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 1-18 are pending and rejected. Claims 19 and 20 are withdrawn.
Election/Restrictions
Applicant’s election without traverse of Group I, claims 1-18 in the reply filed on 8/11/2026 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 Claims 19 and 20 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim.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 8/11/2026.
Drawings
The drawings are objected to as failing to comply with 37 CFR 1.84(p)(5) because they include the following reference character(s) not mentioned in the description: 243 in Fig. 1, it appears as though it should be 243c and S42 and S43 in Fig. 6. Corrected drawing sheets in compliance with 37 CFR 1.121(d), or amendment to the specification to add the reference character(s) in the description in compliance with 37 CFR 1.121(b) 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 § 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 3, 4, and 13 are 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 3, 4, and 13, the claims refer to the “content rate of hydrogen”, however, it is unclear what a “content rate” is. Specifically, a rate is generally a measurement per unit time, making it unclear whether the claims are intending to refer to the speed of changing the hydrogen content or whether the claims are referring to the content of hydrogen alone. For the purposes of examination, either interpretation is considered to meet the claimed limitations. 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 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 1-13 and 16-18 are rejected under 35 U.S.C. 103 as being unpatentable over Yamaguchi, WO 2021171466 A1.
The following citations for Yamaguchi, WO 2021171466 A1 are in reference to the machine translation provided by Espacenet and the figures in the original document.
Regarding claim 1, Yamaguchi teaches a method of processing a substrate (filling a recess on a substrate, 0005), the method comprising:
(a) performing a cycle including supplying a source containing a predetermined element, carbon, and hydrogen to the substrate and supplying a first modifying agent containing nitrogen to the substrate, a predetermined number of times to form, on the substrate, a first film (performing a cycle including the steps of supplying a source gas to a substrate having a recess formed on its surface and supplying a first nitrogen- and hydrogen-containing gas to the substrate, 0005, where the source gas includes those that contain silicon, carbon, and hydrogen, such as diethyl silane, 0043); and
(b) supplying, to the substrate on which the first film is formed, a second modifying agent that is different from the first modifying agent and contains a compound containing a nitrogen-hydrogen bond and a nitrogen-nitrogen bond per molecule or a derivative of the compound (supplying a second nitrogen- and hydrogen-containing gas to the substrate to generate, grow, and flow oligomers containing elements contained in at least one of the source gas, the fist nitrogen- and hydrogen-containing gas and the second nitrogen- and hydrogen-containing gas, 0005, where the second N- and H-containing gas may be diazene, hydrazine, or N3H8).
They teach that the cycle is performed a predetermined number of times (0053). After performing the cycle a predetermined number of times, a post treatment process is performed to modify the oligomer-containing layer formed on the surface and in the recesses of the wafer (0065 and 0069). They teach using a nitrogen gas during the post treatment (0066).
Therefore, they provide the steps of performing a cycle of supplying a source gas meeting the claimed requirements and supplying a first modifying agent meeting the claimed requirements a single time to the substrate, such that it will form the oligomers on the surface and supplying a second modifying agent meeting the claimed requirements to the substrate such that it will modify the first layer formed on the surface.
They further teach performing the process at a temperature of 0 to 150°C and a pressure of 10 to 6,000 Pa (0055, 0057, and 0058).
The instant specification at [0042] indicates that the source gas is provided at a temperature in the range of 150°C to 180°C. The instant specification at [0062] indicates that the first modifying agent is provided at a pressure of 1 to 4000 Pa, preferably 10 to 1000 Pa at the same temperature as the source gas. Therefore, since the process temperature and pressure overlap the claimed range, where they provide oligomers reacting materials meeting the source chemical and first modifying agent requirements, the resulting film is also expected to include the predetermined element (silicon), nitrogen, carbon, and hydrogen bonded to carbon, where the film would also be expected to include these elements when reacting at a lower temperature due to less energy being provided for dissociating the precursors.
The instant specification at [0079] indicates that the temperature of the process when supplying the second modifying agent is in the range of room temperature to 700°C, preferably 150°C to 400°C with a pressure in the range of 1 to 2666 Pa, preferably 67 to 1333 Pa. The instant specification at [0080] indicates that when the temperature of the wafer is less than room temperature, the second modifying agent is hardly activated and when it is not less than room temperature it is activated and when it is 150°C or more is it further activated. At [0081] the instant specification indicates that modifying at a temperature of 400°C or less provides reliable modification and at [0082] it indicates that the temperature is set to room temperature to 700°C so that the reactivity of the second modifying agent can be controlled easily such that the second modifying agent or an intermediate thereof reacts with H bonded to C, H bonded to Si, or Cl bonded to Si.
While they do not teach that the second modifying agent modifies the first film to a second film that is lower in content of the hydrogen bonded to carbon than the first film, since they provide the claimed process steps using materials meeting the claimed requirements and perform the process at a temperature and pressure overlapping the ranges discussed in the instant specification, the process is also expected to modify the first film to a second film having a lower content rate of hydrogen bonded to carbon than the first film.
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 2, Yamaguchi suggests the process of claim 1. They further provide the flow chart demonstrating the steps of the process, where there is no indication that the substrate is exposed to an oxygen-containing atmosphere (0032 and Fig. 4). Therefore, the process is considered to include performing (b) after (a) without exposing to an oxygen-containing atmosphere.
Regarding claim 3, Yamaguchi suggests the process of claim 1. While they do not teach that modifying the first film include reducing the content rate of the hydrogen bonded to carbon over entirety in a thickness direction of the first film, since they provide the process of claim 1, where step (b) is performed after a single cycle of (a), the resulting process is also expected to reduce the content rate of the hydrogen bonded to carbon over entirety in a thickness direction of the first film. 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 4, Yamaguchi suggests the process of claim 1. While they do not teach that modifying the first film to the second film such a reduction in content rate of hydrogen in the first film is larger than a reduction in content rate of carbon in the first film, since they provide the process of claim 1 using materials meeting the claimed requirements and similar processing conditions, the resulting process is also expected to provide a reduction in content rate of hydrogen in the first film that is larger than a reduction in content rate of carbon in the first film. 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 5, Yamaguchi suggests the process of claim 1. They further teach that the cycle of providing the source gas, the first N- and H-containing gas, and the second N- and H-containing gas is repeated a predetermined number of times, i.e., n times, where n is 1 or more (0032). Therefore, the cycle of (a) will be repeated a plurality of times when n is more than one.
Regarding claim 6, Yamaguchi suggests the process of claim 1. There is no indication that plasma is used with the second modifying agent (0032, 0049-0052, and Fig. 4). Therefore, 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 modifying agent in a non-plasma step because Yamaguchi does not indicate or suggest that plasmas is desired.
Regarding claim 7, Yamaguchi suggests the process of claim 1. They further teach that the first N- and H-containing gas includes ammonia, ethylamine, monoethylamine, diethylamine, or triethylamine (0048), such that the first modifying agent is selected from a group including those that contain no nitrogen-nitrogen bond per molecule.
Regarding claim 8, Yamaguchi suggests the process of claim 7. As noted above, they teach selecting the first N- and H-containing gas from a group including ammonia (0048), so as to provide a hydronitrogen-based compound having no nitrogen-nitrogen bond.
Regarding claim 9, Yamaguchi suggests the process of claim 1. They further teach performing the second modifying process at a temperature of 0 to 150°C and a pressure of 10 to 6,000 Pa (0055 and 0058).
The instant specification at [0079] indicates that the temperature of the process when supplying the second modifying agent is in the range of room temperature to 700°C, preferably 150°C to 400°C with a pressure in the range of 1 to 2666 Pa, preferably 67 to 1333 Pa. The instant specification at [0080] indicates that when the temperature of the wafer is less than room temperature, the second modifying agent is hardly activated and when it is not less than room temperature it is activated and when it is 150°C or more is it further activated. At [0081] the instant specification indicates that modifying at a temperature of 400°C or less provides reliable modification and at [0082] it indicates that the temperature is set to room temperature to 700°C so that the reactivity of the second modifying agent can be controlled easily such that the second modifying agent or an intermediate thereof reacts with H bonded to C, H bonded to Si, or Cl bonded to Si.
While Yamaguchi does not indicate that in (b) an intermediate is produced from the second modifying agent and contains nitrogen with a dangling bond per molecule to react with the hydrogen bonded to carbon in the first film to desorb the hydrogen from the first film, since they provide a process having a temperature and pressure overlapping the range described in the specification and using materials meeting the claimed requirements, the process is also expected to provide the claimed features. 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 10, Yamaguchi suggests the process of claim 1. As discussed above for claim 1, where, as discussed above for claim 9, Yamaguchi is considered to provide conditions overlapping a range at which an intermediate is formed for desorbing hydrogen from the first film. Yamaguchi suggests using a first modifying agent and a second modifying agent meeting the claimed requirements such that the activation energy for an intermediate produced due to decomposition of the second modifying agent to desorb the hydrogen bonded to the carbon in the first film is smaller than an activation energy for the first modifying agent to desorb the hydrogen bonded to carbon in the first film. 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 11, Yamaguchi suggests the process of claim 1. They further teach that the second N- and H-containing gas is diazene, hydrazine, or N3H8 (0052).
Regarding claim 12, Yamaguchi suggests the process of claim 1. They further teach that the source gas is selected from those including silicon, carbon, hydrogen, and a halogen, i.e., chlorine, as in dimethyldichlorosilane, etc. (0043). Therefore, since they provide materials meeting the requirements of claims 1 and 12 and the required steps, the process is also expected to modify the first film to the second film in (b) such that the halogen element in the first film desorbs. 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, Yamaguchi suggests the process of claim 1. Since they provide materials meeting the requirements of claim 1 and the required steps, the process is also expected to modify the first film to the second film in (b) such that a reduction is made in the content rate of hydrogen bonded to the predetermined element in the first film. 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 16, Yamaguchi suggests the process of claim 1. They further teach loading wafers onto a boat and moving them into a chamber (0037). They teach that after a predetermined time has elapsed of supplying the first N- and H-containing gas, the valve is closed to stop the supply of the first N- and H-containing gas into the chamber and the gases are removed from the processing chamber by flowing an inert gas for purging (0042, 0047, and Fig. 4). Therefore, a space in which the substrate is located (the chamber) is purged after (a) and before (b).
Regarding claim 17, Yamaguchi suggests the process of claim 1. As discussed above for claim 1, the predetermined number of times is one. Yamaguchi further teaches performing steps (a) and (b) a predetermined number of times, where n is 1 or more, so as to include a plurality of times (0032 and Fig. 4). 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 18, Yamaguchi suggests the process of claim 1, where they further teach suing the process for manufacturing a semiconductor (0001 and 0031).
Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable over Yamaguchi as applied to claim 1 above, and further in view of Hsueh, US 2015/0179316 A1 and Kang, US 2014/0141542 A1.
Regarding claim 14, Yamaguchi suggests the process of claim 1.
They do not teach the features of claim 14.
Hsueh teaches methods of forming nitrides at low substrate temperatures, such as less than 500°C or even less than 400°C (abstract). They teach using nitrogen containing precursors with low dissociation energy such as hydrazine and diazene (abstract). They teach that most common nitrogen containing precursors, such as molecular nitrogen and ammonia, require high deposition temperatures, where they provide slow deposition rates at lower temperatures (0018). They teach that when using precursors having low activation energies, such as hydrazine and diazene, lower temperatures can be used (0019-0020).
Kang teaches methods of forming films on sensitive substrates by exposing the substrate to a silicon-containing reactant in vapor phase, exposing the substrate to an oxidizing reactant in vapor phase and periodically igniting a plasma (abstract and 0003). They teach that when depositing an oxide, the oxidant may flow continuously, but its flow rate may drop when the primary reactant, e.g., BTBAS, is delivered so as to increase the partial pressure of BTBAS during its dosing, thereby reducing the exposure time needed to saturate the substrate surface (0053). They teach that decreasing the flow rate of reactant A during B exposure phases increases the partial pressure of B and thereby increase the driving force of reactant B adsorbing on the substrate surface (0065).
From the teachings of Hseuh and Kang, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have provided the hydrazine or diazene gas at a smaller partial pressure than the ammonia gas because Hseuh indicates that ammonia has a higher activation energy than hydrazine or diazene and Kang teaches that increasing the partial pressure of a gas in a deposition increases the driving force of the reactant adsorbing on the substrate surface such that it will be expected to increase the driving force of ammonia on the surface so as to facilitate its reaction with the surface compared to hydrazine or diazene which will not require as high of a driving force due to the lower activation energy.
Claim 15 is rejected under 35 U.S.C. 103 as being unpatentable over Yamaguchi as applied to claim 1 above, and further in view of Hsueh, US 2015/0179316 A1 and Barik, US 2022/0406595 A1.
Regarding claim 15, Yamaguchi suggests the process of claim 1.
They do not teach the features of claim 15.
Hsueh teaches methods of forming nitrides at low substrate temperatures, such as less than 500°C or even less than 400°C (abstract). They teach using nitrogen containing precursors with low dissociation energy such as hydrazine and diazene (abstract). They teach that most common nitrogen containing precursors, such as molecular nitrogen and ammonia, require high deposition temperatures, where they provide slow deposition rates at lower temperatures (0018). They teach that when using precursors having low activation energies, such as hydrazine and diazene, lower temperatures can be used (0019-0020).
Barik teaches methods for depositing silicon-containing films on a substrate by exposing a substrate to a silicon precursor and a reactant to form the silicon-containing film such as a silicon nitride film (abstract). They teach that the exposures can be sequential or simultaneous (abstract). They teach that exposure to the silicon containing precursor can occur at a different temperature than exposure to the reactant (0062).
From the teachings of Hsueh and Barik, 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 hydrazine or diazene reactant at a lower temperature than ammonia because Hseuh teaches that hydrazine and diazene have a lower activation energy than ammonia such that a lower temperature can be used in deposition and Barik indicates that in a sequential deposition process, different temperatures can be used for different gases such that it will be expected to provide a suitable temperature for the ammonia exposure and a suitable temperature for the diazene or hydrazine exposure.
Conclusion
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718
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