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, 3-16 are pending and rejected. Claims 1 and 16 are amended. Claim 2 is 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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 2/24/2026 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, 3-11, and 13-15 are rejected under 35 U.S.C. 103 as being unpatentable over Vogt, US 2005/0009350 A1 in view of Okada, US 2012/0238107 A1 and Konecni, US 2012/0129351 A1 and as evidenced by Yang, US 2019/0103280 A1.
Regarding claim 1, Vogt teaches a method for forming a carbon-containing film (forming a carbon hard mask layer, abstract and 0001), the method comprising:
preparing a substrate on which a metal-containing film is formed (where the substrate, e.g., a silicon substrate, has a metal layer, 0034 and Fig. 1, indicating that a substrate having a metal-containing film is prepared);
performing a modification process of modifying a surface of the metal-containing film by supplying a silicon-containing gas to the substrate and by exposing the substrate to the silicon-containing gas during a first period of time (where a bonding layer made form a material selected from the group consisting of silicon oxides, silicon oxynitride, and silicon nitride is formed by PECVD, 0015 and 0022, using precursors such as SiH4, N2O and/or NH3, 0042, such that a silicon-containing gas, i.e., silane will be supplied to the substrate during a first period of time to form the bonding layer resulting in modifying a surface of the metal-containing film); and
forming the carbon-containing film on the modified surface of the substrate by exposing the substrate subjected to the modification process to plasma of a processing gas including a carbon-containing gas (where the carbon layer is formed by exposing the substrate to a C-containing precursor such as C2H4 or C3H6, 0021, 0041, and 0046-0047, where the layer is formed by PECVD, 0041 and 0046-0047, indicating that the modified surface of the substrate will be exposed to a plasma of a processing gas including a carbon-containing gas, where the precursors are understood to be gaseous because it is a vapor deposition process).
Vogt further teaches that the metal surface includes AlCu alloys, where a thin (10-40 nm) TiN layer is formed as an antireflection coating on the AlCu (0034). As evidenced by Yang, TiN, SiN, Cu, and SiO2 are hydrophilic (0112). Therefore, Vogt as evidenced by Yang provides preparing a substrate on which a metal-containing film having a hydrophilic surface is formed in the form of TiN.
They do not teach modifying the surface have a hydrophobic layer.
Okada teaches a processing method for forming a structure including an amorphous carbon film (abstract). They teach placing a plurality of target objects in a reaction chamber, each object including an underlying layer on which the structure is to be formed, and performing a primary treatment of forming a hydrophobic layer to cover the underlying layer with the hydrophobic layer by heating the inside of the chamber and supplying a preliminary treatment gas into the reaction chamber (0010). They then perform CVD to form an amorphous carbon film on the hydrophobic layer by heating the inside of the chamber and supplying a hydrocarbon gas into the chamber (0010). They teach that the silicon source gas used for forming a hydrophobic layer of silicon by CVD between the underlying layer and amorphous carbon film includes DCS, HCD, and organo silicon precursors, i.e., BDMAS, DMAS, etc. (0044). They teach that the silicon film serves as a hydrophobic film before the amorphous carbon film is formed so that an abnormal reaction accompanied by etching at the interface between the underlying layer and amorphous carbon film can be prevented so that the surface roughness is smaller (0097). They teach that the amorphous carbon film is formed with better coverage performance and smaller surface roughness (0097).
From the teachings of Okada, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to substituted the bonding layer of Vogt with the hydrophobic layer of Okada because Okada teaches that a hydrophobic layer prevents an abnormal reaction accompanied by etching at the interface between an underlying layer and an amorphous carbon film so that the surface roughness is smaller and it provides better coverage performance, where as evidenced by Yang, the bonding layers of Vogt are hydrophilic, such that it will be expected to provide improved coverage and minimize surface roughness. Therefore, the hydrophilic surface will be modified to be hydrophobic by the application of the hydrophobic layer, where the silicon-containing gas is understood to be physically adsorbed or chemically bonded to the surface so as to provide the hydrophobic layer and the process is done in a non-plasma state.
They do not teach the stress of the deposited layer.
Konecni teaches a method for forming an amorphous carbon layer on a substrate, where a first portion of the layer has a high stress level and a second portion has a low stress level (abstract). They teach that high stress layer and the low stress layer stabilizes pattern distortions arising from the high internal stresses of the etch mask layer (0014). They teach that the high stress portion and the low stress portion may be formed in a PECVD process by positioning a substrate in a processing chamber and providing a gas mixture comprising a hydrocarbon gas and an inert gas to the chamber (0019). They teach that suitable hydrocarbons have the general formula CxHy, where x is 2-4 and y is 2-10 and exemplary hydrocarbons includes propylene, acetylene, etc. (0019). They teach that suitable inert gases include argon and helium (0019). They teach that a high frequency RF power having a power level between about 100 W and about 3,000 W is used to deposit the high stress film for a time necessary to deposit the desired thickness (0020). They teach that the chamber pressure is between about 1 mTorr and about 2 Torr (0020). They teach that the high stress layer is deposited to have a compressive stress greater than 600 MPa, greater than about 800 GPa, or between about 800 MPa and about 2,000 MPa, for example, about 1,200 MPa (0023).
From the teachings of Konecni, 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 Vogt in view of Okada and as evidenced by Yang to have deposited the high stress layer and low stress layer in forming the carbon hardmask layer of Vogt because Konecni teaches that such a mask is desirable for stabilizing pattern distortions arising from the high internal stresses of the etch mask layer such that it will be expected to provide a desirable carbon hardmask structure. Therefore, in the process of Vogt in view of Okada and Konecni and as evidenced by Yang, a carbon-containing film having a stress overlapping or within the claimed range will be deposited on the modified surface when the high stress film is deposited, where the bonding layer is also expected to improve the adhesion of the high stress carbon film as described by Vogt and to be stabilized by the low stress top carbon layer. 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 claims 3-5, Vogt in view of Okada and Konecni and as evidenced by Yang suggest the process of claim 1. Okada teaches using silicon source gases such dichlorosilane (SiH2Cl2), hexachlorodisilane (Si2Cl6), and organic silicon precursors, i.e. BDMAS, etc. (0044).
Regarding claim 6, Vogt in view of Okada and Konecni and as evidenced by Yang suggest the process of claim 1. Okada teaches that when the silicon-containing gas does not contain any chlorine, the incubation time is shortened (0044). They teach supplying DCS for ten minutes in forming the hydrophobic layer on an SiO2 wafer (0112). They teach flowing the silicon-containing gas until a predetermined thickness is reached (0093, 0094, 0107, and 0108). 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 that when providing a non-chlorine gas such as BTBAS, the first time period will be less than 10 minutes, so as to overlap the claimed range because they teach that when using a gas that does not contain chlorine, the incubation time is shorter, where they provide an example of supplying DCS for 10 minutes such that the time for the non-chlorinated gas is expected to be less than 10 minutes. Therefore, the 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.”
Alternatively, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimize the first time to be within the claimed range because Okada teaches supplying the gas until a layer having a predetermined thickness is provided such that by optimizing the time it will be expected to provide a hydrophobic layer having a suitable thickness for processing. 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 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 7, Vogt in view of Okada and Konecni and as evidenced by Yang suggest the process of claim 1. Okada further teaches that during modification is preferably 400°C to 700°C (0092), so as to 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.”
Regarding claims 8 and 9, Vogt in view of Okada and Konecni and as evidenced by Yang suggest the process of claim 1. Vogt further teaches that the metal surface includes AlCu alloys, where a thin (10-40 nm) TiN layer is formed as an antireflection coating on the AlCu (0034). Since Vogt indicates that the silica bonding layer is desirable on the structure including the TiN layer, the silicon bonding layer is also expected to provide desirable bonding due to their structural similarities and because both are indicated as being desirable bonding layers between metals and carbon. Therefore, the metal-containing film that is modified will be a TiN film having a thickness 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.”
Regarding claims 10, 11, 13, and 14, Vogt in view of Okada and Konecni and as evidenced by Yang suggest the process of claim 1. Vogt further teaches using C2H4 or C3H6 as the carbon-containing precursors (0021).
Konecni teaches that suitable hydrocarbons have the general formula CxHy, where x is 2-4 and y is 2-10 and exemplary hydrocarbons includes propylene, acetylene, etc. (0019). They teach including inert gases with the hydrocarbon gases, where suitable inert gases include argon and helium (0019). They teach that a high frequency RF power having a power level between about 100 W and about 3,000 W is used to deposit the high stress film for a time necessary to deposit the desired thickness (0020). They teach that the chamber pressure is between about 1 mTorr and about 2 Torr (0020).
From the teachings of Konecni, 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 their process for deposition of the high stress carbon film because they indicate that such conditions will provide a film with the desired stress. Therefore, the carbon-containing gas will include carbon and hydrogen, the processing gas will include an inert gas, the pressure will overlap the claimed range, and the power will also 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 15, Vogt in view of Okada and Konecni and as evidenced by Yang suggest the process of claim 10. Vogt further teaches that the carbon layer is approximately 80 to 500 nm (0014).
Konecni teaches that the thickness of the low stress portion may be between about 10% and 150% of the thickness of the high stress portion, for example between about 25% and about 75% (0025).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed the high stress carbon-containing film with a thickness of approximately 45 to 400 nm because Vogt teaches forming a carbon layer with a thickness of approximately 80 to 500 nm and Konecni suggests forming the low stress layer to have a thick that is 25-75% the thickness of the high stress layer such that it will be expected to provide a total carbon thickness desired by Vogt with a desirable high stress layer to low stress layer percentage. Therefore, the thickness of the claimed carbon-containing layer will overlap the range of claim 15. 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.”
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Vogt in view of Okada and Konecni and as evidenced by Yang as applied to claims 1 and 10 above, and further in view of Ruelke, US 2011/0104866 A1.
Regarding claim 12, Vogt in view of Okada and Konecni and as evidenced by Yang suggest the process of claim 10.
They do not teach that the processing gas further includes a hydrogen gas.
Ruelke teaches an amorphous carbon material deposited with superior adhesion on dielectric materials formed by applying a thin adhesion layer based on silicon dioxide or carbon-doped silicon dioxide, prior to depositing the carbon material (abstract). They teach using the carbon material as a hard mask layer (abstract and 0002). They teach depositing the carbon layer using a plasma enhanced CVD process (0016). They teach that during the PECVD process, appropriate hydrocarbon gases having the general formula C-xH-y are supplied to the chamber, possibly in combination with additional gases, such as hydrogen, nitrogen, ammonia, argon, helium and the like, thereby enabling adjustment of density and deposition rate for the material layer (0035).
From the teachings of Ruelke, 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 included hydrogen in the processing gas because Ruelke teaches that it is known to include hydrogen when depositing carbon hard mask layers by PECVD, where the inclusion can be used to adjust the density and deposition rate of the material such that it will be expected to be a desirable additive to the processing gas.
Claim 16 is rejected under 35 U.S.C. 103 as being unpatentable over Xing, US 6,573,167 B2 in view of Okada, US 2012/0238107 A1, and Konecni, US 2012/0129351 A1 and as evidenced by Yang, US 2019/0103280 A1.
Regarding claim 16, Xing teaches a carbon hardmask for etching hard-to-etch materials (abstract). They teach forming a bi-layer hardmask that includes a carbon film 134 and an additional layer 136 that may include TiN (Col. 3, lines 39-54 and Fig. 3). They teach that the second hardmask 136 can be used to etch the bottom portion of the capacitor stack, where it is chosen so that it is more etch-resistant in a plasma containing a higher percentage of halogen-based gases suitable for PZT and/or Ir etch (Col. 3, lines 39-54). They teach that the structure includes a substrate 100, a barrier layer 120, a bottom electrode 110, a capacitor dielectric 112, and a top electrode 114 (Col. 2, lines 5-16 and Fig. 3). Therefore, Xing teaches preparing a substrate by forming the desired electrode and dielectric layers, forming a metal-containing film on the substrate (TiN layer for bilayer 136), forming a carbon-containing film on the substrate (for bilayer 134), and forming the hard mask including the metal-containing film and the carbon-containing film in the form of the bi-layer hardmask.
They do not teach modifying the TiN surface.
As discussed above, TiN is hydrophilic as evidenced by Yang and Okada provides the suggestion of modifying the hydrophilic TiN surface to be hydrophobic by exposure to a silicon-containing gas to form a hydrophobic layer, such that it is expected to provide physical or chemical absorption of the silicon-containing gas so as to provide the layer, where plasma is not used.
From the teachings of Okada and as evidenced by Yang, 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 Xing to have modified the TiN layer in the bilayer mask by suppling a silicon-containing gas to the substrate for a first time period so as to form a hydrophobic layer because Okada teaches that a hydrophobic layer prevents an abnormal reaction accompanied by etching at the interface between an underlying layer and an amorphous carbon film so that the surface roughness is smaller and it provides better coverage performance, where as evidenced by Yang, TiN is hydrophilic, such that it will be expected to provide improved coverage and minimize surface roughness. Therefore, the hydrophilic surface will be modified to by hydrophobic by the application of the hydrophobic layer, where the silicon-containing gas is understood to be physically adsorbed or chemically bonded to the surface so as to provide the hydrophobic layer and the process is done in a non-plasma state.
They do not teach the stress of the deposited layer.
Konecni teaches a method for forming an amorphous carbon layer on a substrate, where a first portion of the layer has a high stress level and a second portion has a low stress level (abstract). They teach that high stress layer and the low stress layer stabilizes pattern distortions arising from the high internal stresses of the etch mask layer (0014). They teach that the high stress portion and the low stress portion may be formed in a PECVD process by positioning a substrate in a processing chamber and providing a gas mixture comprising a hydrocarbon gas and an inert gas to the chamber (0019). They teach that suitable hydrocarbons have the general formula CxHy, where x is 2-4 and y is 2-10 and exemplary hydrocarbons includes propylene, acetylene, etc. (0019). They teach that suitable inert gases include argon and helium (0019). They teach that a high frequency RF power having a power level between about 100 W and about 3,000 W is used to deposit the high stress film for a time necessary to deposit the desired thickness (0020). They teach that the chamber pressure is between about 1 mTorr and about 2 Torr (0020). They teach that the high stress layer is deposited to have a compressive stress greater than 600 MPa, greater than about 800 GPa, or between about 800 MPa and about 2,000 MPa, for example, about 1,200 MPa (0023).
From the teachings of Konecni, 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 Xing in view of Okada and as evidenced by Yang to have deposited the high stress layer and low stress layer in forming the carbon hardmask layer using the method of Konecni because Konecni teaches that such a mask is desirable for stabilizing pattern distortions arising from the high internal stresses of the etch mask layer such that it will be expected to provide a desirable carbon hardmask structure on the modified TiN surface. Therefore, in the process of Xing in view of Okada and Konecni and as evidenced by Yang, a carbon-containing film having a stress overlapping or within the claimed range will be deposited on the modified surface when the high stress film is deposited by exposure to plasma of a processing gas including a carbon-containing gas. 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.”
Response to Arguments
Applicant’s arguments provided 2/24/2026 have been fully considered.
In light of the amendments to the claims, the previous 112(a) and 112(b) rejections have been withdrawn.
In light of the amendments to claims 1 and 16, applicant’s arguments are considered persuasive and therefore the rejections have been modified to include Okada and Yang as indicated above.
Conclusion
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718
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