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 1-15 are pending and rejected. Claims 16-20 are withdrawn. Claim 1 is amended.
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 2/19/2016 has been entered.
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 1-15 are rejected under 35 U.S.C. 103 as being unpatentable over Kuratomi, US 2020/0211852 A1 (provided on the IDS of 2/21/2023) in view of Gelatos, US 2018/0158686 A1 (provided on the IDS of 2/21/2023), and Murakami, US 2015/0179462 A1.
Regarding claims 1 and 8-10, Kuratomi teaches a method for processing a substrate (methods for selectively depositing a titanium material atop a substrate, abstract), comprising:
forming a plasma reaction between titanium tetrachloride (TiCl4), hydrogen (H2), and argon (Ar) in a region between a lid heater and a showerhead of a process chamber while providing RF power at a pulse frequency (forming a remote plasma reaction between titanium tetrachloride, hydrogen, and argon in a region between a lid heater and a showerhead of a process chamber, 0005 and 0007, where the plasma is generated by providing pulsed RF energy, 0032, such that it will be pulsed at a frequency); and
flowing reaction products into the process chamber to selectively form a titanium material layer upon a silicon surface of the substrate (flowing reaction products into the process chamber to selectively form a titanium material layer upon a silicon surface of the substrate, abstract and 0005).
They teach that in some embodiments, the RF Power is pulsed with a frequency of about 1 kHz and a duty cycle about 50% (0032). They teach that the titanium material layer selectively deposits on a silicon surface relative to a dielectric surface, where the dielectric surface is silicon oxide or silicon nitride (abstract and 0036).
They do not teach using a pulse frequency and duty cycle within the claimed range.
Gelatos teaches methods to selectively deposit titanium-containing films on silicon-containing surfaces in high aspect ratio features of substrates by PECVD (abstract). They teach that the substrate surface has at least one feature thereon, the at least one feature creating a gap with a bottom, a top, and sidewalls, the bottom comprising a metallic element or alloy, and the sidewalls comprising a metal oxide, a metal nitride, or a metal-oxide-nitride (0008). They teach that the metallic surface comprises Si and the different material, i.e., sidewalls, comprise SiOx or SiN (0024 and Fig. 2). They teach exposing the substrate surface to a PECVD deposition process using titanium and reductant precursors and optionally a carrier gas (0025). They teach that the titanium precursor is TiCl4-, the reductant is hydrogen, and the carrier gas is argon (0025, 0030, 0031, 0035, and 0043). They teach that the substrate is heated to a temperature within a range from about 300°C to less than 500°C (0033). They teach that the frequency of the plasma is in the range of about 10 kHz to about 50 MHz, and all values and subranges therein (0034). They teach that the duty cycle may be in the range of 1 to 90% and all values and subranges therein (0034). They teach that the plasma power may be pulsed, providing power every about 0.00001 to about 100 seconds, so as to provide a pulse frequency of about 0.01 Hz to 100 kHz, for a duration of about 0.0000001 to about 90 seconds and all values and subranges therein (0034). They teach that pulsing the power improves selectivity (0052). They teach that selectivity on SiN and SiOx improves with low duty cycle, but that the deposition rate also decreases, where duty cycles of 10%, 15%, and 25% are used (0058 and Table 6). They provide examples of pulsing at frequencies of 10 kHz and 5 kHz at duty cycles of various ranges including 25%, where pulsing at a 25% duty cycle with a 10 kHz pulse provided the best selectivity (0063 and Table 8).
From the teachings of Gelatos, 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 Kuratomi to have used a duty cycle in the range of 1 to 90% or 10%, 15%, or 25% and a pulse frequency of about 0.01 Hz to 100 kHz or at 5 kHz or 10 kHz or specifically pulsing at a 25% duty cycle with a 10 kHz frequency because Gelatos teaches that such ranges are suitable for selective deposition of titanium-containing films on Si surfaces relative to SiOx or SiN surfaces using PECVD with TiCl4, hydrogen, and argon at a temperature range within the range of Kuratomi such that it will be expected to provide a desirable plasma for the selective deposition. Further, since Gelatos teaches that pulsing the power is desirable for improving the selectivity, pulsing the power using the conditions of Gelatos is also expected to improve the selectivity of the process because it will still be providing pulse plasma containing the desired gases. Therefore, the duty cycle and pulse frequency are suggested to either overlap or be within the claimed range. 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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
As to the flow rates, Kuratomi further teaches that TiCl4 is provided at a flow rate of about 1 to 100 sccm (0030), so as to meet the claimed range. Kuratomi teaches that the flow rate of hydrogen is about 50 to 10000 sccm (0030), so as to overlap the claimed range at the endpoint. Kuratomi teaches that the processing volume is configured to receive about 3.5 liters of argon (0030).
They do not teach using an argon flow rate within the claimed range.
Murakami teaches a method of forming a Ti film on a substrate disposed in a chamber by introducing a processing gas containing TiCl4 gas as a Ti source and an H2 gas as a reducing gas and by generating plasma in the chamber by introducing an Ar gas as a plasma generation gas into the chamber (abstract). They teach converting the Ar gas into plasma to generate Ar ions and acting the Ar ions on the Ti film to promote desorption of Cl from the Ti film (abstract). They teach forming the Ti film on a wafer having an interlayer insulating film 111 on a Si substrate 110, where a contact hole 112 is formed in the interlayer insulating film (0037-0038 and Fig. 2). They teach flowing TiCl4, H2, and Ar to the chamber and generating plasma to form the Ti film on the substrate surface (0040). They teach that the Ar ions promote the desorption of Cl from the inside of the Ti film to provide a low resistance film and they have an etching function so as to remove Ti film on the flat portion or an overhang portion of the opening of the contact hole (0042). They teach increasing a flow rate of the Ar gas to allow the desorption of Cl and to decrease the flow rate of H2 gas more than the related art (0043). They teach that since desorption of Cl is possible by the Ar gas a small amount of H2 gas may be sufficient (0043). They teach that the TiCl4 gals flow rate is 1 to 100 sccm or 20 sccm, the Ar gas flow rate is 100 to 10,000 sccm or 2000 sccm, and the H2 gas flow rate is 20 to 5000 sccm or 20 sccm (0055-0057 and 0064-0066). They teach that the conditions can increase selectivity of the Ti film in the film formation at a low temperature, where the Ti film can be formed at a high film formation rate with respect to Si and at a low film formation rate with respect to SiO2 (0060).
From the teachings of Murakami, 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 Kuratomi in view of Gelatos to have used a TiCl4 flow rate of 1-100 sccm or 20 sccm, an Ar flow rate of 100-10,000 sccm, and an H2 flow rate of 20 to 5000 sccm or 20 sccm because Murakami teaches that such flow rates are desirable in a process of selectively forming Ti on an Si layer using plasma deposition where the flow rates are selected to desorb Cl from the Ti layer using the Ar ions so as to reduce the resistivity such that it will be expected to provide desirable flow rates in the selective deposition process. Therefore, the flow rate of TiCl4 meets the range of claim 1 and overlaps the range of claim 8, the flow rate of H2 overlaps or is within the range of claim 1 and meets the range of claim 9, and the flow rate of Ar overlaps the ranges of claims 1 and 10. 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.” 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 2, Kuratomi in view of Gelatos and Murakami suggest the process of claim 1, where the pulse frequency is suggested to overlap the range of claim 2 or to be within the range of claim 2, i.e. be in the range of about 0.01 Hz to 100 kHz or at 5 kHz or 10 kHz. 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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
Regarding claim 3, Kuratomi in view of Gelatos and Murakami suggest the process of claim 1, where the duty cycle is suggested to be overlap or be within the range of claim 3, i.e., where the duty cycle ranges from 1 to 90% or is 25%. 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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
Regarding claim 4, Kuratomi in view of Gelatos and Murakami suggest the process of claim 1. Kuratomi teaches that the power sources for plasma may be capable of producing up to 3000 Watts of RF energy at a frequency of about 350 kHz to about 60 MHz (0032).
Gelatos teaches that a plasma power may be in the range of about 1 to less than about 700 mWatts/cm2 (0034). They provide an example of using a power of 65 W (92 mW/cm2) (0063), which would correspond to a 300 mm wafer. Therefore, the plasma power range is understood to be about 1.38 to about 969 W. They further provide various experiments to determine the selectivity of the process where the power, frequency, duty cycle, and pressure are varied (0042-0064). They teach that at higher powers, the selectivity decreases, however, a higher deposition rate is provided (Table 3).
Murakami teaches that using a high frequency power in the range of 100 to 3000 W, where if the high frequency power is less than 100 W, the desorption of Cl from the inside of the Ti film and promoting film formation may not sufficiently occur (0049).
From the teachings of Gelatos and Murakami, 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 a plasma power in the range of about 100 to about 969 W or to have optimized the power to be within the claimed range because Kuratomi teaches using an energy source capable of producing up to 3000 Watts, Gelatos suggests that a power range of about 1.38 to about 969 W is suitable when performing a selective deposition of a titanium-containing film by a PECVD process similar to that of Kuratomi, and Murakami teaches that having a power of 100-3000 W is desirable in a similar process, where having a power of less than 100 W does not sufficiently promote the desorption of Cl, and further because Gelatos provides examples of determining the selectivity by varying process variables including power, where increasing the power reduces selectivity, but increases deposition rate, indicating that the power can be optimized by routine experimentation along with duty cycle, pressure, plasma frequency, etc. to provide the required efficiency (deposition rate) and selectivity. 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976). According to MPEP 2144.05 II A, “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claim 5, Kuratomi in view of Gelatos and Murakami suggests the process of claim 1. Kuratomi teaches that the RF energy source is capable of producing RF energy at a frequency of about 350 kHz to about 60 MHz, such as at about 350 kHz (0032).
Gelatos teaches that the frequency may be in the range of 350 kHz to 40 MHz (0034) and they provide an example of using a frequency of 350 kHz (0044).
Murakami teaches that when the Ti film is formed, the frequency of the high frequency power supplied is preferably in a range of 200 kHz to 13.56 MHz (0050).
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 used a plasma frequency of 350 kHz because both Kuratomi and Gelatos teaches that such a frequency is desirable for the selective deposition process, where the range of Murakami overlaps 350 kHz.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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original).
Regarding claim 6, Kuratomi in view of Gelatos and Murakami suggest the process of claim 1. Kuratomi teaches depositing the titanium material to a predetermined thickness such as about 10 angstroms to about 100 angstroms, or about 100 to about 500 angstroms (0041).
Gelatos teaches depositing for ~300 seconds, ~600 seconds (0042, 0044, 0048), where the thickness of the film increases with increasing time of the process (Fig. 4). They also provide an example of pulsing the plasma on for 0.8 seconds and off for 1.1 seconds, where 790 cycles are performed so as to provide a duration of about 1501 seconds, where a cycle is understood to be the total of the on and off time (Table 4).
From the teachings of Kuratomi and Gelatos, 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 deposition time to be within the claimed range because Kuratomi teaches depositing the films to a desired thickness and Gelatos teaches that increasing the deposition time increases the thickness of the film, where deposition times can be ~300, ~600, or 1501 s such that by optimizing the deposition time it will be expected to provide the desired thickness. According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claim 7, Kuratomi in view of Gelatos and Murakami suggest the process of claim 1. Gelatos further teaches using a pressure in the pulsed process of 5 Torr (0051).
Murakami further teaches using a pressure of 0.1 to 10 Torr (0058).
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 pressurized the chamber to 0.1 to 10 Torr or 5 Torr during the plasma reaction because Murakami and Gelatos teaches that such pressures are suitable for the selective deposition of a titanium material by PECVD in a process similar to that of Kuratomi. While 5 Torr is higher than the claimed range, it is considered to be close enough to 3 Torr to expect similar results. Therefore, the pressure overlaps the claimed range or is close enough to expected similar results. 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976). Note MPEP 2144.04(I): Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. Titanium Metals Corp. of America v. Banner, 778 F.2d 775, 783, 227 USPQ 773, 779 (Fed. Cir. 1985) (Court held as proper a rejection of a claim directed to an alloy of "having 0.8% nickel, 0.3% molybdenum, up to 0.1% iron, balance titanium" as obvious over a reference disclosing alloys of 0.75% nickel, 0.25% molybdenum, balance titanium and 0.94% nickel, 0.31% molybdenum, balance titanium. "The proportions are so close that prima facie one skilled in the art would have expected them to have the same properties.").
Alternatively, Gelatos provides various experiments to determine the selectivity of the process where the power, frequency, duty cycle, and pressure are varied (0042-0064). 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 optimized the pressure to be within the claimed range using routine experimentation when pulsing the plasma because Gelatos indicates that such parameters can be varied to determine the desired selectivity. According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claim 11, Kuratomi in view of Gelatos and Murakami suggest the process of claim 1. Kuratomi teaches that the substrate has features having a high aspect ratio, where the silicon surface is at the bottom of the feature and a dielectric surface is disposed on one or more sidewalls of the feature (0019, 0034, 0040, 0041, and Fig. 3A).
Regarding claim 12, Kuratomi in view of Gelatos and Murakami suggest the process of claim 11. Kuratomi teaches that the dielectric surface comprises silicon oxide or silicon nitride (0036 and Fig. 3A).
Murakami also teaches that the interlayer dielectric is silicon dioxide (0060).
Regarding claim 13, Kuratomi in view of Gelatos and Murakami suggest the process of claim 1. Kuratomi teaches depositing the titanium material to a thickness of about 10 angstroms to about 100 angstroms (0041), so as to be within the claimed range.
Murakami also teaches depositing the Ti film to have a thickness of 1 to 10 nm or so, i.e. 10 to 100 Angstroms (0059), so as to be within the claimed range.
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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original).
Regarding claim 14, Kuratomi in view of Gelatos and Murakami suggest the process of claim 1. Kuratomi teaches that the titanium material comprises titanium, titanium silicide, or substantially pure titanium (0041).
Murakami teaches depositing a Ti film that reacts with the Si substrate to form a TiSix film (0040).
Regarding claim 15, Kuratomi in view of Gelatos and Murakami suggest the process of claim 1. Kuratomi teaches adding one or more silane compounds, hydrogen, and a noble gas such as argon to the showerhead to contact the remote plasma reaction, where the one or more silane compounds include one or more of silane, disilane, trisilane, and tetrasilane, or a combination thereof (0061). Therefore, silane, disilane, hydrogen, and argon will be added to the showerhead to contact the plasma reaction.
Claims 1-9 and 11-15 are rejected under 35 U.S.C. 103 as being unpatentable over Kuratomi, US 2020/0211852 A1 (provided on the IDS of 2/21/2023) in view of Gelatos, US 2018/0158686 A1 (provided on the IDS of 2/21/2023), and Basceri, US 2003/0170982 A1.
Regarding claims 1, 8, 9, and 15, Kuratomi teaches a method for processing a substrate (methods for selectively depositing a titanium material atop a substrate, abstract), comprising:
forming a plasma reaction between titanium tetrachloride (TiCl4), hydrogen (H2), and argon (Ar) in a region between a lid heater and a showerhead of a process chamber while providing RF power at a pulse frequency (forming a remote plasma reaction between titanium tetrachloride, hydrogen, and argon in a region between a lid heater and a showerhead of a process chamber, 0005 and 0007, where the plasma is generated by providing pulsed RF energy, 0032, such that it will be pulsed at a frequency); and
flowing reaction products into the process chamber to selectively form a titanium material layer upon a silicon surface of the substrate (flowing reaction products into the process chamber to selectively form a titanium material layer upon a silicon surface of the substrate, abstract and 0005).
They teach that in some embodiments, the RF Power is pulsed with a frequency of about 1 kHz and a duty cycle about 50% (0032). They teach that the titanium material layer selectively deposits on a silicon surface relative to a dielectric surface, where the dielectric surface is silicon oxide or silicon nitride (abstract and 0036).
They do not teach using a pulse frequency and duty cycle within the claimed range.
Gelatos teaches methods to selectively deposit titanium-containing films on silicon-containing surfaces in high aspect ratio features of substrates by PECVD (abstract). They teach that the substrate surface has at least one feature thereon, the at least one feature creating a gap with a bottom, a top, and sidewalls, the bottom comprising a metallic element or alloy, and the sidewalls comprising a metal oxide, a metal nitride, or a metal-oxide-nitride (0008). They teach that the metallic surface comprises Si and the different material, i.e., sidewalls, comprise SiOx or SiN (0024 and Fig. 2). They teach exposing the substrate surface to a PECVD deposition process using titanium and reductant precursors and optionally a carrier gas (0025). They teach that the titanium precursor is TiCl4-, the reductant is hydrogen, and the carrier gas is argon (0025, 0030, 0031, 0035, and 0043). They teach that the substrate is heated to a temperature within a range from about 300°C to less than 500°C (0033). They teach that the frequency of the plasma is in the range of about 10 kHz to about 50 MHz, and all values and subranges therein (0034). They teach that the duty cycle may be in the range of 1 to 90% and all values and subranges therein (0034). They teach that the plasma power may be pulsed, providing power every about 0.00001 to about 100 seconds, so as to provide a pulse frequency of about 0.01 Hz to 100 kHz, for a duration of about 0.0000001 to about 90 seconds and all values and subranges therein (0034). They teach that pulsing the power improves selectivity (0052). They teach that selectivity on SiN and SiOx improves with low duty cycle, but that the deposition rate also decreases, where duty cycles of 10%, 15%, and 25% are used (0058 and Table 6). They provide examples of pulsing at frequencies of 10 kHz and 5 kHz at duty cycles of various ranges including 25%, where pulsing at a 25% duty cycle with a 10 kHz pulse provided the best selectivity (0063 and Table 8).
From the teachings of Gelatos, 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 Kuratomi to have used a duty cycle in the range of 1 to 90% or 10%, 15%, or 25% and a pulse frequency of about 0.01 Hz to 100 kHz or at 5 kHz or 10 kHz or specifically pulsing at a 25% duty cycle with a 10 kHz frequency because Gelatos teaches that such ranges are suitable for selective deposition of titanium-containing films on Si surfaces relative to SiOx or SiN surfaces using PECVD with TiCl4, hydrogen, and argon at a temperature range within the range of Kuratomi such that it will be expected to provide a desirable plasma for the selective deposition. Further, since Gelatos teaches that pulsing the power is desirable for improving the selectivity, pulsing the power using the conditions of Gelatos is also expected to improve the selectivity of the process because it will still be providing pulse plasma containing the desired gases. Therefore, the duty cycle and pulse frequency are suggested to either overlap or be within the claimed range. 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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
As to the flow rates, Kuratomi further teaches that TiCl4 is provided at a flow rate of about 1 to 100 sccm (0030), so as to meet the claimed range. Kuratomi teaches that the flow rate of hydrogen is about 50 to 10000 sccm (0030), so as to overlap the claimed range at the endpoint. Kuratomi teaches that the processing volume is configured to receive about 3.5 liters of argon (0030). Kuratomi also teaches adding one or more silane compounds, hydrogen, and a noble gas such as argon to the showerhead to contact the remote plasma reaction, where the one or more silane compounds include one or more of silane, disilane, trisilane, and tetrasilane, or a combination thereof (0061). Therefore, silane, disilane, hydrogen, and argon will be added to the showerhead to contact the plasma reaction as required by claim 15.
They do not teach using an argon flow rate within the claimed range.
Basceri teaches CVD methods of forming titanium silicide comprising layers on substrates (abstract). They teach feeding TiCl4 and at least one silane to a chamber for a period of time effective to plasma enhance chemical vapor deposit a titanium silicide comprising layer on the substrate (0018). They teach that plasma generation can be direct within the chamber or remote therefrom (0018). They teach that exemplary processing gases include SiH4 at from 0.5 sccm to 10 sccm, TiCl4 at from 50 sccm to 150 sccm, Ar at from 2,000 sccm to 6,000 sccm, He at from 1,000 sccm to 2,000 sccm, and H2 at from 200 sccm to 10,000 sccm in a 6.55 liter chamber (0018).
From the teachings of Basceri, 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 Kuratomi in view of Gelatos to have used a TiCl4 flow rate of 1-150 sccm, an Ar flow rate of 2,000-6,000 sccm, and an H2 flow rate of 20 to 10,000 sccm because the ranges overlap the ranges taught by Kuratomi and Basceri for depositing a Ti-containing layer using plasma deposition such that it will be expected to provide desirable flow rates in the selective deposition process. Therefore, the flow rate of TiCl4 overlaps the ranges of claims 1 and 8, the flow rate of H2 overlaps the ranges of claims 1 and 9, and the flow rate of Ar overlaps the range of claim 1. 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.” 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 2, Kuratomi in view of Gelatos and Basceri suggest the process of claim 1, where the pulse frequency is suggested to overlap the range of claim 2 or to be within the range of claim 2, i.e. be in the range of about 0.01 Hz to 100 kHz or at 5 kHz or 10 kHz. 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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
Regarding claim 3, Kuratomi in view of Gelatos and Basceri suggest the process of claim 1, where the duty cycle is suggested to be overlap or be within the range of claim 3, i.e., where the duty cycle ranges from 1 to 90% or is 25%. 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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
Regarding claim 4, Kuratomi in view of Gelatos and Basceri suggest the process of claim 1. Kuratomi teaches that the power sources for plasma may be capable of producing up to 3000 Watts of RF energy at a frequency of about 350 kHz to about 60 MHz (0032).
Gelatos teaches that a plasma power may be in the range of about 1 to less than about 700 mWatts/cm2 (0034). They provide an example of using a power of 65 W (92 mW/cm2) (0063), which would correspond to a 300 mm wafer. Therefore, the plasma power range is understood to be about 1.38 to about 969 W. They further provide various experiments to determine the selectivity of the process where the power, frequency, duty cycle, and pressure are varied (0042-0064). They teach that at higher powers, the selectivity decreases, however, a higher deposition rate is provided (Table 3).
Basceri teaches using a plasma generating power in the range from 200 to 600 Watts (0015).
From the teachings of Gelatos and Basceri, 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 a plasma power in the range of about 100 to about 969 W or to have optimized the power to be within the claimed range because Kuratomi teaches using an energy source capable of producing up to 3000 Watts, Gelatos suggests that a power range of about 1.38 to about 969 W is suitable when performing a selective deposition of a titanium-containing film by a PECVD process similar to that of Kuratomi, and Basceri teaches that having a power of 200-600 W is desirable in a similar process which is within the range suggested by Gelatos, and further because Gelatos provides examples of determining the selectivity by varying process variables including power, where increasing the power reduces selectivity, but increases deposition rate, indicating that the power can be optimized by routine experimentation along with duty cycle, pressure, plasma frequency, etc. to provide the required efficiency (deposition rate) and selectivity. 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976). According to MPEP 2144.05 II A, “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claim 5, Kuratomi in view of Gelatos and Basceri suggests the process of claim 1. Kuratomi teaches that the RF energy source is capable of producing RF energy at a frequency of about 350 kHz to about 60 MHz, such as at about 350 kHz (0032).
Gelatos teaches that the frequency may be in the range of 350 kHz to 40 MHz (0034) and they provide an example of using a frequency of 350 kHz (0044).
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 used a plasma frequency of 350 kHz because both Kuratomi and Gelatos teaches that such a frequency is desirable for the selective deposition 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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original).
Regarding claim 6, Kuratomi in view of Gelatos and Basceri suggest the process of claim 1. Kuratomi teaches depositing the titanium material to a predetermined thickness such as about 10 angstroms to about 100 angstroms, or about 100 to about 500 angstroms (0041).
Gelatos teaches depositing for ~300 seconds, ~600 seconds (0042, 0044, 0048), where the thickness of the film increases with increasing time of the process (Fig. 4). They also provide an example of pulsing the plasma on for 0.8 seconds and off for 1.1 seconds, where 790 cycles are performed so as to provide a duration of about 1501 seconds, where a cycle is understood to be the total of the on and off time (Table 4).
From the teachings of Kuratomi and Gelatos, 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 deposition time to be within the claimed range because Kuratomi teaches depositing the films to a desired thickness and Gelatos teaches that increasing the deposition time increases the thickness of the film, where deposition times can be ~300, ~600, or 1501 s such that by optimizing the deposition time it will be expected to provide the desired thickness. According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claim 7, Kuratomi in view of Gelatos and Basceri suggest the process of claim 1. Gelatos further teaches using a pressure in the pulsed process of 5 Torr (0051).
Basceri teaches that a preferred chamber pressure range is from 3 to 6 Torr (0015).
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 pressurized the chamber to 3 to 6 Torr during the plasma reaction because Basceri and Gelatos teaches that such pressures are suitable for the selective deposition of a titanium material by PECVD in a process similar to that of Kuratomi. Therefore, the pressure overlaps the claimed range. 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
Alternatively, Gelatos provides various experiments to determine the selectivity of the process where the power, frequency, duty cycle, and pressure are varied (0042-0064). 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 optimized the pressure to be within the claimed range using routine experimentation when pulsing the plasma because Gelatos indicates that such parameters can be varied to determine the desired selectivity. According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claim 11, Kuratomi in view of Gelatos and Basceri suggest the process of claim 1. Kuratomi teaches that the substrate has features having a high aspect ratio, where the silicon surface is at the bottom of the feature and a dielectric surface is disposed on one or more sidewalls of the feature (0019, 0034, 0040, 0041, and Fig. 3A).
Regarding claim 12, Kuratomi in view of Gelatos and Basceri suggest the process of claim 11. Kuratomi teaches that the dielectric surface comprises silicon oxide or silicon nitride (0036 and Fig. 3A).
Regarding claim 13, Kuratomi in view of Gelatos and Basceri suggest the process of claim 1. Kuratomi teaches depositing the titanium material to a thickness of about 10 angstroms to about 100 angstroms (0041), so as to be within the claimed range. 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.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original).
Regarding claim 14, Kuratomi in view of Gelatos and Basceri suggest the process of claim 1. Kuratomi teaches that the titanium material comprises titanium, titanium silicide, or substantially pure titanium (0041).
Basceri teaches forming a titanium silicide layer (abstract).
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over Kuratomi in view of Gelatos and Basceri as applied to claim 1 above, and further in view of Yamasaki, US 2015/0322571 A1.
Regarding claim 10, Kuratomi in view of Gelatos and Basceri suggest the process of claim 1, where it is suggested to use an argon gas flow rate of 2,000-6,000 sccm (0018).
They do not teach a flow rate within the claimed range.
Yamasaki teaches a process of forming a Ti film on a wafer by supplying TiCl4 gas, H2 gas, and Ar gas (0036 and 0038). They teach that the flow rates of TiCl4, H2, and Ar are about 5 to 50 sccm, about 5 to 10,000 sccm, and about 100 sccm to 5,000 sccm (0038). They teach applying a high frequency power to an electrode to form a plasma of the gases containing TiClx, Ti, Cl, H, and Ar (0039).
From the teachings of Yamasaki, 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 a flow rate argon in the range of 100 to 6,000 sccm because Yamasaki teaches that a suitable range is from 100 to 5000 sccm, suggesting that a range of 100-6000 sccm (incorporating the ranges of both Yamasaki and Basceri) will provide a suitable flow rate of argon. Therefore, the range will overlap the range of claim 10. 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.”
Response to Arguments
Applicant’s arguments provided 2/19/2026 have been fully considered.
In light of the amendments to the claims, the previous 112 rejection has been withdrawn.
In response to applicant's argument that the claimed process provides benefits of reducing byproduct and improves productivity of high selectivity junction TiSix deposition, the fact that the inventor has recognized another advantage which would flow naturally from following the suggestion of the prior art cannot be the basis for patentability when the differences would otherwise be obvious. See Ex parte Obiaya, 227 USPQ 58, 60 (Bd. Pat. App. & Inter. 1985). Specifically, since Kuratomi in view of Gelatos and Murakami of Basceri suggest the process of claim 1, similar benefits are expected to also result.
Regarding Applicant’s argument over Murakami being directly counter to Applicants method, it is noted that while Murakami teaches forming a direct plasma, the inclusion of argon in the gas mixture at the ratio suggested by Murakami is still expected to be applicable to the claimed process because it will provide argon in the gas mixture at a higher ratio so as to etch the chlorine on the surface of the substrate to remove it from the film. Specifically, while Applicant indicates that the process traps reaction products within the showerhead, since it also results in forming a film on the substrate surface, not all products will be trapped in the showerhead and the resulting argon plasma that exits through the showerhead will then be able to remove chlorine from the surface of the substrate.
Further, a new rejection has been made with the new reference of Basceri which suggests overlapping flow rates in a remote plasma deposition process.
Conclusion
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718
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