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 1-4, 6-13, and 16-28 are pending and rejected. Claims 29-32 are withdrawn. Claim 1 is amended. Claims 5, 14, and 15 are cancelled.
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 7/23/2026 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 1-4, 6-13, 16-21, 23, 24, 26, and 27 are rejected under 35 U.S.C. 103 as being unpatentable over Kang, US 2014/0141542 A1 in view of Rueger, US 2005/0284360 A1, Sobell, “Hollow Cathode Plasma Electron Source for Low Temperature Deposition of Cobalt Film by Electron-Enhanced Atomic Layer Deposition”, 2021, Li, “Electron beam injection from a hollow cathode plasma into a downstream reactive environment: Characterization of secondary plasma production and Si3N4 and Si etching”, 2020, Kim, US 2022/0205099 A1, and Citla, US 2022/0351969 A1.
Regarding claims 1, 13, and 20, Kang teaches depositing films on sensitive substrates (abstract). They teach forming the films using plasma-activated surface-mediated reactions in which a film is grown over multiple cycles of reactant adsorption and reaction, where one or more reactants adsorb to the substrate surface and then react to form a film on the surface by interaction with plasma (0032). They teach that the cycle includes delivery/adsorption of reactant A in phase 120, delivery/adsorption of reactant B in phase 140, sweep of B out of the reaction chamber, and applying plasma to drive a surface reaction of A and B to form the film layer on the surface in phase 180 (0046, 0061, and Fig. 1A). They teach that reactant A flows continuously during the film deposition process and plasma is ignited while reactant A is in the gas phase (0061 and Fig. 1). They teach providing the reactants in the vapor phase (0003, 0045, 0055, 0066, 0067, 0122, 0123). They teach that the cycle typically contains an exposure phase for each reactant and during the exposure phase, a reactant is delivered to a process chamber to cause adsorption of the reactant on the substrate surface (0063). They teach that reactants A and B are allowed to mingle in the gas phase process, where reactants A and B are chosen so that they can co-exist in the gas phase without appreciably reacting with one another under conditions encountered in the chamber prior to application of plasma energy or activation of the surface reaction (0064). They teach selecting the reactants so that the reaction has a sufficiently high activation energy that there is negligible reaction at the desired deposition temperature absent plasma activation (0064). They teach that the plasma activation phase drives the reaction of the one or more reactants adsorbed on the substrate surface (0073). They teach that principal reactants contain an element that is solid at room temperature and contributes to the film formed, where examples include titanium and aluminum (0047). They teach that auxiliary reactants are not principal reactants and include ammonia, oxygen, alkyl amines, etc. (0047). They teach that for the deposition of metal oxides or metal nitrides, any appropriate metal-containing reactants and co-reactants may be used (0049). They teach depositing metal-containing films such as oxides and nitrides of aluminum, titanium, hafnium, etc. and using reactants such as tetraethoxytitanium, tetrakis-dimethyl-amido titanium, etc. (0086). They teach that when the deposited film contains nitrogen, a nitrogen-containing reactant such as ammonia is used (0087). They teach that an advantage of the continuous flow embodiment is that the established flow avoids the delays and flow variations caused by transient initialization and stabilization of flow associated with turning the flow on and off (0051). They teach that the reactant that flows continuously is an auxiliary reactant (0053). They teach depositing on sensitive substrates such as Si, silicon nitride, and silicon oxide (0034), such that they deposit on solid substrates.
Therefore, they teach forming a titanium nitride film by a plasma-activated CFD process, where the film is understood to be a conductive layer as indicated by claim 20 by contacting at least a portion of a surface of a solid substrate with a volatile metal precursor (i.e., titanium-containing precursor, where they indicate that the reactants are provided in the vapor phase), in the presence of a reactive background gas (auxiliary reactant such as ammonia that flows continuously), where the volatile metal precursor chemisorbs or physisorbs to at least a portion of the surface of the solid substrate to provide a precursor-adsorbed substrate surface (since the precursor adsorbs to the substrate), removing excess volatile metal precursor from the precursor-adsorbed substrate surface (sweeping reactant B, i.e. non-auxiliary reactant), and contacting at least a portion of the metal-precursor adsorbed substrate surface with a plasma in the presence of the reactive background gas.
They do not teach contacting the substrate with an electron beam.
Rueger teaches forming a layer of material on a surface by ALD methods using electron bombardment of the chemisorbed precursor (abstract). They teach providing energy transfer in an ALD process with little or no sputtering using electron exposure to provide the energy (0013). They teach that by using electrons as the carriers of energy to the chemisorbed precursor during an ALD cycle, collisions in which significant amounts of momentum transfer occur (as in a PEALD process) are substantially reduced or non-existent (0013). They teach that the process includes providing a precursor including a metal component to the process chamber for chemisorption of the precursor on an underlying surface, removing any excess precursor from the process chamber, contacting the chemisorbed precursor with electrons, and providing a reactant in the process chamber for converting the chemisorbed precursor to a monolayer or less of material (0014). They teach that the precursor includes a metal component such as titanium in TiCl4 or it may be an organometallic precursor (0040). They teach that the reactant may include any reactant suitable for use in converting the chemisorbed species present on the deposition surface as part of an ALD cycle, e.g., provide a reducing atmosphere (0046). They teach that the invention uses energetic electron bombardment to provide sufficient energy to promote ligand removal in an atmosphere including a reactant gas for converting the chemisorbed species to a material for forming the layer being deposited or otherwise modifying the chemisorbed species (0049). They teach that the reactant is in the process chamber when the chemisorbed species is bombarded by electrons where the energetic electrons transfer energy to the process, allowing the reactant to react with the chemisorbed precursor and to strip away unwanted ligands to drive the surface reaction (0071). They teach that since the activation energy for the surface reaction is provided by the energetic electrons, the reaction does not generally occur without the energy provided by the electron bombardment because the process temperature is kept below the temperature required for thermal activation (0072). They teach that the film thickness is controlled by repeating the ALD cycle as desired (0074).
From the teachings of Rueger, 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 Kang to have used an electron beam to have supplied the energy for driving the surface reaction in the formation of the TiN film because Rueger teaches that such a process provides energy for forming a film by ALD (similar to the CFD process of Kang) while reducing or eliminating sputtering that can occur in the plasma deposition process such that it will be expected to provide the energy as needed for performing the reaction while providing the benefit of reducing or eliminating sputtering. Further, since Rueger teaches that the process conditions are controlled so that the reaction is driven by the electrons as opposed to thermally driven and Kang teaches continually supplying an auxiliary reactant, where ammonia as an auxiliary reactant, where gas-phase reactions do not occur, 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 continuously supplied NH3 during the process because the conditions will be set so that the reaction between the reactant and the precursor do not occur in the vapor phase in the absence of the energetic electrons. Therefore, the surface will be contacted with a volatile metal precursor in the presence of a background gas (ammonia) and the metal precursor-adsorbed substrate surface will be contacted with the reactive background gas (ammonia) during the electron beam exposure so as to provide the energy to the ammonia co-reactant for forming the TiN film.
They do not teach generating the electron beam using HC-PES.
Sobell teaches using a HC-PES for rapid nucleation and low temperature deposition of cobalt films using EE-ALD (abstract). They teach that the HC-PES displayed high electron currents, rapid ALD cycling, and low susceptibility to chemical interference (abstract). They teach that the high currents from the HC-PES yielded rapid nucleation of the films (abstract). They teach that HC-PES are much more robust and produce higher currents than electron guns based on hot filaments (pg. 042403-2, section I). They teach that the HC-PES produces an electron beam with high currents and provides the advantage of rapid on/off switching (pg. 042403-6, section IV A). Sobell teaches using an electron current of 10 mA (pg. 042403-7, section IV B), 72 mA (pg. 042403-8, section IV B), and 65 mA (pg. 042403-9, section IV B).
Li teaches a material etching system developed by combining electron injection from a direct current hollow cathode electron source with a downstream reactive environment of a remote CF4/O2 low temperature plasma (abstract). They teach that HC EB source allow us to inject electron beams into a fairly high-pressure gas (up to 100 s of mTorr) and cover an area that can be fairly large (pg. 033001-2, section 1). They teach using an HC EB source with low and adjustable electron energy to allow electron beam injection into a relatively high-pressure (~mTorr) environment (pg. 033001-2, section 1). They teach that the pressure in the HC source (Torr level) is significantly higher than the chamber pressure below because of a choked flow connection (pg. 033001-2, section II). They teach that the reaction chamber pressure was kept at 2-100 mTorr during processing (pg. 033001-2, section II). Therefore, Li teaches that electrons from an HC-PES can be injected into a gas in a chamber having a pressure in the range of 2-100 mTorr or ~mTorr.
From the teachings of Sobell and Li, 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 Kang in view of Rueger to have used a HC-PES as the electron beam source with a current of 10 mA, 65 mA, or 72 mA because Sobell teaches that such an electron beam source provides the benefits of high electron currents, rapid on/off switching, and rapid nucleation in ALD, where such currents are used, and Li teaches that an HC-PES can be used to inject electrons into a reactive gas in a chamber such that it will be expected to provide a desirable source of electrons with a suitable current for interacting with the ammonia gas for the electron enhanced deposition process. Therefore, the electron current will be within the range of claim 13. 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).
They do not teach the pressure of the reactive background gas.
Kang teaches using a pressure of between about 2 and 10 torr for forming the protective layer (0103), where they teach that low pressure can reduce damage to the substrate (0035).
Rueger teaches that during electron bombardment (e.g., operation of an electron gun), the chamber pressure is generally needed to be low to generate and provide for electron bombardment (0086). Rueger further teaches that the electron source provides electrons having a mean energy that is greater than about 30 eV and/or less than about 100 KeV or greater than about 100 eV and/or less than about 5 KeV (0064).
Sobell teaches that HC-PES designs conveniently operate at pressures of 10-500 mTorr (pg. 042403-2, section I). They teach using argon gas to produce the electron beam (Fig. 1). They teach that it is important to maintain a lower pressure in the chamber so as to provide a pressure differential across the aperture of the hollow cathode cavity (pg. 042403-47, section II. C., and Fig. 2). Sobell teaches using low energy (100-200 eV) electrons (abstract).
As noted above, Li teaches that electrons from an HC-PES can be injected into a gas in a chamber having a pressure in the range of 2-100 mTorr or ~mTorr.
Kim teaches a method for forming a Group IV transition metal containing film by PEALD in which (a) a substrate is exposed to a vapor of a Group IV transition metal containing film forming composition, (b) the substrate is exposed to a co-reactant, and the steps of (a) and (b) are repeated until as desired thickness of the Group IV transition metal containing film is deposited on the substrate (abstract, 0008-0011, and 0039). They teach that the co-reactant is ammonia (0019-0020). They teach that the substrate may be any suitable substrate used in semiconductors, photovoltaics, etc., where examples include wafers such as silicon, silica, glass, GaAs, etc. (0120), such that they deposit the films on solid substrates. They teach that the Group IV transition metal containing film is a nitride film (0028), such that when using a titanium precursor (0012), the film will be a titanium nitride film, where titanium nitride films are conductive metal nitrides (0120), so as to provide a conductive layer. They also teach using ammonia as the co-reactant when the target is a conductive film (0124). They teach that the co-reactant may be treated by a plasma in order to decompose the reactant into its radical form (0126). They teach that the ALD conditions within the chamber allow the disclosed Group IV transition metal-containing film forming composition adsorbed or chemisorbed on the substrate surface to react and form a Group IV transition metal-containing film on the substrate (0129). They teach that plasma-treating the co-reactant may provide the co-reactant with the energy needed to react with the Group IV transition metal-containing film forming composition (0129). They teach that the co-reactant can be introduced continuously to the reactor while the Group IV transition metal-containing film forming composition is pulsed, while activating the co-reactant sequentially with a plasma, provided that the Group IV transition metal-containing film forming composition and the non-activated co-reactant do no substantially react at the chamber temperature and pressure conditions (0131). They teach that the temperature and the pressure within the reactor are held at conditions suitable for ALD, where the pressure may be between about 10-3 torr and about 100 Torr (0122).
Citla teaches methods for forming an integrated circuit structure including generating a plasma comprising ions in a process volume, bombarding an electrode with the ions to cause the electrode to emit electrons and form an electron beam, and contacting a dielectric material with the electron beam to cure a dielectric material (abstract). They teach that a beam energy of the electron beam is approximately equal to the ion bombardment energy of the electrode, which typically can range from 10 eV to 20,000 eV (0048). They teach that at least a portion of the electron beam propagates through the process volume and reacts with process gases near the substrate (0049). They teach that with utilization of suitable process gases, such as helium, argon, hydrogen, ammonia, disilane, methane, etc., and combinations thereof, the electron beam induces curing reactions on the substrate (0049). They teach that the electron beams, generate chemically reactive radicals and ions which adsorb to the surface of the substrate and form a chemically reactive layer of the surface of the substrate (0049). They teach that the electron beam induces chemical reacts to liberate certain species in a substrate such as oxygen, or add one or more species to a substrate such as nitrogen (0050). They teach that the pressure during the electron beam curing process is between about 3.0 mTorr and about 100 mTorr (0050). They teach forming the electron beam from a reaction including a process gas comprising one or more of argon, ammonia, etc. at a pressure in the range of 3 to 100 mTorr (0093). Therefore, they teach that an electron beam can be used to activate a gas such as ammonia using a beam having energy of 10 eV to 20,000 eV with a pressure in the range of 3 to 100 mTorr.
From the teachings of Rueger, Sobell, Li, Kim, and Citla, 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 an ammonia background gas pressure in the range of 3 mTorr to about 100 mTorr with an electron beam having an energy of 100-200 eV because Li teaches that HC-PES can be used to inject electrons into a gas having a pressure in the range of 2-100mTorr, Citla teaches an electron beam can be used to activate a gas such as ammonia using a beam having energy of 10 eV to 20,000 eV with a pressure in the range of 3 to 100 mTorr for surface reactions, Kim indicates that PEALD (similar to the CFD process of Kang) can be performed at a pressure of 0.01 mTorr to 100 Torr, Kang teaches using lower pressures prevent damage to the substrate, where Sobell indicates that such an electron energy is desirable for ALD, which is within the range of Rueger and Citla such that it will be expected to provide a suitable pressure and electron beam energy for forming the electron beam and interacting with the ammonia gas in the electron enhanced deposition process. Therefore, the background gas will have a pressure close to the claimed range and an energy overlapping 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.” According to MPEP 2144.05(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."). Therefore, while the pressure range suggested by Kang in view of Rueger, Sobell, Li, Kim, and Citla of 3-100 mTorr is higher than the claimed range, the range is considered to be close enough to the claimed range to expected similar results (i.e., 3 mTorr is considered to be close enough to 1 or 2 mTorr to expect similar results).
Alternatively, since Sobell indicates that the pressure differential is desirable and Li teaches that the electrons can be injected into a gas having a pressure in the range of 2-100 mTorr, 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 optimize the pressure of the ammonia gas to be within the claimed range so as to provide a suitable differential pressure for the process while providing sufficient ammonia for the EE-ALD process. 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).
Therefore, the electron beam will have an energy overlapping the claimed range and the reactive background gas will have pressure close enough to render the claimed range obvious or optimized to be within the claimed range.
Regarding claims 2-4, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Kang teaches using titanium precursors such as tetraethoxytitanium and tetrakis-dimethyl-amido titanium (0086), so as to provide metal-organic complexes in the form of an amide of titanium or an alkoxide of titanium. They also provide trimethyl aluminum, i.e., an alkyl of aluminum, hafnium tetrakis (ethylmethylamide), i.e., an amide of hafnium, bis(cyclopentadienyl) manganese and bis(n-propylcyclopentadienyl) magnesium, i.e., cyclopentadienyl compounds of Mg or Mn (0086). Therefore, the metal-organic complexes will include Hf, Al, and Ti.
Regarding claims 6 and 7, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Kang further teaches using ammonia as an auxiliary reactant (0087), so as to provide a nitride gas.
Regarding claims 8-10, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Kang further teaches depositing the films on substrates such as silicon, cobalt, SiGe, SiC, silicon nitride, SiO2, metal oxides, lanthanide-oxides, noble metals, etc. (0034), such that the substrate incudes a semiconductor, metal, metal oxide, etc., and will comprise silicon and specifically silicon nitride and silicon dioxide.
Regarding claim 11, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1.
As discussed above, Kim teaches depositing a TiN film by PEALD using the same substrates as Kang (silica, silicon, etc.). Kim further teaches that each pulse of the Group IV transition metal-containing film forming composition may last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 seconds to about 80 seconds (0132).
From the teachings of 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 contacted the substrate with the volatile metal precursor for a time ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 seconds to about 80 seconds because Kim teaches that such an exposure time is suitable for forming a TiN film by PEALD which is a process similar to that of Kang on substrates used by Kang such that it will be expected to provide a suitable time of the adsorption of the metal precursor to the substrate. Therefore, the contacting time will overlap 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.”
Regarding claim 12, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Rueger teaches that the precursor and reactant are provided at a pulse duration sufficient to perform its intended function, where the reactant is pulsed for a duration sufficient for converting the chemisorbed species to the desired material (0082).
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 electron beam exposure to be within the claimed range because Rueger teaches using a time sufficient for converting the chemisorbed species to the desired material such that the time will be optimized for providing the film on the surface as desired. 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 claims 16 and 17, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Kang teaches that the damage to the substrate is prevented by depositing a thin protective layer at a relatively low temperature and/or at a relatively low pressure (0035). They teach that the CFD temperature is generally between about 20 and 400°C or between about 20 and 100°C (0057), such that the temperature is within or overlapping the claimed range.
Rueger also teaches keeping the temperature below the temperature required for thermal activation so that the process is electron-induced rather than thermally-induced (0072).
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 temperature of between about 20 and 400°C, between about 20 and 100°C, or to have optimized the temperature to be within the claimed range for steps (a) and (b) so as to prevent the thermal reaction between the precursors so as to ensure that the process is electron-induced because Kang indicates that such temperature ranges are suitable for the CFD process using continuously flowed auxiliary reactant and because it is indicates as being desirable to avoid gas phase reactions which are dependent on temperature such that the ranges and optimization of temperature is expected to provide desirable results. 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.” 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 19, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Rueger further teaches that the growth rate on average is about 0.2 to about 3 A/cycle, where the deposition process is continued until a layer of desired thickness is built up on the surface of interest (0081). Therefore, the steps of (a) and (b) are repeated to increase the conductive film thickness, where the average growth per cycle is expected to overlap 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.”
Regarding claim 21, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 20, where it is suggested to deposit a TiN film. Kang teaches that sweeping the process station may avoid gas phase reactions where reactant B is susceptible to plasma activation, where sweeping may remove surface adsorbed ligands that may otherwise remain and contaminate the film (0071). 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 film to have a purity within the claimed range because Kang indicates that it is desirable to prevent contaminants in the film, where a TiN film is desired, where since they suggest forming the film using the claimed process, the resulting film is also expected to have a purity within the claimed range. 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). 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 claims 18, 23, 24, 26, and 27, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 20. Kang teaches performing the cycles a suitable number of times to deposit a desired film thickness (0062). They teach depositing a protective layer having a thickness of less than about 100 Å or greater than 100 Å (0104).
Rueger teaches that during each deposition cycle the growth rate on average is from about 0.2 to about 3 A/cycle (0081).
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 performed less than 33 or less than 500 cycles of steps (a) and (b) so as to provide a film having a thickness of less than 100 A and to have performed more than 33 or more than 500 cycles to provide a thickness of greater than 100 A because Kang teaches that such a thickness is desirable for forming a protective layer and Rueger teaches that in the EE-ALD process, the average growth per cycle is 0.2 to 3 A such that it will be expected to provide a suitable number of cycles for providing the desired thickness. Therefore, the number of cycles and the thickness of the films will overlap the ranges of claims 23-24 and 26-27. 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.”
Alternatively, since Kang teaches forming a film thickness overlapping the ranges of claims 24 and 27, where the EE-ALD cycles are repeated to provide the desired thickness and they suggest performing the process of claim 1 to form a TiN film, 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 number of cycles to be within the claimed ranges so as 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).
Further, as to claim 18, since they suggest performing less than 33 or less than 500 cycles of the claimed process, using substrate materials meeting the requirements of claims 8-10, using precursors meeting the requirements of claims 2-4, and a background gas meeting the requirements of claims 6 and 7, the resulting process is also expected to provide nucleation in about 7 cycles. 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)”.
Claim 22 is rejected under 35 U.S.C. 103 as being unpatentable over Kang in view of Rueger, Sobell, Li, Kim, and Citla as applied to claim 20 above, and further in view of Sanchez, US 2019/0161358 A1.
Regarding claim 22, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 20.
They do not teach the ratio of Ti:N.
Sanchez teaches forming titanium nitride films by PEALD using titanium precursors including halides and organic groups with ammonia as a reactant (abstract, 0020, 0282, 0285, 0310, and 0319). They teach that the titanium nitride film throughout the specification is listed without reference to their proper stoichiometry, i.e., Ti3N4 (0353). They teach that the layers may include TikNl- layers where l and k range from 1 to 6 (0353).
From the teachings of Sanchez, 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 film to have a stoichiometry of Ti3N4 (so as to provide a Ti:N ratio of 3:4) because Sanchez teaches that this is the proper stoichiometry for a TiN film, where such a film can be formed by PEALD such that it will be expected to provide a desirable TiN film. Further, since they suggest forming the TiN film by the claimed process, the resulting film is expected to have the claimed Ti:N ratio. Therefore, the Ti:N ratio will meet 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 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)”.
Claims 25 and 28 are rejected under 35 U.S.C. 103 as being unpatentable over Kang in view of Rueger, Sobell, Li, Kim, and Citla as applied to claims 23 and 26 above, and further in view of Gatineau, US 2011/0206862 A1.
Regarding claims 25 and 28, Kang in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claims 23 and 26.
They do not teach the resistivity of the films.
Gatineau teaches vapor deposition methods for depositing TiN films using precursors such as Ti(iPr3Cp)(NMe2)3, Ti(Me5Cp)(NMe2)3, etc. (0010). They teach that at least part of the titanium-containing precursor is deposited onto the substrate to form a titanium-containing layer on the substrate which is then reacted with a vapor of a plasma-treated reactant, such as ammonia, to form a TiN layer (0010-0011). They teach that the process is a PEALD process (abstract). They teach that the TiN film has a resistivity between approximately 100 micro-ohm-cm to approximately 1,000 micro-ohm-cm (0024). They teach that optimization of the plasma time, plasma power, and/or pulse duration can improve the resistivity of the film (0060).
From the teachings of Gatineau, 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 process, such as the energy of the electrons, electron exposure, and/or pulse duration to form the TiN film having a resistivity in the range of approximately 100 to 1000 micro-ohm-cm because Gatineau teaches that such a resistivity is desirable for a TiN film formed by PEALD and Rueger teaches using electrons as an energy source instead of plasma to provide improved results, where the electrons are suggested to supply the energy for reaction, such that by optimizing the energy of the electrons, electron exposure, and/or pulse duration it is expected to also be capable of providing a TiN film with a resistivity in the range of 100 to 1000 micro-ohm-cm. Further, since Kang in view of Rueger, Sobell, Li, Kim, Citla, and Gatineau suggest depositing the TiN film using the process of claims 23 and 26, the resulting film is also expected to provide a resistivity meeting the claimed range. Therefore, the films are optimized to have a resistivity overlapping the claimed ranges. 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.” 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). 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)”.
Claims 1-4, 6-13, 16-18, 20-24, 26, and 27 are rejected under 35 U.S.C. 103 as being unpatentable over Takamure, US 2015/0099072 A1 in view of Rueger, US 2005/0284360 A1, Sobell, “Hollow Cathode Plasma Electron Source for Low Temperature Deposition of Cobalt Film by Electron-Enhanced Atomic Layer Deposition”, 2021, Li, “Electron beam injection from a hollow cathode plasma into a downstream reactive environment: Characterization of secondary plasma production and Si3N4 and Si etching”, 2020, Kim, US 2022/0205099 A1, and Citla, US 2022/0351969 A1.
Regarding claims 1, 13, and 20, Takamure teaches a method of promoting nucleation and/or growth of a conductive film on a solid substrate (forming a Ti-containing film on a substrate, abstract, where the Ti-containing film is a TiN film, 0005, so as to be conductive as indicated by claim 20, where the substrate is silicon, 0109, so as to provide a solid substrate), the method comprising:
(a) contacting at least a portion of a surface of the solid substrate with a volatile metal precursor in the presence of a reactive background gas, wherein the volatile metal precursor is chemisorbed or physisorbed to at least a portion of the surface of the solid substrate to provide a metal precursor-adsorbed substrate surface (introducing TDMAT and/or TDEAT in a pulse to a reaction space where a substrate is placed while continuously introducing an ammonia-free reactant to the reaction space, 0034, where the reactant gas is H2 and/or N2, 0037, where the material adsorbs on the surface of a substrate, 0040 and 0052, where the process uses gases, 0030); and
(b) removing excess volatile metal precursor from the precursor-adsorbed substrate surface (where the nitrogen, hydrogen, and/or oxygen flows continuously and functions as a purge gas between the pulse of the precursor feed and the pulse of RF power, 0038 and Fig. 6, such that excess volatile metal precursor will be removed during the purge step); and
(c) contacting at least a portion of the metal precursor-adsorbed substrate surface with a plasma (applying RF power in a pulse to the reaction space, 0034 and Fig. 6).
They teach that the PEALD process is a surface plasma treatment method as opposed to a PECVD process which is a gas-phase reaction method (0052).
They do not teach contacting with an electron beam.
As discussed above, from the teachings of Rueger, 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 Takamure to have used an electron beam to have supplied the energy for driving the surface reaction in the formation of the TiN film because Rueger teaches that such a process provides energy for forming a film by ALD while reducing or eliminating sputtering that can occur in PEALD such that it will be expected to provide the energy as needed for performing the reaction while providing the benefit of reducing or eliminating sputtering. Further, since Rueger teaches that the process conditions are controlled so that the reaction is driven by the electrons as opposed to thermally driven and Takamure teaches continually supplying the reactant, where gas-phase reactions do not occur since it is a PEALD process, 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 continuously supplied the H2 and/or N2 during the process because the conditions will be set so that the reaction between the reactant and the precursor do not occur in the vapor phase in the absence of the energetic electrons. Therefore, the surface will be contacted with a volatile metal precursor in the presence of a background gas (H2 and/or N2) and the metal precursor-adsorbed substrate surface will be contacted with the background gas during the electron beam exposure so as to provide the energy to the reactants for forming the TiN film. It is noted that the restriction dated 7/1/2025 only required an election of a hydride, oxide, nitride, sulfide, or halide gas as the background gas and since nitride gas was elected in the response dated 8/22/2025, the use of N2 is considered to read on the elected species even if it is not specifically ammonia.
They do not teach generating the electron beam using HC-PES.
As discussed above, from the teachings of Sobell and Li, 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 Takamure in view of Rueger to have used a HC-PES as the electron beam source with a current of 10 mA, 65 mA, or 72 mA because Sobell teaches that such an electron beam source provides the benefits of high electron currents, rapid on/off switching, and rapid nucleation in ALD, where such currents are used, and Li teaches that an HC-PES can be used to inject electrons into a reactive gas in a chamber such that it will be expected to provide a desirable source of electrons with a suitable current for interacting with the ammonia gas for the electron enhanced deposition process. Therefore, the electron current will be within the range of claim 13. 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).
As to the energy of the beam and the reactive gas background pressure, as discussed above, from the teachings of Rueger, Sobell, Li, Kim, and Citla, 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 an ammonia background gas pressure in the range of 3 mTorr to about 100 mTorr with an electron beam having an energy of 100-200 eV because Li teaches that HC-PES can be used to inject electrons into a gas having a pressure in the range of 2-100mTorr, Citla teaches an electron beam can be used to activate a gas such as ammonia using a beam having energy of 10 eV to 20,000 eV with a pressure in the range of 3 to 100 mTorr for surface reactions, Kim indicates that PEALD can be performed at a pressure of 0.01 mTorr to 100 Torr, Takamure teaches using a PEALD process, where Sobell indicates that such an electron energy is desirable for ALD, which is within the range of Rueger and Citla such that it will be expected to provide a suitable pressure and electron beam energy for forming the electron beam in an ammonia gas in the CFD deposition process. Therefore, the background gas will have a pressure close to the claimed range and an energy overlapping 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.” According to MPEP 2144.05(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."). Therefore, while the pressure range suggested by Takamure in view of Rueger, Sobell, Li, Kim, and Citla of 3-100 mTorr is higher than the claimed range, the range is considered to be close enough to the claimed range to expected similar results (i.e., 3 mTorr is considered to be close enough to 1 or 2 mTorr to expect similar results).
Alternatively, since Sobell indicates that the pressure differential is desirable and Li teaches that the electrons can be injected into a gas having a pressure in the range of 2-100 mTorr, 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 optimize the pressure of the ammonia gas to be within the claimed range so as to provide a suitable differential pressure for the process while providing sufficient ammonia for the EE-ALD process. 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).
Therefore, the electron beam will have an energy overlapping the claimed range and the reactive background gas will have pressure close enough to render the claimed range obvious or optimized to be within the claimed range.
Regarding claims 2-4, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Takamure further teaches using tetrakis(dimethylamino)titanium (TDMAT) or tetrakis(diethylamino)titanium (TDEAT) as a precursor (0005). Therefore, the volatile metal precursor includes a metal-organic complex of titanium and specifically an amide of titanium.
Regarding claims 6 and 7, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Takamure further teaches using H2 and/or N2 as the reactive gas (0006 and 0037), such that the reactive gas includes a hydride and a nitride gas.
Regarding claims 8 and 9, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Takamure further teaches using silicon substrates (0109), therefore, the solid substrate comprises a semiconductor that comprises silicon.
Regarding claim 10, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 8.
They do not teach that the substrate is specifically one of the listed materials.
As discussed above, Kim teaches depositing a TiN film by PEALD. Kim further teaches that the substrate may be any material used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing (0067). They teach that he substrate may have layers including silicon layers, SiO2, SiN, crystalline silicon layers, metal layers, etc. (0067).
From the teachings of 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 used a substrate such as SiO2, SiN, or crystalline silicon as the substrate because Kim teaches that such substrates are desirable for depositing TiN film by PEALD such that it will be expected to provide a suitable substrate.
Regarding claim 11, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Takamure further teaches supplying the precursor for a time of 0.2 seconds to 2 seconds or 0.3 seconds (Table 1 and Table 8). Therefore, the time for contacting the volatile metal and the solid substrate is 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.”
Regarding claim 12, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Rueger teaches that the precursor and reactant are provided at a pulse duration sufficient to perform its intended function, where the reactant is pulsed for a duration sufficient for converting the chemisorbed species to the desired material (0082).
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 electron beam exposure to be within the claimed range because Rueger teaches using a time sufficient for converting the chemisorbed species to the desired material such that the time will be optimized for providing the film on the surface as desired. 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 claims 16 and 17, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1. Takamure further teaches using a temperature of 70°C to 250°C (Table 1). They indicate that controlling the temperature and the RF power can change the film properties, where a lower temperature provides less carbon in the film (0067, Table 17, and Table 18).
Rueger also teaches keeping the temperature below the temperature required for thermal activation so that the process is electron-induced rather than thermally-induced (0072).
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 temperature of 70°C to 250°C (so as to include a range of about 70°C), or to have optimized the temperature to be within the claimed range for steps (a) and (b) so as to control film properties and to prevent the thermal reaction between the precursors so as to ensure that the process is electron-induced because Takamure indicates that such temperature ranges are suitable for the process using continuously flowed reactants and because it is indicates as being desirable to avoid gas phase reactions which are dependent on temperature such that the ranges and optimization of temperature is expected to provide desirable results. 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.” 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 claims 18, 23, 24, 26, and 27, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claims 1 and 20. Takamure teaches forming the Ti-containing film to a thickness of about 0.3 nm to about 60 nm, typically about 0.06 nm to about 300 nm (0044), i.e., 30 A to about 600 A or about 0.6 A to about 3000 A.
Rueger teaches that during each deposition cycle the growth rate on average is from about 0.2 to about 3 A/cycle (0081).
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 performed a range of about 0.2 to 15000 cycles of steps (a) and (b) so as to provide a film having a thickness in the range desired by Takamure because Takamure teaches that such a thickness is desirable and Rueger teaches that in the EE-ALD process, the average growth per cycle is 0.2 to 3 A such that it will be expected to provide a suitable number of cycles for providing the desired thickness. Therefore, the number of cycles and the thickness of the films will overlap the ranges of claims 23-24 and 26-27. 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.”
Alternatively, since Takamure teaches forming a film thickness overlapping the ranges of claims 24 and 27, where the EE-ALD cycles are repeated to provide the desired thickness and they suggest performing the process of claim 1 to form a TiN film, 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 number of cycles to be within the claimed ranges so as 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).
Further, as to claim 18, since they suggest performing about 0.2 to 15000 cycles of steps (a) and (b) of the claimed process, using substrate materials meeting the requirements of claims 8 and 9, using precursors meeting the requirements of claims 2-4, and a background gas meeting the requirements of claims 6 and 7, the resulting process is also expected to provide nucleation in about 7 cycles. 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 21, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 1, where it is suggested to deposit a TiN film. Takamure teaches that TDMAT and TDEAT have no bonds such as Ti-C and Ti-H, where all four hands of Ti are Ti-N bonds such that nitrogen can be incorporated into the film and carbons can be easily removed so as to remove carbon impurities (0051). They teach that the films are constituted substantially or predominantly by the elements TiN, but that it does not exclude unsubstantial elements and unsubstantial amounts of material elements (0039). They provide an example of using N2/H2 reactant gas at a substrate temperature of 80°C and an RF power of 400, 600, and 1000 W where no carbon is detected (Table 11).
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 film to have a purity within the claimed range because Takamure indicates that it is desirable to prevent impurities in the film, where a TiN film is desired having predominantly Ti and N, where since they suggest forming the film using the claimed process, the resulting film is also expected to have a purity within the claimed range. 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). 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 22, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claim 20. Takamure further provides an example where the film is formed to have 34 atomic % Ti and 45 atomic % N (Table 18), such that the film will have a Ti:N ratio of about 3:4. Further, since they provide the claimed process, the resulting process is also expected to result in a Ti:N ratio 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.” 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)”.
Claims 25 and 28 are rejected under 35 U.S.C. 103 as being unpatentable over Takamure in view of Rueger, Sobell, Li, Kim, and Citla as applied to claims 23 and 26 above, and further in view of Gatineau, US 2011/0206862 A1.
Regarding claims 25 and 28, Takamure in view of Rueger, Sobell, Li, Kim, and Citla suggest the process of claims 23 and 26. Takamure teaches that it is desirable for the sheet resistance of the TiN film to be lower (0054).
They do not teach the resistivity of the films.
As discussed above, Gatineau teaches forming TiN films, where they also teach using N2 as a reactant for the film (0011).
From the teachings of Gatineau, 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 process, such as the energy of the electrons, electron exposure, and/or pulse duration to form the TiN film having a resistivity in the range of approximately 100 to 1000 micro-ohm-cm because Gatineau teaches that such a resistivity is desirable for a TiN film formed by PEALD and Rueger teaches using electrons as an energy source instead of plasma to provide improved results, where the electrons are suggested to supply the energy for reaction, such that by optimizing the energy of the electrons, electron exposure, and/or pulse duration it is expected to also be capable of providing a TiN film with a resistivity in the range of 100 to 1000 micro-ohm-cm. Further, since Takamure in view of Rueger, Sobell, Li, Kim, Citla, and Gatineau suggest depositing the TiN film using the process of claims 23 and 26, the resulting film is also expected to provide a resistivity meeting the claimed range. Therefore, the films are optimized to have a resistivity overlapping the claimed ranges. 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.” 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). 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)”.
Response to Arguments
Applicant’s arguments provided 6/23/2026 have been fully considered. In light of the amendments to the claims the rejection has been modified with the new references of Li and Citla as discussed above.
Regarding Applicant’s arguments over Sobell not having a reactive background gas, the new reference of Li has been included to indicate that an HC-PES can be used to inject electrons into a reactive gaseous environment using a pressure overlapping the claimed range.
Regarding Applicant’s argument over the pressure and the energy of the electron beam, the new reference of Citla has been included to indicate that electrons having an energy overlapping the claimed range can be used to activate ammonia using a pressure similar to the claimed range.
Conclusion
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718
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