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 1-16 and 19 are pending and rejected. Claims 17 and 18 are withdrawn. Claims 1-15 are amended.
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 3, 4, and 8-12 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 3 and 4, the claims have been amended to state “supplying the fourth processing gas including the N-H bond and having a composition different from that of the second processing gas to the substrate”, where (a) and (d) are performed Y times, Y being a natural number of one or greater, after (d), however, in claim 1, the fourth gas includes hydrogen and a second element different from the first element and the second processing gas includes the N-H bond. The instant specification lists various gases used as the fourth processing gas, where the gases do not include an N-H bond and there is no indication that the fourth process gas is flowed along with the gas including the N-H bond. Therefore, the claims are considered to include new matter. Appropriate action is required without adding new matter.
Regarding claims 8-10, the claims have been amended to indicate that the fourth processing gas including the N-H bond and having a composition different from that of the second processing gas is supplied during the temperature rise, however, as noted above, the fourth gas is not indicated as including the N-H bond and there is no indication that the fourth gas and the gas having the N-H bond are flowed together. It is noted that the specification describes using the second or third gases for the heat treatment process, where the second gas includes an N-N bond and an N-H bond and the third gas includes the N-H bond (0003, 0055, 0067-0068). Therefore, the claims are considered to include new matter. Appropriate action is required without adding new matter.
Regarding claims 11 and 12, the claims state “in (b) the fourth processing gas including the N-H bond and having a composition different from that of the second processing gas is supplied”, however, as noted above, the fourth processing gas does not have the N-H bond and as depicted in Fig. 6, the fourth gas is not provided in a step including the N-H bond. Therefore, the claims are considered to include new matter. Appropriate action is required without adding new matter.
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 3, 4, and 8-12 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 and 4, the claims have been amended to state “supplying the fourth processing gas including the N-H bond and having a composition different from that of the second processing gas to the substrate”, where (a) and (d) are performed Y times, Y being a natural number of one or greater, after (d), however, in claim 1, the fourth gas includes hydrogen and a second element different from the first element and the second processing gas includes the N-H bond. Therefore, it is not clear whether claims 3 and 4 are intended to state “supplying a third processing gas including the N-H bond and having a composition different from that of the second processing gas to the substrate”, where (a) and (e) are performed Y times after (d) as is suggested by Fig. 6 of the instant specification. Further, the instant specification lists various gases used as the fourth processing gas, where the gases do not include an N-H bond. Therefore, the claims are being interpreted as though a third gas is supplied including the N-H bond and having a composition different from the second processing gas and where (a) and (e) are performed Y times after (d) as is supported by the specification. Appropriate action is required without adding new matter.
Regarding claims 8-10, the claims have been amended to indicate that the fourth processing gas including the N-H bond and having a composition different from that of the second processing gas is supplied during the temperature rise, however, as noted above, the fourth gas is not indicated as including the N-H bond. It is noted that the specification describes using the second or third gases for the heat treatment process, where the second gas includes an N-N bond and an N-H bond and the third gas includes the N-H bond (0003, 0055, 0067-0068). For the purposes of examination, the claims are being interpreted as though the third processing gas including the N-H bond is provided as is supported by the specification. Appropriate action is required without adding new matter.
Regarding claims 11 and 12, the claims states “in (b) the fourth processing gas including the N-H bond and having a composition different from that of the second processing gas is supplied”, however, as noted above, the fourth processing gas does not have the N-H bond and as depicted in Fig. 6, the fourth gas is not provided in a step including the N-H bond. For the purposes of examination, the claim is being interpreted as though claim 11 reads in (b), a third processing gas including the N-H bond and having a composition different from that of the second processing gas is supplied as is supported by the specification. 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 1-4, 11-16, and 19 are rejected under 35 U.S.C. 103 as being unpatentable over Clark, US 2008/0241382 A1 in view of Ogawa, US 2020/0194269 A1.
Regarding claims 1 and 2, Clark teaches a method of processing a substrate (a method for forming a strained metal nitride film on a substrate, abstract), comprising:
(a) supplying a first processing gas containing a first element and a halogen to a substrate (exposing a substrate to a gas pulse of a metal precursor at step 322, 0092 and Fig. 3B, where the metal precursors include those having a metal element and a halogen, 0060, 0061, 0082-0084);
(b) supplying a second processing gas including an N-N bond and an N-H bond to the substrate (exposing the substrate to a gas pulse containing a first nitrogen precursor or a gas pulse containing a first nitrogen precursor and a second nitrogen precursor in a first ratio at step 324, where the first and second nitrogen precursors are selected from gases including ammonia and hydrazine, 0093 and Fig. 3B, such that the process gas will include an N-N bond and an N-H bond in hydrazine or in a mixture of hydrazine and ammonia); and
(c) performing (a) and (b) X times, X being a natural number, in a state where the substrate is heated to a temperature of 250°C or lower to form a first film containing the first element (where steps 322 and 324 are repeated a first number of times, 0096 and Fig. 3B, where an example include performing the steps 3, 2, and 1 times so as to provide a natural number of 1 or greater, 0100, and where the temperature of the substrate is controlled in a range from approximately 150°C to 350°C, 0031, so as to overlap the range of claims 1 and 2).
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.”
Clark teaches that the metal halide precursor includes TiCl4 (0060), where the film formed includes titanium nitride (abstract and 0024). They also teach that the film deposited can be a strained metal nitride or metal silicon nitride film (0015).
They do not teach supplying a fourth gas including hydrogen and a second element different from the first element to the substrate, where the fourth gas is provided for a time overlapping step (a).
Ogawa teaches a method of manufacturing a semiconductor device, including forming a metal nitride film substantially not containing a silicon atom on a substrate by sequentially repeating: (a) supplying a metal-containing gas and a reducing gas, which contains silicon and hydrogen and does not contain a halogen, to the substrate in a process chamber, (b) removing the metal-containing gas and the reducing gas that remain in the process chamber, (c) supplying a nitrogen-containing gas to the substrate, and (d) removing the nitrogen-containing gas remaining in the process chamber (abstract and Fig. 4). They teach using the process to form a TiN film where TiCl4 gas is supplied as a metal-containing gas, and a SiH4 gas is supplied as a reducing gas (0053 and Fig. 4). They teach that the TiCl4 and SiH4 gases are removed from the chamber and then NH3 gas is supplied as the nitrogen-containing gas (0053 and Fig. 4). They teach that after a predetermined time of supplying TiCl4, the supply of SiH4 is begun such that the TiCl4, SiH4, and N2 gases are supplied simultaneously to the wafer, where the supply of SiH4 continues after the supply of TiCl4 is stopped (0061, 0063, and Fig. 4). They teach that the process is repeated a predetermined number of times to form a TiN film having the desired thickness (0070). They teach that HCl is a byproduct of the TiCl4/NH3 reaction, where HCl can be adsorbed on the surface of the TiN film which reduces the deposition rate (0004). They teach that SiH4 reacts with HCl to provide SiCl4 and H2, which is discharged from the reaction so as to reduce the HCl in the film (0064). They teach that the process efficiently discharges HCl generated during film formation, allowing for an increased deposition rate, lowers the film resistivity, and improves the oxidation resistance (0073-0076). They teach that the pressure, flow rate, and time for supplying the silicon precursor can be adjusted to increase the Si content of the film and form a TiSiN film (0062, 0064, and 0118).
From the teachings of Ogawa, 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 Clark to have supplied a fourth gas including hydrogen and a second element different from the first element in the form of SiH4 to the substrate during a period overlapping with (a), i.e., the supply of TiCl4 and for a predetermined time after (a) because Ogawa teaches that such a process flow can be used to remove HCl from the film to increase the deposition rate, reduce resistivity, and provide oxidation resistance in the process of forming a TiN film using a process similar to that of Clark, where the process parameters such as pressure, flow rate, and supply time can be used to increase or minimize the silicon content in the film such that it will be expected to provide the benefits described by Ogawa while providing the strained TiN or TiSiN film by changing the pressure, flow rate, or flow time of the SiH4 gas.
Regarding claims 3 and 4, Clark in view of Ogawa suggests the process of claims 1 and 2. Clark further teaches supplying a second gas pulse of the metal precursor at step 326 and exposing the substrate to a gas pulse containing the second nitrogen precursor or a gas pulse containing the first nitrogen precursor and the second nitrogen precursor in a second ratio different from the first ratio at step 328 (0094 and Fig. 3B). As noted above, the first and second nitrogen precursors are selected from ammonia and hydrazine (0093). They teach repeating steps 326 and 328 a second number of times prior to repeating steps 322 and 324 (0097 and Fig. 3B), where an example is provided of performing the steps 1, 2, and 3 times (0100). Therefore, they provide supplying a third processing gas including the N-H bond (ammonia and hydrazine) and having a composition different from that of the second processing gas to the substrate (where the composition is different due to the different ratio of ammonia and hydrazine), and performing (a) and (e) Y times, where Y is a natural number of 1 or greater, after (d) to form a second film containing the first element on the first film.
Alternatively, they provide an example where hydrazine is provided to form a first metal nitride film and ammonia is used to form a second metal nitride film on the first metal nitride film (0016). 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 used hydrazine as the first gas for step (b) and ammonia as the second gas for step (d) because they indicate that hydrazine can be used as the first gas and ammonia can be used as the second. Therefore, the third process gas will include the N-H bond from ammonia and will have a composition different from that of the second processing gas (which would be hydrazine so as to include the N-H and N-N bond).
Regarding claims 11 and 12, Clark in view of Ogawa suggests the process of claims 1 and 2. As noted above for claims 3 and 4, Clark teaches and/or suggests supplying a third process gas including the N-H bond and having a composition different from that of the second processing gas after supplying the second processing gas. Therefore, providing the third processing gas after supplying the silicon precursor, i.e., steps 326 and 328, is considered to meet the requirements of claims 11 and 12 because it provides steps (a) and (b) with a processing gas including the N-H bond and having a composition different from that of the second processing gas.
Alternatively, since they indicate that in step 324, the gas can include a mixture of hydrazine and ammonia (0093 and Fig. 3B), step (b) will include a second process gas including an N-N bond and an N-H bond in hydrazine and a third process gas will be included having the N-H bond in ammonia where it will have a different composition than the second processing gas.
Regarding claims 13 and 14, Clark in view of Ogawa suggests the process of claim 1. Clark further teaches forming a strained metal silicon nitride film by exposing a substrate to a gas pulse containing a metal precursor at step 622, exposing the substrate to a gas pulse containing a first nitrogen precursor or a gas pulse containing the first nitrogen precursor and a second nitrogen gas precursor in a first ratio in step 624, where steps 622 and 624 are sequentially performed a first number of times (0130-0131, 0134, and Fig. 6B). They teach that the first and second nitrogen precursors are selected from ammonia and hydrazine (0131). They teach in step 626, the substrate is exposed to a gas pulse containing a silicon precursor followed by step 628 where the substrate is exposed to a gas pulse containing the second nitrogen precursor or a gas pulse containing the first nitrogen precursor and the second nitrogen precursor in a second ratio different from the first ratio (0132 and Fig. 6B). As discussed above, the metal nitride precursors are selected from precursors that include halides. Therefore, they provide step a) of providing a metal precursor that includes a halide and then supplying a third processing gas after step (a) and after step (c), where the fourth processing gas contains a second element different from the first element, i.e., silicon compared to the metal of the first element, so as to form a film containing a second element on the first film.
As discussed above, Ogawa teaches that the process conditions can be tuned to increase or minimize the amount of silicon provided in the film. 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 silicon precursor at conditions minimizing the amount of inclusion during step 622 of Clark and then to have provided only the silicon precursor at step 626 so as to form the silicon layer in forming the TiSiN film so as to have controlled the amount of silicon included in the film. Alternatively, 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 conditions to include the silicon precursor while flowing SiH4 during step (a) and after step (a) so as to provide the desired amount of silicon to the film, where in such a case, the third processing gas and the fourth processing gas are the same, having a second element different from the first element, where the second element is included into the film.
Regarding claim 15, Clark in view of Ogawa suggests the process of claim 1. Clark further teaches that (b) is performed before (d) (0092-0093, 0096, and Fig. 3B).
Regarding claim 16, Clark in view of Ogawa suggests the process of claim 1. Clark further teaches forming the strained metal nitride in a semiconductor device (abstract), such that the method is included in manufacturing a semiconductor device.
Regarding claim 19, Clark in view of Ogawa suggests the process of claim 1. Clark further teaches supplying N2H4 for forming a first metal nitride film (0016), where since they supply a gas containing an N-N and N-H bond, the surface of the substrate is also expected to be NH-terminated as described at paragraph 0051 of the instant specification. 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)”.
Alternatively, Clark teaches forming the strained metal nitride or metal silicon nitride film in a stack where an oxide film 116 is formed and a conductive layer 117 is formed (0022-0024 and Fig. 1). They teach that the conductive layer 117 and the film 118 may be composed of the same metal nitride or metal silicon nitride film (0024). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed the TiN or TiSiN film on the oxide layer 116 using the process of Clark in view of Ogawa because Clark teaches that the films can be the same material and they provide a process for forming the material such that it will be expected to form the TiN or TiSiN layer as desired. Therefore, the process will include forming the layer on an oxide surface, such that the hydrazine gas will also be expected to form the NH-terminations as described in the instant specification at [0051].
Claims 5-7 are rejected under 35 U.S.C. 103 as being unpatentable over Clark in view of Ogawa as applied to claims 1-3 above, and further in view of Vaartstra, US 2004/0043604 A1 and Kim, US 2006/0014385 A1.
Regarding claims 5-7, Clark in view of Ogawa suggests the process of claims 1-3.
They do not teach heat-treating the substrate at a temperature higher than the temperature of (d) after (d).
Vaartstra teaches a method of forming refractory metal nitride layers (including silicon nitride layers) on a substrate by an ALD process (abstract and 0016). They teach providing a vapor that includes one or more refractory metal precursor compounds of the formula MYn, where M is selected from a group including Ti and Y is a halogen atoms such as F, Cl, I, or combinations thereof (0012). They teach providing a vapor that includes one or more disilazanes, where silane is an alternative to the disilazane (0012 and 0038). They teach providing nitrogen sources such as ammonia, hydrazine, etc. and combinations thereof (0043). They teach that the ALD process is performed at temperatures of about 25°C to about 400°C (0052). They teach that after layer formation on the substrate, an annealing process can be performed in situ in a nitrogen atmosphere or an ammonia atmosphere (0062). They teach annealing at a temperature within the range of about 400°C to about 1000°C (0062). Therefore, Vaartstra teaches performing an ammonia annealing step on ALD films, where formed films include TiSiN and where the annealing temperature is higher than the deposition temperature.
Kim teaches forming a first titanium nitride layer by CVD or ALD using TiCl4 and ammonia and depositing a second titanium nitride layer on the first by CVD at a second temperature with TiCl4 and ammonia (abstract). They teach forming a lower metal layer composed of TiSiN by a CVD or process or an ALD process (0066). They teach that a thermal annealing process may be performed on the lower metal layer to minimize the chlorine content inside the lower metal layer (0066). They teach that after forming a first titanium nitride layer, the chlorine element inside the layer can be removed by exposing the layer to only an ammonia gas (0041).
From the teachings of Vaartstra and Kim, 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 annealed the TiSiN film in ammonia at a temperature in the range of 400°C to 1000°C (so as to be higher than the deposition temperature) because Vaartstra teaches that it is desirable to anneal a TiSiN film formed by an ALD process similar to that of Clark in view of Ogawa and Kim teaches that thermally annealing a TiSiN film reduces the chlorine content in the layer, where flowing ammonia helps to reduce chlorine in a TiN layer such that it will be expected to desirably treat the film while also reducing any residual chlorine. Therefore, the process will comprise heat-treating the substrate at a temperature higher than the temperature during deposition after the step of repeating the process. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.”
Claims 8-10 are rejected under 35 U.S.C. 103 as being unpatentable over Clark in view of Ogawa as applied to claims 1-3 above, and further in view of Vaartstra, US 2004/0043604 A1, Kim, US 2006/0014385 A1, and Raaijmakers, US 6,348,420 B1.
Regarding claims 8-10, Clark in view of Ogawa suggests the process of claims 1-3.
As noted above Vaartstra and Kim provide the suggestion of annealing the films at a temperature higher than the temperature used in (c), where they suggest annealing in ammonia. Vaartstra teaches annealing in situ in the deposition chamber (0062).
They do not teach flowing ammonia to the substate during the temperature rise to the higher temperature.
Raaijmakers teaches performing multiple sequential processes in situ in a single-wafer processing chamber in forming dielectric stacks of high quality (abstract). They teach that the process forms silicon oxide, nitride, and/or oxynitride followed by in situ silicon nitride deposition (abstract). They teach annealing can also be conducted in situ, reducing transition time without commensurate loss in reaction rates (abstract). They teach that after deposition, the second or deposited dielectric layer is annealed to improve the quality the layer, where the anneal is a high temperature ammonia anneal that densifies the silicon nitride layer by reacting any excess silicon and producing more stoichiometric Si3N4 (Col. 11, lines 38-53). They teach forming a dielectric stack comprising interfacial oxynitride and overlying silicon nitride on a substrate followed by performing an in situ anneal (Col. 15, lines 14-37). They teach that after forming the dielectric stack, silane flow is stopped while nitrogen and ammonia flow are maintained at the same flow rate as during nitride deposition while the temperature is ramped from 780°C to about 900°C and the anneal is maintained for about 60 seconds (Col. 15, lines 21-37).
From the teachings of Vaartstra and Raaijmakers, 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 performed the annealing treatment while flowing ammonia and increasing the temperature to the annealing temperature because Vaartstra teaches performing an anneal in the same chamber, where the annealing can be done in ammonia, and Raaijmakers teaches annealing a nitride in ammonia gas in situ by flowing ammonia while increasing the temperature so as to react excess silicon with ammonia, where they indicate that performing the process in situ reduces transition time without commensurate loss in reaction rates such that it will be expected to reduce the chlorine content while increasing the temperature for annealing while providing the benefits described by Raaijmakers. Therefore, the process will comprise (f) heat-treating the substrate at a temperature higher than the temperature of (c) after (c) (i.e., after forming the film), wherein a third processing gas including the N-H bond having a composition different than that of the second processing gas (i.e., ammonia) is supplied to the substrate during the temperature rise to the higher temperature.
Response to Arguments
Applicant’s arguments dated 2/17/2026 have been fully considered.
In light of the amendments to the claims, the previous objections have been withdrawn.
In light of the amendments the claims, new 112(b) rejections have been made as indicated above.
Further, in light of the amendment to claim 1, the rejection using Chen has been withdrawn and the rejection using Clark has been modified as indicated above.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CHRISTINA D MCCLURE whose telephone number is (571)272-9761. The examiner can normally be reached Monday-Friday, 8:30-5:00 EST.
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718 /GORDON BALDWIN/Supervisory Patent Examiner, Art Unit 1718
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