DETAILED ACTION
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 April 8 , 2026 has been entered.
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 .
In the amendment filed on April 8, 2026, claims 1, 3, 8 – 10, 12 – 20, 22 – 33 are pending. Claims 1, 10, 16, 18, 19 have been amended and claims 2, 4 – 7, 11, 21 have been canceled. Claims 23 – 33 have been added.
Specification
The disclosure is objected to because of the following informalities: on page 12 lines 5 – 10, the described organosilicon precursor is trimethylsilylamine, but the formula immediately following the chemical name is not trimethylsilamine, but rather trisilylamine. As evidenced by CAS Registry: 7379-79-5, trimethylsilylamine has the
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following structure:
It appears then that the intended organosilicon precursor is either that described by the recited structure and that the name is in error or vice versa.
Appropriate correction is required.
Claim Rejections - 35 USC § 112
The following is a quotation of the first paragraph of 35 U.S.C. 112(a):
(a) IN GENERAL.—The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor or joint inventor of carrying out the invention.
The following is a quotation of the first paragraph of pre-AIA 35 U.S.C. 112:
The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor of carrying out his invention.
Claims 1, 3, 8 – 10, 12 – 20, 22 – 33 are rejected under 35 U.S.C. 112(a) or 35 U.S.C. 112 (pre-AIA ), first paragraph, as failing to comply with the written description requirement. The claim(s) contains subject matter which was not described in the specification in such a way as to reasonably convey to one skilled in the relevant art that the inventor or a joint inventor, or for applications subject to pre-AIA 35 U.S.C. 112, the inventor(s), at the time the application was filed, had possession of the claimed invention.
Regarding claims 1 and 10:
The claims have been amended to recite that a resultant polysilazane chain “has a number average molecular weight (Mn) of from 40 to 1000 g/mol”. The originally filed disclosure does not expressly recite the added claim limitation. Applicant states in their reply filed on April 8, 2026 that the amendments to the claims are supported by at least [0013] – [0014], [0064] – [0065], [0075] as formatted in the PG-Publication of the present application, i.e. page 2 lines 18 –26, page 9 lines 9 – 16, and page 15 lines 1 – 7 of the originally filed specification.
While there is no in haec verba requirement, newly added claims or claim limitations must be supported in the specification through express, implicit, or inherent disclosure. See MPEP 2163.02 and In re Oda, 443 F.2d 1200, 170 USPQ 268 (CCPA 1971).
The recitations of purported support generally indicate that an average molecular weight is within the specified values. However, as indicated in the previous Office Action filed on June 11, 2025 (see page 3, item 5), the term “average molecular weight” in the context of polymers is ambiguous. Average molecular weight, in itself, is not a term of art assigned with specific value, but instead use to demonstrate a concept of how to characterize polymers. As evidenced by “Molecular weight”. DoITPoMS. University of Cambridge. 2022 [archived]. Retrieved from https://www.doitpoms.ac.uk/tlplib/polymerbasics/mw.php (of record), there are multiple methods to define an average molecular weight, and those methods do not arrive at the same number as they would describe different characteristics of a given sample of synthetic polymer. Conversely, a single value provided for an average molecular weight describes very different characteristics of such a given sample depending on the species of average molecular weight being discussed.
At issue is whether there is reasonable possession of the underlying characteristics of the described polymer to the specific value recited in the originally filed disclosure, especially in view of the description of such polymers being created by reaction of an organosilicon precursor with nitrogen-containing free radicals generated from a remote plasma. No express support for such a link is provided.
Additionally, there is insufficient evidence within the instant disclosure to provide a reasonable inference that implies that the “average molecular weight” is referring to the number average molecular weight, such as contemplation of the formed polymers polydispersity index, the use of known short-hand symbols for number average molecular weight such as Mn, or clear indications and/or examples of reaction conditions that would lead to a given number average molecular weight.
In their reply filed on April 8, 2026, the Applicant submitted that the description of short polysilazane chains and repeat units, and oligomeric molecular weights would readily lead one of ordinary skill in the art to recognize that what is being discussed is the number average molecular weight, as that is the standard for oligomer chain length.
The Examiner respectfully disagrees with that such descriptions would have lead one of ordinary skill in the art to have recognized that the term “average molecular weight” refers to the number average molecular weight. As a first matter, the support for repeating units refer to general formulas where the described Si – N repeat unit would have substituents. See formula 1 – 1 of the originally filed disclosure as an example of chains with substituents. Furthermore, the recitations merely indicate what species of polysilazane chain may result from the execution of the steps, not a range of the total products of the reaction of free radicals and organosilicon precursors for e.g other polysilazane chains or chains that would be longer or shorter than those disclosed. The Examiner further notes that the claims Because the disclosed methods involve techniques that can create multiple products alongside the claimed (single?) polysiloxane chain. New or amended claims which introduce elements or limitations that are not supported by the as-filed disclosure violate the written description requirement. See, e.g., In re Lukach, 442 F.2d 967, 169 USPQ 795 (CCPA 1971)
Thus, the amendment introduces New Matter. Accordingly, there is no reasonable conveyance to one of ordinary skill in the art that the inventor or joint inventor has possession of the claimed invention at the time the application was filed.
Claim Rejections - 35 USC § 103
The rejections of the claims under 35 USC § 103 in the previous Office Action are withdrawn due to Applicant amendment.
Claim(s) 1, 3, 8, 9, 10, 22 – 29, 30, 31, 33 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liang et al. US 20110159703 A1 (hereinafter “Liang”) in view of Mays et al. US 20190035673 A1 (hereinafter “Mays”).
Regarding claim 1, 3, 8, 9, 10, 22, 23, 24, 25, 27, 29, 30, 31, 33:
Liang is directed to a method of forming dielectric layers, including both silicon and nitrogen containing layers [silicon nitrides] as well as silicon, oxygen containing layers after an optional conversion step [silicon oxides] and mixtures thereof (Abstract, [0006]; [0022]). As exemplified by Fig. 1, Liang discloses a method comprising:
introducing a silicon-nitrogen precursor into a plasma-free substrate processing region of a processing chamber with a substrate situated within the processing chamber (Fig. 1, Fig. 4A, ; [0018] – [0019]);
using a remote plasma source and/or a plasma region of the processing chamber separated from the plasma-free substrate processing region by a showerhead 453 (Fig. 4A; [0036] – [0037]), remotely activating a nitrogen-containing co-reactant such as ammonia in mixture with N2 and H2 ([0026], meeting claim 8) to form nitrogen-containing radical, and then subsequently introducing such radicals into the plasma free substrate processing region of the processing chamber ([0019] – [0021]);
reacting the silicon-nitrogen precursor and nitrogen-containing co-reactant to form a flowable film of silicon nitride polymers that is deposited onto the substrate ([0022] – [0023]); and (in another embodiment)
curing the deposited silicon nitride polymers in an atmosphere containing oxygen [e.g. ozone] and annealing in an inert environment to form densified silicon oxide [meeting claim 22] film domains containing Si–O–Si bonds (Fig. 2 210; [0029] – [0030]).
The silicon-nitrogen precursor can be e.g. silylamines such as trisilylamine [ N(SiH3)3 , an organosilicon precursor having the claimed formula, where all R groups are hydrogen] and form short chained polysilazane polymers ([0019], [0023]). Liang discloses that the flowability is due, at least in part, to the presence of such short chained polysilazane polymers.
Liang does not expressly teach that a polysilazane chain generated from execution of the steps of the claimed method would have a number average molecular weight of from 40 to 1000 g/mol; and does not expressly teach that the generated polysilazane chain being deposited on the substrate comprises the recited repeating units.
With regards to the polysilazane chain generated from execution of the steps of the claimed method having a number average molecular weight of from 40 to 1000 g/mol:
In analogous art, Mays is directed semiconductor apparatus and methods of forming isolation trenches for such apparatus (Abstract; [0003], [0014]). Mays discloses that their embodiments of their method comprises: depositing a flowable film from vapor phase precursors, such as trisilylamine, and ammonia/ammonia radicals ([0015], [0019], [0029], [0072] – [0076]; Claim 21) at temperatures less than 500°C. Mays further discloses that in embodiments the method results in polymer chains that are short enough [which skews numerical average molecular weight] to condense, flow and fill e.g trenches, but also long enough to build a high molecular weight polymer. According to Mays, a high degree of polymerization, which corresponds to molecular weight, helps to minimize volatilization of the reacted product, minimizes flowable film shrinkage, and increases final ceramic yield ([0015]).
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 Liang to form at least in part flowable polysilazane chains having the numerical average molecular weight as a matter of routine experimentation of the reaction conditions of the method (e.g. reaction temperature) in order to balance the length of polymer chains [i.e. repeating units] and the molecular weight of each chain [including numerical average molecular weight]; sufficiently short polymer chains are required for the flowability of the produced polysilazane chains yet high molecular weight chains is required for optimal end-results such as maximized density and ceramic yield, as suggested by Mays. 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.
With regards to the generated polysilazane chain being deposited on the substrate comprises the recited repeating units:
Liang discloses that the precursor may be trisilylamine. As evidenced by CAS Registry: 13862-16-3, trisillylamine has the following structure:
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Such a substructure in monomeric form corresponds to the recited unit formula:
It is reasonable to presume that the resultant polysilazane structure of at least some of the deposited flowable film is inherent to Liang in view of Mays. Support for said presumption is found in the use of like materials and like processes (i.e. trisilylamine as a precursor, a silicon precursor that is a monomer of the same structure as discussed above, ammonia based free radicals, see and compare paragraph [0024] of Liang concerning temperature conditions) which would result in the claimed property. The burden is upon the Applicant to prove otherwise. In re Fitzgerald 205 USPQ 594.
Additionally and alternatively, the presently claimed polysilazane structure would be implicitly taught to be present once the flowable film is provided due to the clear correspondence and the general fact that polymers are formed from monomeric units. "[I]n considering the disclosure of a reference, it is proper to take into account not only specific teachings of the reference but also the inferences which one skilled in the art would reasonably be expected to draw therefrom." In re Preda, 401 F.2d 825, 826, 159 USPQ 342, 344 (CCPA 1968).
Regarding claim 26:
Liang discloses that the substrate may comprise trenches/gaps [recessed feature] (Fig. 2, [0027]), and that the deposited flowable film fills such gaps ([0028]).
Regarding claim 28:
Liang discloses that the nitrogen reactants may originate from a remote plasma system that travels through a gas inlet assembly 411 that is distinct and different from a gas supply channel for supplying precursor within the showerhead itself ([0036] – [0037]).
Regarding claim 32:
In an alternative embodiment, a first annealing can be performed in an oxygen environment to further transition [convert] to silicon oxide bonds ([0029]).
Claim(s) 12, 13, 16, 17, 18, 19, 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liang in view of Mays as applied to claims 1, 3, 8, 9, 10, 22 – 29, 30, 31, 33 above, and further in view of Mallick et al. US 20140051264 A1 (hereafter “Mallick”).
Regarding claim 12, 13, 16, 17, 18, 19, 20:
Liang discloses that the curing of the film comprises exposure to an ozone-containing atmosphere ([0029]).
Liang in view of Mays does not expressly teach that the curing/annealing comprises exposing the flowable film to at least of water or ultraviolet rays in addition to the ozone. Additionally, Liang in view of Mays does not expressly teach that the curing/annealing of the flowable film by steam and ozone occurs at a temperature of 150°C to 450°C and at a pressure of 400 Torr to 800 Torr; or alternatively that the curing/annealing of the flowable film in an atmosphere of vapor at a temperature of 200°C to 600°C, wherein the vapor comprises at least one of water vapor or an acid vapor of hydrochloric acid or acetic acid.
Mallick is directed to methods of depositing initially flowable dielectric films on substrates followed by a treatment to form a silicon oxide film [comprising Si – O – Si bonds] (Abstract). The initially flowable dielectric films are silicon and nitrogen containing materials, i.e. having Si –N(H) – Si bonds and formed from a silicon and nitrogen precursor and remote plasma-formed radical nitrogen precursors e.g ( –NH) ([0008]).
Like Liang, Mallick further discloses curing/annealing the initially flowable films with ozone, but also teaches curing in combination with ultraviolet light irradiation ([0048]) or by thermal annealing in a steam atmosphere ([0047]). Such a treatment performs the conversion of silicon to nitride bonds to silicon to oxygen bonds. The annealing can convert a portion of the nitrogen to oxygen as opposed to all nitrogen bonded to silicon ([0010]). The deposition with initially flowable silicon-nitride films to silicon oxide films allow for the formation of dense silicon oxide films with fewer stress cracks ([0029]), which is important for electrical isolation between device structures in semiconductor applications ([0003]).
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 Liang in view of Mays by tuning the curing and annealing processes taught by Liang, including the inclusion of UV light or water for curing, to produce a film having at least a few Si–O–Si bonds because Mallick teaches that such a curing is useful for producing silicon oxide films and suggests silicon oxynitride films which can be dense and with minimal stress cracks, useful for electrical isolation.
Mallick also discloses that the steam [water vapor] annealing can be performed at substrate temperatures between 200°C to 1050°C and at water vapor pressure range between 1 Torr to 760 Torr ([0047]); and that ozone treatment can be performed between room temperature to 600°C at an implied pressure of ambient (760 torr) ([0048]).
Additionally, Mallick discloses that the initially flowable films can also be annealed in an atmosphere containing both water vapor and acid vapor [therefore treating a first portion and second portion simultaneously] ([0050]). While Mallick does not expressly teach that the acid is one of hydrochloric acid or acetic acid, the Examiner takes official notice that such acids are known by those of ordinary skill in the art as commonly available and readily volatized into vapor. It would therefore have been obvious to one of ordinary skill in the art to have used such acids for producing acid vapor due to the ready availability of the acids and their known ability to readily provide H+ ion, which Mallick identifies as critical ([0050]).
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.
Claim(s) 14 is/are rejected under 35 U.S.C. 103 as being unpatentable over Liang in view of Mays and Mallick as applied to claims 12, 13, 16, 17, 18, 19, 20 above, and further in view of Lubomirsky et al. US 20070298585 A1 (hereafter “Lubomirsky”).
Regarding claim 14:
Liang in view of Mays and Mallick does not expressly teach that the curing/annealing of the flowable film by ozone is performed at a temperature of less than 100°C and subsequently exposing the flowable film to ultraviolet rays (radiation) at a pressure of less than 150 Torr.
With regards to the ozone treatment:
Mallick discloses that the ozone treatment can be performed between room temperature to 600°C at an implied pressure of ambient (760 torr) ([0048]).
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.
With regards to the exposure to ultraviolet rays:
In analogous art, Lubomirsky is directed to depositing dielectric films onto substrates (Abstract). The dielectric films may be deposited as flowable films ([0022], [0024], [0029]) followed by treatment (e.g. curing and annealing) to harden the dielectric by reducing hydroxyl groups that would be present ([0023]). The curing/annealing treatments include ultraviolet (UV) curing of the film at pressures between e.g. 1 to 2 Torr ([0034], [0038]).
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 Liang in view of Mays and Mallick by setting the chamber pressure during UV treatment at less than 150 Torr, e.g. 1 to 2 Torr, because Lubomirsky teaches that UV treatment at such pressures is effective at densifying dielectric films.
Claim(s) 15 is/are rejected under 35 U.S.C. 103 as being unpatentable over Kalutarage in view of Mallick as applied to claims 1, 3, 8, 9, 10, 22 – 29, 30, 31, 33 above, and further in view of Fukazawa et al. US 8003174 B2 (hereafter “Fukazawa”).
Regarding claim 15:
Liang in view Mays does not expressly teach that the annealing of the cured flowable film occurs in an atmosphere of nitrogen at temperature of 1050°C.
Fukazawa is directed to methods of forming dielectric films from liquid/flowable intermediate films (Abstract; col 3 lines 57 – 62, col 9 line 65 – col 10 line 65). Fukazawa discloses that the flowable intermediate film is then subsequently annealed in an atmosphere comprising nitrogen gas at a temperature between 50°C to 1100°C (col 3 lines 30 – 40, col 6 lines 1 – 25). The annealing treatment allows for impurities within the curing film to be discharged as well as conversion of Si – N bonds to Si – O bonds (col 6 lines 5 – 20, col 7 lines 15 – 30).
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 Kalutarage in view of Mallick by annealing curing/cured the flowable films in an atmosphere of nitrogen because Fukazawa teaches that such an annealing treatment further allows for impurities to be expelled from the curing/cured film and further continues the conversion of Si – N to Si – O bonds. With regards to the temperature of annealing, 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.
Response to Arguments
Applicant’s arguments filed April 8, 2026, with respect to the rejection(s) of the claim(s) under 35 USC 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 Liang.
Conclusion
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
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