Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Election/Restrictions
Applicant’s election without traverse of Group I, claims 1-18 in the reply filed on 8/4/2026 is acknowledged.
Claims 19 and 20 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 8/4/2026.
Drawings
The drawings are objected to as failing to comply with 37 CFR 1.84(p)(4) because reference character “115” has been used to designate both the boat elevator and the shutter opening/closing mechanism (the shutter opening/closing mechanism is 115s in paragraph 0029 of the specification). Corrected drawing sheets in compliance with 37 CFR 1.121(d) are required in reply to the Office action to avoid abandonment of the application. Any amended replacement drawing sheet should include all of the figures appearing on the immediate prior version of the sheet, even if only one figure is being amended. Each drawing sheet submitted after the filing date of an application must be labeled in the top margin as either “Replacement Sheet” or “New Sheet” pursuant to 37 CFR 1.121(d). If the changes are not accepted by the examiner, the applicant will be notified and informed of any required corrective action in the next Office action. The objection to the drawings will not be held in abeyance.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
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, 7-12, and 16-18 are rejected under 35 U.S.C. 103 as being unpatentable over Ota, US 2015/0325427 A1 in view of Takeda, US 2021/0202213 A1.
Regarding claim 1, Ota teaches a method of processing a substrate (forming an oxycarbonitride film, an oxycarbide film, or an oxide film on a substrate, abstract), comprising:
forming an oxide film containing a predetermined element over the substrate by performing a first cycle a first predetermined number of times (forming an oxycarbonitride film, an oxycarbide film, or an oxide film on a substrate by performing a cycle a number of times, abstract and 0070), the first cycle including:
(a) forming a first layer containing the predetermined element terminated with a halogen element over the substrate by supplying a first precursor containing the predetermined element and the halogen element to the substrate (supplying a chlorosilane-based source to form a silicon-containing layer containing silicon and chlorine, 0075, 0085, and Fig. 3, where they provide HCDS at a temperature in the range of 350°C to 600°C and a pressure in the range of 20 to 1330 Pa, which is within the ranges described in [0051] of the instant specification and HCDS is indicated as being a suitable precursor at [0062] of the instant specification, such that the first layer is also expected to be terminated with a halogen element over the substrate);
(b) forming a second layer containing the predetermined element over the substrate by supplying a second precursor containing the predetermined element to the substrate over which the first layer is formed (supplying an aminosilane-based source to cause a reaction between the silicon-containing layer and the aminosilane-based gas, 0075, 0092, and Fig. 3); and
(c) oxidizing the second layer by supplying an oxidizing agent to the substrate over which the second layer is formed (flowing oxygen to oxidize the first layer, 0076 and Fig. 3).
They do not teach that the second precursor includes the predetermined element and a single amino group bonded to the predetermined element in one molecule. They teach using an aminosilane such as 3DMAS, 4DMAS, BTBAS, 2DEAS, etc. (0090 and 0094).
Takeda teaches forming a SiN film on a wafer by supplying a first precursor gas such as DCS, purging, supplying a second processing gas such as ammonia, purging, and repeating the cycle (0066, 0069, 0071, 0077, 0087, and 0093). They teach that the process can also be used to form SiO films, Sic films, SiOC films, SiOCN films, and SiON films (0104). They teach that the precursor gas can be an aminosilane gas such as 4DMAS, 3DMAS, BTBAS, diethylaminosilane, dipropylaminosilane, diisopropylaminosilane, butylaminosilane, etc. (0105). They teach using a reaction gas such as oxygen as an oxygen source (0109).
From the teachings of Takeda, 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 Ota to have used a monoaminosilane such as diethylaminosilane, dipropylaminosiane, diisopropylaminosilane, or butylaminosilane as the aminosilane precursor because Ota broadly teaches using an aminosilane with specific examples of 3DMAS, 4DMAS, and BTBAS and Takeda teaches that such monoaminosilanes are suitable alternatives to these precursors in a deposition with oxygen for forming silicon and oxygen containing films such that it will be expected to provide simple substitution of one known aminosilane for another.
Regarding claim 7, Ota in view of Takeda suggest the process of claim 1. Ota further teaches that the first precursor gas is hexachlorodisilane (0047), such that it includes a bond between two elements in one molecule, wherein the two elements are both the predetermined element, i.e., silicon.
Regarding claim 8, Ota in view of Takeda suggest the process of claim 1. Ota further teaches providing HCDS at a temperature in the range of 250 to 700°C, 350 to 650°C, and more preferably 350 to 600°C and a pressure of 1 to 13300 Pa or 20 to 1330 Pa (0085). They teach flowing HCDS at a rate of 1 to 1000 sccm and nitrogen at a rate of 100 to 10000 sccm (0085). They teach that the silicon layer is formed by self-decomposition of HCDS (0086).
The instant specification at paragraph 0051 indicates that step (a) is performed at a temperature of 350 to 700°C, specifically 500 to 600°C at a pressure of 1 to 10,000 Pa or 10 to 1333 Pa, where the precursor flows at 0.01 to 3 slm or 0.1 to 1 slm, with an inert gas flow rate of 0 to 10 slm. Paragraph 0062 of the instant specification indicates that the first precursor may be hexachlorodisilane.
Therefore, Ota in view of Takeda provide flowing a precursor meeting the claimed requirements, where it is indicated as being suitable in the instant specification, at a temperature overlapping the range discussed in the instant specification, at a pressure within the range discussed in the instant specification, at a flow rate overlapping the range discussed in the instant specification, and with an inert gas flow within the claimed range, where the precursor can self-decompose, such that the processing conditions are also considered to overlap a range at which the bond between the two elements in the first precursor is broken. 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 9, Ota in view of Takeda suggest the process of claim 7. Ota further teaches that the first precursor is HCDS (0085), such that the first precursor gas does not contain hydrogen in the molecule.
Regarding claim 10, Ota in view of Takeda suggest the process of claim 1. As discussed above, Takeda suggests using diethylaminosilane, dipropylaminosiane, diisopropylaminosilane, or butylaminosilane as the aminosilane precursor, such that the bonding hand other than that bonded to the single amino group is bonded to hydrogen.
Regarding claim 11, Ota in view of Takeda suggest the process of claim 1. Ota further teaches that the oxygen-containing gas is oxygen, nitrous oxide, nitrogen monoxide, nitrogen dioxide, ozone, carbon monoxide, carbon dioxide, etc. (0099 and 0110), such that the oxygen-containing gas includes those that do not contain hydrogen.
Regarding claim 12, Ota in view of Takeda suggest the process of claim 1. Ota further teaches that the oxygen is thermally activated by non-plasma (0097 and 0099), such that it is supplied in a non-plasma state.
Regarding claims 16 and 17, Ota in view of Takeda suggest the process of claim 1. Ota further teaches repeating steps 1 to 3 multiple numbers of times (0111 and Fig. 3). They teach that the oxygen gas is provided to add an O-component to the first layer (0099). They teach that by extending the thermal oxidation time, or increasing an oxidation power in the thermal oxidation, a major portion of the N-component is desorbed, to thereby, reduce the N-component to an impurity level or for it to substantially disappear (0099). They teach that the SiOCN or SiOC film can also be formed using a sequence in which providing the chlorosilane-based source and the aminosilane-based source multiple times prior to supplying the oxygen-containing source (0116-0121 and Fig. 4). They teach that the ratio of the silicon-component, the carbon-component, and the nitrogen component can be properly controlled and the controllability of the composition ratio of the SiOCN film or the SiOC film can be improved (0122). They teach that the process can be used for laminating a film composed of two kinds or more thin films (0159). They teach that by performing the first sequence and the third sequence, a laminated film in which an SiOCN film and a SiOC film are alternately laminated, and an SiOCN and SiO film are alternately laminated, etc. (0159, Fig. 5, and Fig. 7).
Takeda teaches forming SiO, SiC, SiOC, SiOCN, and SiON films (0104). They teach using the monoaminosilane precursors and oxygen as an oxidizing agent for forming the films (0105 and 0109). They teach forming the film by supplying the reaction gas after supplying the precursor gas and alternately supplying the gases (0103).
From the teachings of Ota and Takeda, 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 optimized the steps of the cycle to repeat steps (b) and (c) without performing (a) a number of times because Ota teaches that providing oxygen increases the oxygen content in the film, where the time can be extended for including more oxygen, that steps (a) and (b) can be repeated for tuning the composition of the film, and that multiple types of films can be laminated, including SiOC, SiOCN, and SiO films, and Takeda teaches alternately supplying a monoaminosilane gas and an oxygen gas for forming films such as SiOC, SiOCN, and SiO films such that it will be expected to tune the composition of the film for forming a laminated layer. Therefore, in a second cycle or being included in the first, (b) and (c) will be repeated multiple times, where this is also considered to provide executing (b) and (c) multiple times in the first cycle.
Regarding claim 18, Ota in view of Takeda suggest the process of claim 1. Ota further teaches that the method is for manufacturing a semiconductor device (0002).
Claims 1-4 and 11-17 are rejected under 35 U.S.C. 103 as being unpatentable over Pore, US 9,812,320 B1 in view of Kumakura, US 2020/0279757 A1.
Regarding claim 1, Pore teaches a method of processing a substrate (a method of filling one or more gaps on a substrate, abstract), comprising:
forming an oxide film containing a predetermined element over the substrate by performing a first cycle a first predetermined number of times (performing a cyclic deposition process for forming a SiO layer, Col. 3, line 34 to Col. 4, line 21, Fig. 2, and Fig. 3), the first cycle including:
(a) forming a first layer containing the predetermined element terminated with a halogen element over the substrate by supplying a first precursor containing the predetermined element and the halogen element to the substrate (providing a first reactant so as to form no more than about one monolayer, where the first reactant can be selected from diiodomethylsilane or alkylchlorosilanes, Col. 3, line 36-38, Col. 9, lines 17-20, Fig. 2, and Fig. 3, where since they provide gases containing halogens, the first layer is also expected to contain the predetermined element and be terminated with a halogen element);
(b) forming a second layer containing the predetermined element over the substrate by supplying a second precursor containing the predetermined element to the substrate over which the first layer is formed (introducing a second reactant to the substrate with a second dose, where the second reactant is an aminosilane, Col. 3, line 39-40, Col. 9, line 33-37, Fig. 2, and Fig. 3); and
(c) oxidizing the second layer by supplying an oxidizing agent to the substrate over which the second layer is formed (providing a third reactant to the substrate to react with at least one of the first and second reactant, Col. 3, lines 48-50, where the third reactant is oxygen or ozone to provide the SiO layer, Col. 6, line 11-13, Col. 9, line 40-42, and Fig. 3, such that the second layer will be oxidized by an oxidizing agent (ozone or oxygen) to provide SiO).
They do not specifically teach that the aminosilane includes a single amino group, however, they teach that the second reactant is provided with a saturating second dose to reach the bottom area of the surface of the gap (abstract).
Kumakura teaches forming a film having a thickness that differs along a depth direction of a recess (abstract). They teach that the precursor may be selected to control the depth of the protective film to be formed (0080). They teach that for forming a protective film only on the upper portion of the pattern, among aminosilane-based gases, it is preferable to use aminosilane gas having two or three amino groups, rather than aminosilane gases having one amino group (0080). They teach that to form the protective films at a deep position of the pattern; it is preferable to use monovalent aminosilane gas (0080).
From the teachings of Kumakura, 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 selected a monoaminosilane as the second precursor gas because Kumakura teaches that such an aminosilane is more capable of forming a film at a deep position in a pattern compared to a divalent or trivalent aminosilane and Pore teaches providing the second precursor to reach the bottom of the feature such that it will be expected to be more capable of reaching the bottom of the feature compared to other aminosilanes. Therefore, the second precursor will include the predetermined element (silicon) bonded to a single amino group as in the monoaminosilane and be provided to form a second layer containing the predetermined element over the substrate.
Regarding claim 2, Pore in view of Kumakura suggests the process of claim 1. Pore further teaches that the oxide film is formed in a recess structure on the substrate (abstract and Fig. 3-5).
Regarding claims 3 and 14, Pore in view of Kumakura suggest the process of claim 1. Pore further teaches providing the first precursor at a subsaturating dose so that it reaches only a top area of the surface having the gaps and providing the second reactant with a saturating dose so that it reaches the bottom of the gaps (Col. 1, lines 54-65 and Fig. 3-5). Therefore, (b) is executed under dosing conditions so that the second precursor is adsorbed to the substrate by supplying the second precursor to the substrate over which the first layer is not formed. Further, the density of the first layer formed at the upper surface is larger than the density of the first layer formed at the bottom end of the side surface of the recess structure, as required by claim 14.
Regarding claim 4, Pore in view of Kumakura suggest the process of claim 3. Kumakura further teaches that by a combination with the processing parameters such as the processing time, the temperature of the stage, and the pressure in the processing chamber, the controllability of the unsaturated state may be improved (0080). From the teachings of Kumakura, 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 also controlled the temperature and pressure of the process to control the saturation of the second precursor because Kumakura teaches that temperature and pressure can be used to control the unsaturation/saturation state of a precursor in a gap on a substrate and Pore teaches providing the second precursor to reach the bottom of the feature such that temperature and pressure are also expected to facilitate movement of the precursor to the bottom of the gap.
Regarding claim 11, Pore in view of Kumakura suggest the process of claim 1. Pore further teaches using oxygen or ozone as the oxidizing agent (Col. 6, lines 11-13 and Col. 9, lines 40-42), such that the oxidizing agent does not contain hydrogen.
Regarding claim 12, Pore in view of Kumakura suggest the process of claim 1. Pore further teaches that some embodiments include using plasma (Col. 4, lines 62-67). They also teach that the apparatus for performing the process can optionally be provided with an RF source for producing plasma (Col. 8, lines 10-17). 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 provided the oxidizing agent in a non-plasma state because Pore teaches that the apparatus for performing the process can optionally be provided with an RF source and that in some embodiments plasma is used, suggesting that the process can also be performed in a non-plasma state.
Regarding claim 13, Pore in view of Kumakura suggest the process of claim 1. As discussed above for claims 3 and 14, they suggest forming the second layer over the substrate to be adsorbed on a surface of the substrate over which the first layer is not formed. They teach using an apparatus provided with a heater to activate the reactions by elevating the temperature of one or more of the substrate, the first, second, and third reactants (Col. 7, line 66 to Col. 8, line 9). They also provide examples of the process where the deposition is done at temperatures of 300°C and 400°C (Col. 6, line 31-45), indicating that the process is done at an elevated temperature.
While they do not teach that the second layer includes a dangling bond due to desorption of the single amino group, since they provide a monoaminosilane, using the precursor for deposition, where they teach activating the reactant using a heater for deposition, the resulting process is also expected to result in forming a dangling bond to provide deposition of the second precursor. 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 15, Pore in view of Kumakura suggest the process of claim 1. As discussed above, Pore teaches providing (a) at a subsaturated dose in a process of filling the gap, where Kumakura indicates that the saturation of a dose can also be controlled by controlling the pressure. Kumakura further teaches that the coverage on the substrate can be set by adjusting the processing time, where having a shorter processing time decreases the amount of material on the bottom of the features (0059 and Fig. 6).
Pore teaches providing the first precursor to block further deposition in the top of the gap of the second reactant (Col. 3, lines 51-59). They teach using the process to fill the gap (abstract and Fig. 5). 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 modified the pressure and/or the processing time in step (a) as the cycles progress so as to decrease the amount of (a) provided top because Pore teaches filling the gap, where the precursor provided in (a) blocks the top from deposition, where Kumakura indicates that pressure and processing time can tune the degree of coverage such that it will be expected to reduce the amount of surface blocked from deposition during filling of the gap so as to fill the gap.
Regarding claims 16 and 17, Pore in view of Kumakura suggest the process of claim 1. Pore further teaches performing a second cycle not including (a) but including (b) and (c), i.e., performing look 205 that includes steps 202 and 203 (Col. 4, lines 15-21 and Fig. 2). Further, the process is also considered to provide the first cycle of (a), (b), and (c), where (b) and (c) are executed multiple times.
Claims 5 and 6 are rejected under 35 U.S.C. 103 as being unpatentable over Pore in view of Kumakura as applied to claim 1 above, and further in view of Yan, US 2016/0099143 A1.
Regarding claim 5, Pore in view of Kumakura suggest the process of claim 1, as discussed above for claim 3, Pore teaches providing the first precursor as a subsaturated does and the second precursor at a saturated dose (abstract).
They do not teach that the partial pressure of the second precursor supplied to the substrate in (b) is greater than a partial pressure of the first precursor supplied to the substrate in (a).
Yan teaches a process for depositing SiO2 using an aminosilane compound as a silicon precursor (abstract). They teach that the amount of Si precursor adsorbed onto the substrate surface may be controlled by adjusting the partial pressure of the Si precursor and/or the amount of time the substrate surface is exposed to the gaseous Si precursor (0045). They teach that lower partial pressures and/or shorter exposure times may be used to produce sub-monolayer coverage, or higher partial pressures and/or longer exposure times may be used to produce saturated coverage (0045).
From the teachings of Yan, 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 provided the second precursor in (b) at a greater partial pressure than the first precursor supplied in (a) because Yan teaches that providing a higher partial pressure increases the saturation of the precursor on the substrate and Pore teaches providing the second precursor to saturate the substrate and the first precursor at a subsaturation dose such that it will be expected to provide the first and second precursor at the desired saturation regimes.
Regarding claim 6, Pore in view of Kumakura and Yan suggest the process of claim 5. As discussed above for claim 4, Kumakura teaches controlling the pressure to control the saturation of the precursor. They further teach that by setting the pressure in the processing chamber to be low, the progress of film formation on the lower portion of the pattern may be made slow (0059). 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 set the pressure in the space where the substrate exists in (b) to be higher than the pressure in the space where the substrate exists in (a) because Kumakura teaches that a lower pressure provides less growth on the bottom of a recess and Pore desires low growth on the bottom in (a) and higher growth on the bottom in (b) such that it will be expected to provide suitable pressure conditions for achieving the desired saturation of the precursors.
Conclusion
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/CHRISTINA D MCCLURE/ Examiner, Art Unit 1718
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