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 1-20 are pending and rejected. It is noted that the claims are not addressed in numerical order to simplify the rejection.
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 text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
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, 2, 5-12, 14, and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Haukka, US 2017/0037513 A1 (provided on the IDS of 6/28/2024) in view of Korolik, US 9,449,843 B1 and Shero, US 2011/0198736 A1 (provided on the IDS of 6/28/2024).
Regarding claims 1, 2, 8, and 20, Haukka teaches methods for selectively depositing a material on a first metal or metallic surface of a substrate relative to a second dielectric surface of the substrate (abstract). They teach that passivation chemicals or blocking agents such as self-assembled monolayers may be used for selective deposition (0010). They teach that the metal or metallic surface comprises one or more transition metals such as Al, Cu, Co, Ni, W, or a noble metal such as Ru (0012). They teach that the second surface comprises -OH groups such as SiO2 (0010), so as to provide an adjacent dielectric surface. They teach that the substrate is cleaned before contacting the substrate with a first reactant, the pretreatment comprises reducing the oxidized portion of the metal or metallic surface of the substrate (0020). They teach depositing the layer by ALD (0010). Therefore, they teach selectively depositing a layer atop a substrate having a metal surface comprising copper, cobalt, or tungsten and an adjacent dielectric surface (SiO2), where an oxide of the metal is removed or reduced, a self-assembled monolayer may be formed, and a layer is selectively deposited atop the metal surface by ALD.
They do not teach reducing the metal oxide using the claimed process.
Korolik teaches methods of selectively etching metals from a surface relative to silicon-containing layers such as silicon oxide (abstract). They teach performing an oxidation operation which creates a thin uniform metal oxide which is then removed by exposing the metal oxide to a metal-halogen precursor in a substrate processing region (abstract). They teach that the metal oxide may be removed to completion and the etch may stop once the uniform metal oxide layer is removed leaving behind an unoxidized portion of the metal (abstract and Col. 1, lines 42-59). They teach that the etches may be used to uniformly trim back material on high aspect ratio features (abstract). They teach that the metal layer may consist of a first metal element such as titanium, molybdenum, tungsten, aluminum, etc. or may be a transition metal, such that it would include copper and cobalt (Col. 2, lines 9-13 and Col. 4, lines 34-44). They teach that the metal-and-halogen-containing precursor comprises a second metal and a halogen (Col. 2, lines 34-53). They teach that the second metal element may have an atomic number of 22-24, 40-42, 72-73, or 74 and may include Cl (Col. 2, line 54 to Col. 3, line 6). They teach that the metal element of the metal-and-halogen-containing precursor may be niobium or may be a transition metal, where examples include niobium pentahalides (Col. 6, lines 1-25). They teach that the first metal and the second metal elements may be the same or different, where they provide an example of niobium chloride etching an oxidized layer of titanium (Col. 6, lines 26-44). They teach holding the substrate at a temperature appropriate for the metal layer and the metal-halide precursor, where the substrate temperature may be between 300°C and 400°C (Col. 7, lines 32-51). They teach that the reactions may proceed thermally, where the pressure within the substrate processing region may be between 1 Torr and 10 Torr (Col. 8, lines 52-67). They teach that the metal-and-halogen-containing precursor may include only a single atom of the metal element but multiple atoms of the halogen element to make vaporization easier and promote volatility of the reaction product on the metal surface (Col. 6, line 1-25), indicating that the reaction byproduct will be volatile.
From the teachings of Korolik, 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 Haukka to have removed the metal oxide from the tungsten, copper, or cobalt surface using a metal halide such as NbCl5 (niobium pentachloride) at a temperature between 300°C and 400°C and a pressure of 1 to 10 Torr because Korolik teaches that niobium pentahalides, where the halide can be chloride, can be used to selectively remove oxides from tungsten and transition metals over silicon oxide, where the oxide is removed to completion to leave an unoxidized surface behind, where the process provides uniform etching such that it will be expected to selectively remove the oxide from the metal surface while not affecting the silicon oxide surface for the selective deposition process. Therefore, the pressure and temperature are within the claimed ranges.
They do not teach that the self-assembled monolayer is an organosilane layer.
Shero teaches methods of forming mixed SAMs for preventing undesirable growth or nucleation on exposed surfaces inside a reactor (abstract). They teach adsorbing a self-assembled monolayer having long-chain molecules over surfaces to be deactivated, followed by adsorbing short-chain molecules over portions of the surfaces on which the long-chain molecules were not adsorbed, to form a mixed self-assembled monolayer (0038 and Fig. 3A). They teach that vapor phase monomer can be delivered to reactor surfaces or a substrate (0038). They teach that the surface to be protected by the mixed SAM from undesirable growth or nucleation can include dielectric surfaces such as SiO-2- surfaces, where SAM precursors best adsorb onto dielectric surfaces (0039). They teach that the first-chain molecules which are adsorbed include organic compounds such as octadecyltrichlorosilane, etc. (0040), i.e. organosilane-based self-assembled monolayers. They teach providing a substrate having exposed conductor surfaces and exposed insulator surfaces, adsorbing a self-assembled monolayer having long-chain molecules over the exposed insulator surface; adsorbing short-chain molecules over the exposed insulator surfaces on which the long-chain molecules were not adsorbed; and performing an ALD process to selectively deposit film over the exposed conductor surfaces relative to the so treated insulator surfaces (0094 and Fig. 7). They teach that the conductor surfaces can comprise metal surfaces that are cleaned of native oxide or hydroxyl groups to avoid deactivation by the SAM to be formed (0095). Therefore, Shero teaches forming organosilane-based SAMs on dielectric surfaces relative to metal surfaces, where the metal surfaces are cleaned of native oxide prior to applying the SAMs so as to provide selective deposition on the metal surface.
From the teachings of Shero, 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 an organosilane-based SAM on the dielectric (SiO2) surfaces because Haukka teaches that SAMs can be used for the selective deposition process and Shero teaches that such SAMs a desirable in deactivating SiO2 surfaces over metal surface for selective deposition such that it will be expected to block the dielectric surface as desired.
Haukka teaches that the invention may be directed to selective deposition in forming integrated circuit fabrication (0069), which is done on semiconductor substrates (0003). Shero also teaches that the method is used for forming semiconductor devices such as integrated circuits (0011). 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 the process of Haukka in view of Korolik and Shero to have used the process in semiconductor device fabrication because both Haukka and Shero indicate that selective deposition processes are used in forming integrated circuits in semiconductors.
Therefore, Haukka in view of Korolik and Shero provide the process of selectively depositing a layer atop a substrate having a metal surface comprising copper, cobalt, or tungsten and an adjacent dielectric surface (SiO2) comprising contacting concurrently the metal surface with NbCl5 at a pressure within the claimed range and a temperature meeting the range of claim 1 while overlapping the range of claim 2 to convert a metal component of a surface metal oxide to a volatile product to form an exposed metal surface, growing an organosilane-based SAM atop the dielectric surface, and selectively depositing a layer atop the exposed metal surface of the substrate by ALD, where the SAM will inhibit deposition of the layer atop the dielectric surface. Further, since the exposure is done to the surface of the metal, it will result in forming an exposed metal surface atop the metal surface as required by claim 8. While they do not teach that the byproduct of a copper, cobalt, or tungsten surface with NbCl5 results in a volatile metal chloride, since they provide the claimed process using a pressure within the claimed range and a temperature meeting the claimed range, the resulting process is also expected to result in a volatile metal halide. 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)”. 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.”
Regarding claim 5, Haukka in view of Korolik and Shero suggest the process of claim 1. Korolik further teaches that the metal-and-halogen containing precursor is a process gas (Col. 2, lines 14-33 and Col. 12, lines 65-67), such that it will be a gas.
Regarding claim 6, Haukka in view of Korolik and Shero suggest the process of claim 1. Korolik further teaches purging the chamber of oxygen after exposure to the oxygen precursor (Col. 4, lines 4-33 and Col. 9, lines 1-16). 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 ensured that the chamber is oxygen free when contacting with the metal halide because Korolik teaches purging the chamber of the oxygen precursor prior to exposure and because the process is done to remove oxide from the surface such that it will ensure that the surface is not re-oxidized and that no gas-phase reactions occur.
Regarding claim 7, Haukka in view of Korolik and Shero suggest the process of claim 1, where Haukka teaches that the metal is tungsten (0012).
Regarding claim 9, Haukka in view of Korolik and Shero suggest the process of claim 1. Shero teaches that the monomers that form the SAM can be delivered in vapor forms (0031), such that when growing the organosilane based SAM, the substrate will be exposed to a gas comprising an organosilane.
Regarding claims 10-12, Haukka in view of Korolik and Shero suggest the process of claim 1. Shero further teaches that the SAMs are formed from silanes such as octadecyltrichlorosilane, alkylaminosilanes, haloalkylsilanes, and alkyldisilazanes (0039-0040 and 0042). They teach that SAM precursors are introduced into a reactor in vapor form at a temperature of between about 80 and 400°C and a pressure between about 0.01 and 100 Torr (0055).
From the teachings of Shero, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have provided the SAM process gas to the reactor at a temperature range of 80-400°C and a pressure of between about 0.01 and 100 Torr and to have selected a SAM such as octadecyltrichlorosilane because Shero indicates that such a temperature and pressure are suitable for providing the SAM precursor vapor, where octadecyltrichlorosilane is a suitable SAM for preventing growth or nucleation on dielectric surfaces. Therefore, the SAM will have a C18 alkyl chain as required by claim 10 and be provided at a temperature overlapping the range of claim 11 and at a pressure overlapping the range of claim 12. 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.”
Regarding claim 14, Haukka in view of Korolik and Shero suggest the process of claim 1. Shero teaches removing oxide groups from the conductor surface to avoid deactivation by the SAM to be formed (0095). They also teach providing the SAM to the substrate where there is no indication that oxygen is needed (0055 and 0096).
Korolik teaches that oxygen oxidizes the surface of the metal (Col. 2, lines 14-33 and Col. 2, lines 54-67).
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 grown the organosilane SAM in an oxygen-free chamber because Shero does not indicate that oxygen is needed and because Shero teaches that oxide groups need to be removed from the conductor surface to prevent deactivation, where Korolik indicates that oxygen oxidizes the metal surface such that it will prevent oxidation and subsequent deactivation of the metal.
Claims 13 and 16 are rejected under 35 U.S.C. 103 as being unpatentable over Haukka in view of Korolik and Shero as applied to claim 1 above, and further in view of Chakraborty, WO 2016/138284 A1 (provided on the IDS of 6/28/2024).
Regarding claim 13, Haukka in view of Korolik and Shero suggests the limitations of instant claim 1.
They do not teach the time required to grow the SAM.
Chakraborty teaches methods for selective deposition using self-assembled monolayers by growing an organosilane based SAM atop an exposed silicon-containing surface (abstract). They teach growing the organosilane based self-assembled monolayer by exposing the substrate to a solution comprising a liquid organosilane where the organosilanes have long alkyl chains (0018). They teach that the substrate is dipped in the solution for about 2 to about 3 hours to form the self-assembled monolayer on the silicon-containing surface (0019). They teach that the organosilane molecules have a chemical affinity to the oxide in a silicon oxide surface (0019).
From the teachings of Chakraborty, 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 grown the organosilane base SAM for a time of about 2 to about 3 hours because Chakraborty indicates that such a time frame is needed for growing an organosilane SAM on a silicon-containing surface such as SiO2 such that it will be expected to provide the desirable and predictable result of contacting the surface for a time sufficient for growing a SAM on the dielectric surface. It is noted that while Chakraborty uses a liquid silanes and Haukka in view of Korolik and Shero use gas-phase silanes, the time would also be expected to be sufficient because it will still result in the SAM material being in contact with the surface for the same time whether as a gas or liquid. 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 optimized the time for growing the SAM to be within the claimed range through routine experimentation so as to ensure that the SAM has reacted with the dielectric surface as desired to ensure that the SAM will effectively prevent growth on the dielectric region. 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 16, Haukka in view of Korolik and Shero suggests the limitations of instant claim 1. Shero further teaches removing the SAM after deposition by a thermal anneal (0090).
They do not teach the temperature for the SAM removal.
Chakraborty teaches forming a first SAM on a metal surface, growing a second SAM atop an exposed silicon-containing surface where the SAM is organosilane based, heating the substrate to remove the first SAM atop the exposed metal surface, selectively depositing a layer atop the exposed metal surface, and heating the substrate to a temperature of about 500 to about 1000°C to remove the second SAM from the exposed silicon-containing surface (0005). They teach depositing low-k dielectric layer on the exposed silicon surface, where the low-k layer is suitable for semiconductor device fabrication (0021). They teach that after heating to about 500°C to about 1000°C to remove the SAM from the silicon-containing surface the substrate may undergo further processing as necessary for completion of a semiconductor device (0022). Therefore, Chakraborty teaches heating at about 500-1000°C to remove an organosilane based SAM, where it is desirable to remove the SAM after selectively depositing a coating in manufacturing a semiconductor device.
From the teachings of Shero and Chakraborty, 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 heated the substrate to a temperature of about 500-1000°C to remove the organosilane based SAM because Shero teaches removing the SAM by a thermal anneal and Chakraborty teaches that such a process removes an organosilane based SAM so that the substrate can undergo further processing as necessary for a semiconductor device such that it will be expected to provide the desired and predictable result of removing the organosilane based SAM to prepare the substrate for further processing. Therefore, Haukka in view of Korolik, Shero, and Chakraborty suggest heating the substrate to a temperature 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).
Claim 15 is rejected under 35 U.S.C. 103 as being unpatentable over Haukka in view of Korolik and Shero as applied to claim 1 above, and further in view of Hankins, US 7,045,170 B1 (provided on the IDS of 6/28/2024).
Regarding claim 15, Haukka in view of Korolik and Shero suggest the limitations of instant claim 1. Shero teaches using alkylaminosilanes (0040).
They do not teach that the organosilane based SAM comprises tris(dimethylamino)octadecylsilane.
Hankins teaches a method for depositing an anti-stiction coating on a MEMs device by reacting the vapor of an amino-functionalized silane precursor with a silicon surface of the MEMs device in a vacuum chamber (abstract). They teach that the aminofunctionalized silane precursor comprises at least one silicon atom, at least one reactive amino pendant, and at least one hydrophobic pendant (abstract). They teach that the amino-functionalized silane precursor is highly reactive with the silicon surface where vapor deposition of the amino-functionalized silane coating provides a uniform surface morphology and strong adhesion to the silicon surface (abstract). They teach that the number and type of hydrocarbon pendants attached to the silicon atom can be varied where X is a hydrocarbon pendant that can include —(CH2)nCH3, where n is an integer from 1 to 20 (Col. 4, line 52 through Col. 5, line 21). They teach that the number and type of reactive amine pendants attached to the silicon atom can also be varied where examples include three N(Y2) groups, where Y can be —CH3 (Col. 5, lines 22-55 and Col. 6, lines 5-59), such that the groups can be dimethylamino groups. Therefore, they teach that the amino-functionalized silane can have three amino groups where the groups can be dimethylamino groups and that the silane has at least one hydrophobic pendant that can include 1-20 alkyl groups such that the formula includes tris(dimethylamino)octadecylsilane. They teach that the amino groups react immediately with the silicon oxide surface and do not require the addition of water vapor to effectuate the reaction (Col. 3, lines 22-36). They teach that the process is directed to chemical vapor deposition of self-assembled monolayers from amino-functionalized silane precursors (Col. 4, lines 27-30).
From the teachings of Hankins, 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 Haukka in view of Korolik and Shero to have used tris(dimethylamino)octadecylsilane to form the SAM on the dielectric surface because Hankins indicates that such a SAM is highly reactive with a silicon oxide surface, and that vapor deposition of the amino-functionalized silane coating provides a uniform surface morphology and strong adhesion to the silicon surface, and because Shero teaches that aminosilanes can be used as the SAMs such that it will be expected to provide the desired and predictable result of forming a desirable SAM with good adhesion and reactivity. Therefore, Haukka in view of Korolik, Shero, and Hankins suggests using tris(dimethylamino)octadecylsilane
Claims 17 and 18 are rejected under 35 U.S.C. 103 as being unpatentable over Haukka in view of Korolik and Shero as applied to claim 1 above, and further in view of Isobe, US 2016/0362784 A1 and Kim, US 6,800,542 B2.
Regarding claims 17 and 18, Haukka in view of Korolik and Shero suggest the process of claim 1. Korolik teaches using that the metal elements of the metal-and-halogen-containing precursor includes titanium, zirconium, molybdenum, tungsten, rhenium, etc., where the metal element may be a transition metal (Col. 6, lines 1-25). They teach that specific examples include tungsten pentahalides or tungsten hexahalides, etc. (Col. 6, lines 1-25).
They do specifically teach using ruthenium precursors.
Isobe teaches forming a titanium oxide film by pulsing TiCl-4 as a precursor gas, purging with an inert gas, and then pulsing water as an oxygen containing gas (0053, 0060, 0062, 0064, and Fig. 4). They teach that other film forming precursors gases can be used as an alternative to titanium such as those containing tungsten, ruthenium, cobalt, zirconium, etc. (0138). They teach that specific examples of the precursor gas include tungsten hexachloride, tungsten hexafluoride, and ruthenium trichloride (0139). Therefore, they teach that ruthenium trichloride is a precursor gas that can be used in a film forming process as an alternative to tungsten hexachloride.
Kim teaches a method for fabricating a Ru thin film by ALD using RuXn, where n is 2 or 3 as a Ru precursor (abstract). They teach providing a Ru precursor gas at a temperature in the range of 100°C to 900°C (Col. 4, lines 16-30).
From the teachings of Isobe and Kim, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used ruthenium (II) chloride or ruthenium trichloride as the metal-and-halogen-containing precursor because Korolik teaches using transition metal chlorides as the precursor, where a specific example is tungsten hexachloride, Isobe indicates that ruthenium trichloride is a precursor gas that is used as an alternative to tungsten hexachloride in a film forming process, suggesting that they have similar reactivities, and Kim teaches that in an ALD process either RuCl2 or RuCl3 can be used, where they have similar chemical structures, suggesting that they have similar reactivities, and where the precursors can be provided as gases at a temperature overlapping the range of Korolik (and the claimed range), such that it will be expected to provide desirable transition metal chlorides as process gases for the oxide etching process.
Claims 3 and 4 are rejected under 35 U.S.C. 103 as being unpatentable over Haukka in view of Korolik and Shero as applied to claim 1 above, and further in view of Isobe, US 2016/0362784 A1, Wu, US 2016/0305020 A1 (provided on the IDS of 6/28/2024), and Kim, US 6,800,542 B2.
Regarding claim 3, Haukka in view of Korolik and Shero suggest the process of claim 1. Korolik teaches using that the metal elements of the metal-and-halogen-containing precursor includes titanium, zirconium, molybdenum, tungsten, rhenium, etc., where the metal element may be a transition metal (Col. 6, lines 1-25). They teach that specific examples include tungsten pentahalides or tungsten hexahalides, etc. (Col. 6, lines 1-25). They teach that the oxygen-containing precursor and/or the substrate processing region may be hydrogen-free (Col. 4, lines 4-33). They teach that hydrogen may end up adding material to metals such that the etch process does not proceed at a desirable rate (Col. 8, lines 30-41). They teach that the flow of precursors into the substrate processing region may further include one or more relatively inert gases such as He, N2, Ar (Col. 9, lines 50-57). They teach that the inert gas may be included to improve process uniformity (Col. 9, lines 50-57).
They do not teach contacting the metal surface with the one or more metal halides together with further contacting with hydrogen.
As discussed above Isobe provides the suggestion of using RuCl3 as the metal-and-halide-containing precursor.
Wu teaches using tungsten chloride to metal or metal containing films by CVD or ALD (abstract). They teach a delivery system for the vaporization and/or sublimation of WCl6 where an inert carrier gas such as hydrogen, nitrogen, helium, or argon is flowed through the interior volume of the vessel and combines with the gaseous phase of the precursor material to provide a precursor-containing gaseous stream (0075). Therefore, Wu teaches that hydrogen can be used with tungsten chloride as an inert carrier gas as an alternative to He, Ar, or nitrogen.
Kim teaches a method for fabricating a Ru thin layer by using RuXn, where n is 2 or 3 as a Ru precursor (abstract). They teach injecting a reductive reaction gas into the reaction chamber (abstract). They teach that hydrogen has been used as a reaction gas, but that the temperature has to be set over 600°C in order to activate hydrogen (Col. 1, lines 36-41 and Col. 2, lines 4-14).
From the teachings of Wu and Kim, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used hydrogen as a carrier gas when using RuCl3 as the metal halide because Wu teaches that it is known to use hydrogen as an inert carrier gas for WCl6 (a metal-and-halide-containing gas of Korolik) and Kim teaches that for hydrogen to react with RuCl3 the temperature must be over 600°C (greater than the range suggested by Korolik) such that it will be expected to provide a suitably inert carrier gas for the process so as to improve the uniformity as indicated by Korolik and not to add material to the metal since the temperature will not be high enough to activate the hydrogen.
Regarding claim 4, Haukka in view of Korolik, Shero, Isobe, Wu, and Kim suggest the process of claim 3. Korolik further teaches that the metal oxide is removed to completion, where the etch stops once the metal oxide layer is removed, leaving behind an unoxidized portion of the metal (Col. 1, lines 42-59). While they do not teach the time required for etching, 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 etch time to be within the claimed range because Korolik indicates that the process will stop when the oxide is removed, indicating that the etching time will be dependent on the degree of oxidation such that by optimizing the exposure time to be within the claimed range it will be expected to provide a sufficient time for removing the oxide layer. 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).
Claim 19 is rejected under 35 U.S.C. 103 as being unpatentable over Haukka in view of Korolik and Shero as applied to claim 1 above, and further in view of Choi, US 2017/0073809 A1.
Regarding claim 19, Haukka in view of Korolik and Shero suggest the process of claim 1, where they suggest using NbCl5 as the metal halide. Korolik teaches that the metal-and-halogen-containing precursor may include multiple atoms of the halogen element (Col. 6, lines 1-25).
They do not teach using NbCl4.
Choi teaches manufacturing a metal chalcogenide thin film by supplying a vaporized metal precursor; supplying a chalcogen-containing as; and forming a thin film by reacting the metal precursor with the chalcogen-containing gas on a growth substrate at a first temperature condition (abstract). They teach that the first temperature condition may be 300 to 850°C (0011). They teach that the gasified metal precursor may be formed by heating a metal powder selected from metal halides such as NbCl4 and NbCl5 (0013-0014). They teach depositing the film by CVD (0048).
From the teachings of Choi, 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 NbCl4 as a simple substitution for NbCl5 because Choi teaches that they are alternatives to one another in a CVD process, suggesting that they have similar reactivity, where they are gasified at a temperature overlapping the range of Korolik, and because Korolik broadly teaches using niobium chloride as a metal halide such that it will be expected to provide a simple substitution while also expecting the desired and predictable result of etching the metal oxide. According to MPEP 2144.09(I): A prima facie case of obviousness may be made when chemical compounds have very close structural similarities and similar utilities. "An obviousness rejection based on similarity in chemical structure and function entails the motivation of one skilled in the art to make a claimed compound, in the expectation that compounds similar in structure will have similar properties." Specifically, since NbCl4 and NbCl5 have similar structures, Korolik teaches using niobium chloride, and Choi suggests that they can be alternatives to one another, the chemical compounds are expected to have similar utilities.
Response to Arguments
Applicant's arguments filed 2/2/2026 have been fully considered.
Regarding Applicant’s argument that there is no motivation to modify Haukka to use the process of Korolik and the method of Korolik is directly counter to Haukka because it would result in the metal oxide being adsorbed on the metallic surface, it is noted that Haukka teaches pretreating the surface to remove oxides prior to adsorbing the metal halide precursor (0020-0021). Korolik teaches that exposing the oxide surface to a halide such as NbCl5 results in removing the oxide, where they provide conditions selected for removing the oxide. Therefore, exposing the surface to NbCl5 is not expected to result in the gas adsorbing on the surface because Haukka teaches that it adsorbs on to a metal surface that has the oxides reduced (so as to provide a metallic surface) as opposed to having an oxide surface and because Korolik indicates that it will remove or etch oxides such that they provide specific conditions selected for removing the oxide. Further, Korolik indicates that the process provides selective etching of the oxide on the metal surface over a silicon oxide surface, where the oxide is removed to completion to leave an unoxidized surface being to provide uniform etching such that it is expected to provide the desirable and predictable result of removing the oxides while not affecting the silicon oxide surface so as to provide the metal surface and dielectric surface prepared for selective deposition as desired by Haukka.
Regarding Applicant’s argument that the precursors of Haukka are already selectively adsorbed, it is noted that Haukka teaches that passivation chemicals or blocking agents may be used such as self-assembled monolayers (0010). Therefore, the suggestion to use the organosilane-based SAMs suggested by Shero to ensure that the process is selective is considered to be compatible with the teachings of Haukka.
Regarding Applicant’s arguments that the modification of Haukka with Korolik would result in a metal surface in which the metal halide is adsorbed onto the surface, which would then result in the formation of a silane layer over the metal surface due to the interaction of the adsorbed metal halide with the organosilane, as noted above Haukka teaches removing oxides prior to adsorbing the metal halide and Korolik provides the suggestion to supply the metal halide under conditions suitable for the etching and removal of the oxide from the metallic surface. Korolik further teaches that the process results in leaving the remaining portion of the metal-containing layer intact (Col. 2, lines 34-53), such that there is no indication that at the conditions suggested the metal halide will be adsorbed onto the surface. Therefore, when providing the organosilane, which is indicated as deactivating SiO2 surfaces over metal surfaces by Shero, the SAM is expected to successfully form over the SiO2 surface as opposed to the remaining metal surface resulting from the metal halide oxide removal step. While Applicant argues that Haukka in combination with Korolik does not result in an exposed metal surface, it is not clear why it would not. Specifically, the combination suggests the claimed process step of exposing the metal surface (where the metal surface is one of the claimed materials) to NbCl5 under conditions meeting the claimed ranges, where Korolik indicates that the oxide will be removed. Therefore, if the combination does not result in providing an exposed metal surface, then the claimed process would also not result in providing an exposed metal surface. Further, the combination is not expected to destroy the selectivity of the process because it is expected to remove oxides from the metal surface, apply a SAM to the SiO2 surface to ensure selectivity, such that the resulting film will be deposited on the exposed metal surface.
Conclusion
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718 /GORDON BALDWIN/Supervisory Patent Examiner, Art Unit 1718
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