to be suitable for the purpose of being a silicon precursor. The courts have held that the selection of a known material/device/product based for its intended use supports a prima facie case of obviousness. Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945), Ryco, Inc. v. Ag-Bag Corp., 857 F.2d 1418, 8 USPQ2d 1323 (Fed. Cir. 1988). Additionally regarding claim 17, the resultant structure produced by the method would also have been rendered obvious for the reasons set forth above.
Regarding claims 2, 3:
Ueda does not expressly teach that the deposition plasma power is greater than the second treatment plasma power, especially between 400W and 100W.
However, Ueda does disclose that the power for igniting a hydrogen + nitrogen plasma or a nitrogen without hydrogen plasma may be between 10W to 2000W ([0078] – [0079]). Furthermore, Ueda discloses an embodiment where the first plasma treatment also acts as providing the second reactant for depositing the SiN film (Fig. 5; [0096], [0117]). The plasma power described for deposition and hydrogen pretreatment is disclosed to be higher than the plasma power for the subsequent nitrogen without hydrogen treatment ([0119]). Finally, Ueda discloses that low power nitrogen plasma treatment helps realize the deposition of highly conformal SiN films that are thicker at the bottom and thinner at the top.
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the disclosed embodiments of Ueda in view of Iijima to have deposition plasma powers that are greater than the second treatment plasma power because Ueda suggests that the plasma power for deposition may be the same as the plasma power used for the hydrogen+nitrogen plasma treatment and that it is advantageous to have the nitrogen without hydrogen plasma treatment at a lower power than the plasma power used in the creation of an SiN film in order to help form conformal SiN films with desired profiles. With regards to the amount of deposition plasma power, in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d 1362, 1365-66(Fed. Cir. 1997). See MPEP 2144.05
Regarding claim 4:
Ueda discloses that the [second treatment] plasma power applied during the nitrogen-only plasma treatment step may be 300W ([0079]).
Regarding claim 5:
Ueda discloses that the plasma power applied between the hydrogen+nitrogen plasma treatment step and the nitrogen without hydrogen plasma treatment step may be equal (Fig. 3, [0051], [0077] – [0079]), or that the plasma power applied during the hydrogen+nitrogen plasma treatment step (e.g. 550 W) is larger than the plasma power applied during the nitrogen without hydrogen plasma pretreatment step (e.g. 300 W) (Fig. 5, [0051], [0077] – [0079]).
Regarding claim 6:
Ueda discloses that the [second treatment] plasma power applied during the nitrogen without hydrogen plasma treatment step may be 550W ([0079]).
Regarding claim 11:
Ueda discloses that the deposition cycles, including treatments, may be performed at temperatures between 25°C and 700°C ([0081]).
Regarding claim 12:
Ueda discloses that the pressure of the reaction chamber during processing may be maintained from about 0.01 torr to about 50 torr1 ([0082]).
Regarding claim 15:
Ueda discloses depositing the silicon nitride film onto sidewalls of a trench structure (Abstract).
Regarding claim 16:
Ueda discloses that in some embodiments the side-wall wet etch rate (WER) to the top WER , which includes the middle of a sidewall surface, may be 0.01 to 0.03 ([0024]).
Claim(s) 7,19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Ueda in view of Iijima as applied to claims 1 – 6, 8 – 9, 11 – 13, 15 – 17, 20 above, and further in view of Suemori et al. US 10,559,458 B1 (hereafter “Suemori”).
Regarding claims 7 and 19:
Ueda in view of Iijima discloses that in general, a generic nitrogen precursor may be used for forming the silicon nitride film and that a pulse of the generic nitrogen precursor may be supplied ([0031]).
Ueda does not expressly teach that the nitrogen reactant is selected from the recited group and that the hydrogen reactant is selected from the recited group.
Suemori is directed to methods of forming a nitrogen-incorporated silicon oxide film, an oxygen-incorporated silicon nitride film, or an intermediate silicon oxynitride film (Abstract; col 1 line 50 – col 2 line 20). Suemori discloses the use of an oxidizing gas and a nitriding gas which may be supplied together during a step of the plasma-enhanced atomic layer deposition (PEALD) technique (col 8 lines 10 – 20, col 9 lines 45 – 65, col 12 lines 55 – 65, col 14 lines 5 – 45). The oxidizing gas can be a gas containing nitrogen such as N2O, NO and combinations of ammonia or nitrogen gas with oxygen gas. Suemori discloses that an initial SiN film with SiON films improve the adhesion of SiO films onto substrates (col 7 lines 1 – 11). Furthermore, Suemori discloses that for the purpose of forming a silicon nitride film, a gas containing nitrogen can be NH3 and/or N2 + H2 (col 14 lines 5 – 15).
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the method of Ueda in view of Iijima by having the nitrogen reactant include/be selected to be either N2O or NO because Suemori suggests that the incorporation of oxidizing gases such as N2O or NO allows for gradient films between SiN to SiO that would improve the adhesion of SiO films onto substrates.
Claim(s) 10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Ueda in view of Iijima as applied to claims 1 – 6, 8 – 9, 11 – 13, 15 – 17, 20 above, and further in view of Nguyen et al. US 2014/0273530A1 (hereafter “Nguyen”).
Regarding claim 10:
Ueda in view of Iijima does not expressly teach that a volumetric follow ratio of the hydrogen reactant to the nitrogen reactant during the overlap period is between about 0.0003:1 and about 0.1:1.
Nguyen is directed to methods of modifying films comprising SiN with post-deposition treatments using plasmas (Abstract). The use of post deposition plasma modifies the residual stress and the wet etch rate of the treated films and can be fine tuned/modulated (Table 1; [0031], [0034]). In an example, Nguyen discloses a post deposition treatment using a plasma generated from nitrogen gas and ammonia and its effect on the stress and wet etch rate relative to other post deposition treatments (Table 1). Nguyen discloses that combinations of Ar, He, NH3, N2 and H2 modifies the stress and morphology of the treated silicon nitride film by removing hydrogen atoms from the extant silicon atoms and extant hydrogen atoms found in a silicon nitride film before treatment ([0034]). The amount of hydrogen removed from silicon atoms relative to the amount of hydrogen removed from nitrogen atoms within the silicon nitride film, i.e. the SiH/NH selectivity, is controlled by the choice of plasma gases and implicitly their concentrations ([0034], [0100]).
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have to have modified the method of in view of Iijima by having a volumetric flow ratio of hydrogen reactant (e.g. hydrogen or ammonia) to nitrogen reactant (e.g. nitrogen) during the overlap period within the claimed range of ratios as a matter of routine experimentation to arrive at desired film stresses and wet etch rates for the SiN film and adjustment of such film stresses as taught by Nguyen. Discovery of optimum value of result effective variable in known process is ordinarily within skill of art. In re Boesch, CCPA 1980, 617 F.2d 272, 205 USPQ215.
Response to Arguments
Applicant’s arguments, filed June 11, 2025, with respect to the rejection(s) of claim(s) 1, 4-9 and 11-17 under 35 USC §102 and §103 have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Iijima and Nguyen.
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 extension fee 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 date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to JOSE I HERNANDEZ-KENNEY whose telephone number is (571)270-5979. The examiner can normally be reached M-F 6:30-3:30.
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/JOSE I HERNANDEZ-KENNEY/
Primary Examiner
Art Unit 1717
1 The disclosure states “ton”, but the term is a typo of torr, as evidenced by the patent granted from the PG-Pub disclosure. See US 10580645 B2.