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 .
Claim Status
Claims 23, 31, 33, 38, 40, 43-47, and 49 are pending and rejected. Claims 1-22, 24-30, 32, 34-37, 39, 41-42, and 48 are cancelled. Claims 23, 38, 43, and 46 are amended.
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 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 23, 31, and 33 are rejected under 35 U.S.C. 103 as being unpatentable over Yu, US 2019/0390340 A1 (provided on the IDS of 10/4/2021) in view of Vayrynen, WO 2020/003000 A1, Cooper, US 2018/0122687 A1, and Kostamo, US 2005/0208754 A1.
Regarding claims 23, Yu teaches a method of depositing a film (abstract), the method consisting of:
pre-treating a substrate surface having a metal surface and a dielectric surface (where the substrate can be exposed to a pretreatment process to reduce, anneal, etc., 0030, and where the surface includes dielectric and a metal surface, 0016);
exposing a substrate surface to an organometallic precursor comprising a metal selected from the group consisting of molybdenum, tungsten, osmium, rhenium, iridium, nickel, and ruthenium (where the substrate is exposed to a metal precursor, where the metal precursor includes ligands such as an optionally alkyl substituted cyclopentadiene ring, an optionally alkyl substituted benzene ring, a p-cymene ligand, an open or closed diene, an aromatic ligand, etc., where a specific example is p-cymene ruthenium 1,5-hexadiene, 0014 and 0101-0102, such that the metal precursor is organometallic since it includes organic ligands, i.e. has metal-organic bonds, and where the metal includes molybdenum, tungsten, nickel, and ruthenium, 0102-0103) ;
purging the substrate surface (purging the process chamber using an inert gas, 0085, 0098, 0108, and Fig. 7, such that the substrate surface will also be purged);
exposing the substrate surface to a first exposure of an iodine-containing reactant comprising a species having a formula RIx, where R is one or more of a C1-C10- alkyl, cycloalkyl, alkenyl, or alkynyl group and x is in a range of 1 to 4 to form a carbon-less iodine-containing metal film having a carbon content less than or equal to 20 atomic percent (where the substrate is exposed to an alkyl halide comprising iodine such as diiodomethane (CH2I2) or iodoethane (H5C2I), 0014 and 0091, such that the iodine-containing reactant comprises a species having a formula meeting the limitations of claim 1, where a metal film is formed that comprises less than or equal to about 20 atomic % carbon, abstract, 0014, and 0115, such that it is considered to be carbon-less because the carbon content is within the claimed range, and where the film comprises 0.02 to 5 atomic % iodine, 0114, indicating that the film will comprise iodine);
purging the substrate surface (where a purge gas is provided to purge the process chamber, 0085, 0098, and Fig. 7, such that the substrate surface will be purged); and
exposing the carbon-less iodine-containing metal film to a second exposure of the iodine-containing reactant to form a metal film having a resistivity less than or equal to 15 µΩ-cm (where the process is repeated, 0086, such that the exposure will be repeated, and where the metal layer has a resistivity of less than or equal to about 20 µohm-cm, 0117, so as to overlap the claimed range).
Therefore, the resistivity of the film overlaps the range of claim 23, i.e., be less than or equal to about 20 µohm-cm for forming the metal film. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
Yu further teaches selectively depositing a metal film on a metal surface over a dielectric surface (abstract).
They do not teach that the substrate surface is exposed to the organometallic precursor, the first exposure of the iodine-containing reactant, and the second exposure of the iodine-containing reactant sequentially.
Vayrynen teaches a method of depositing a metal-containing material using cyclic deposition techniques such as ALD (abstract). They teach that the metal-containing material can include one, two, or three or more metals (pg. 3, lines 9-22). They teach that the cyclic deposition process can include providing a first gas-phase reactant comprising a first metal to a reaction chamber to form a first metal species and providing a second gas-phase reactant comprising a compound having a general formula of R-M-H (pg. 3, lines 9-22). They teach that the method can include ALD which is based on typically self-limiting reactions, whereby sequential and alternating pules of reactants are used to deposit about one atomic or molecular monolayer of material per deposition cycle (pg. 21, lines 19-30 and Fig. 2). They teach that the order of providing a first gas-phase reactant and providing a second gas-phase reactant may be such that the substrate is first contacted with the second gas-phase reactant followed by the first gas-phase reactant (pg. 22, line 32 through pg. 23, line 6). They teach that the cyclical deposition process may comprise contacting the substrate with the first gas-phase reactant one or more times prior to contacting the substrate with the second gas-phase reactant one or more times and similarly may alternatively comprise contacting the substrate with the second gas-phase reactant one or more times prior to contacting the substrate with the first gas-phase reactant one or more times (pg. 22, line 32 through pg. 23, line 6). They teach that the method may include an additional process step comprising contacting the substrate with a third vapor phase reactant comprising a reducing agents such as hydrogen, ammonia, etc. (pg. 23, lines 17-29). They teach that if the third vapor phase reactant comprising a reducing agent is used, it may be introduced into the reaction chamber and contact the substrate at a number of process stages in an exemplary cyclical deposition method (pg. 23, lines 30-34). Therefore, Vayrynen teaches depositing a metal film using ALD where the first precursor and/or second precursor are provided one or more times before exposing the substrate to the other precursor.
From the teachings of Vayrynen, 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 Yu to have exposed the substrate to the organometallic precursor, the first exposure of the iodine-containing reactant, and the second exposure of the iodine-containing reactant sequentially because Vayrynen teaches that it is known to expose a substrate to a precursor or reactant one or more times prior to exposing it to another precursor in a cyclical deposition which is indicated as being an ALD process such that it will be expected to provide a suitable sequence during the deposition while also ensuring the that self-limiting reaction has reached completion, i.e., it ensures that the surface is saturated with the reactant or precursor. Therefore, the process will consist of the claimed process steps which are either repeated or are performed singly when depositing a single cycle.
They do not teach pre-treating the substrate using a hydrogen anneal.
Cooper teaches cobalt compounds used as precursors for selectively depositing cobalt films (abstract). They teach providing a substrate to a reactor where the substrate comprises at least one patterned dielectric layer and at least one patterned conductive metal layer (0037). They teach performing a pre-treatment to remove contaminants from the surface of the substrate (0038). They teach pre-treating the conductive metal surface prior to deposition to remove contaminants such as organic impurities and metal oxides (0108). They teach that the pre-treatment process may comprise heating a structure comprising a conductive metal surface in the presence of a reducing gas such as hydrogen at 100-500°C (0108).
From the teachings of Cooper, 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 pre-treated the substrate surface by heating in hydrogen at 100-500°C because Cooper teaches that such a process removes contaminants such as oxides from a metal surface prior to deposition such that it will be expected to remove contaminants from the metal surface to provide a clean surface for deposition. Therefore, the pre-treatment will be a hydrogen anneal process performed at a temperature 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976). Therefore, the substrate will be exposed to the hydrogen anneal process (in the pre-treatment), the organometallic precursor, the first exposure of the iodine-containing reactant, and the second exposure of the iodine-containing reactant sequentially.
They do not teach the flow rate or pressure during the reduction process.
Kostamo teaches a method for forming a conductive thin film by depositing a metal oxide by ALD and then at least partially reducing the metal oxide thin film by exposing the metal oxide thin film to a gaseous inorganic reducing agent such as hydrogen (abstract). They teach that in the reduction process the temperature is in the range of about 50°C to about 400°C, about 100°C to about 350°C, and even more preferably about 150°C to about 300°C (0117). They teach that the pressure in the reaction space is preferably about 0.1 mbar (0.075 torr) to over atmospheric pressure, more preferably about 0.5 (0.375 Torr) to about 50 mbar (37.5 Torr) during the reduction (0119). They provide an example of reducing using thermal hydrogen as a reducing agent, where the temperature is set in the range of about 270-320°C and hydrogen flows at 500 sccm to reduce copper oxide (0143).
From the teachings of Kostamo, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have performed the hydrogen anneal process by flowing 500 sccm of hydrogen using a pressure in the range of about 0.375 to about 37.5 Torr because Kostamo teaches that such a flow rate and pressure are suitable for reducing oxides using hydrogen such that it will be expected to provide desirable conditions for the pre-treatment process for reducing oxides. Therefore, the flow rate will be within the claimed range and the pressure will overlap the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.”
Regarding claim 31, Yu in view of Vayrynen, Cooper, and Kostamo suggests the limitations of instant claim 23. Yu further teaches that the alkyl halide has the general formula R-X, where R is an alkyl, alkenyl, aryl, or other carbonaceous group (0090). They teach that R comprises one to two, one to four, or one to six carbon atoms (0091). They provide examples of iodoethane (H5C2I) or diiodomethane (CH2I2) (0091), indicating that the formula can be either RI or RI2. Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used a halide of RI or RI2 in which R is an alkenyl because Yu indicates that a suitable R group is an alkenyl, where the R group can be attached to one or two iodine atoms such that it will be expected to provide a suitable halide for the process. Therefore, x will be within the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original).
Regarding claim 33, Yu in view of Vayrynen, Cooper, and Kostamo suggests the limitations of instant claim 23. Yu further teaches that the metal film has a carbon content less than or equal to 20 atomic percent or less than or equal to about 15 atomic % carbon (0115). Yu further teaches that the metal layer comprises less than or equal to about 3 atomic % oxygen (0116), so as to be within the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original).
Claims 38 and 40 are rejected under 35 U.S.C. 103 as being unpatentable over Yu, US 2019/0390340 A1 (provided on the IDS of 10/4/2021) in view of Cooper, US 2018/0122687 A1, Kostamo, US 2005/0208754 A1, Vayrynen, WO 2020/003000 A1, and Sharma, US 2020/0194268 A1.
Regarding claim 38, Yu teaches a method of depositing a film (abstract), the method consisting of:
pre-treating a substrate surface having a metal surface and a dielectric surface (where the substrate can be exposed to a pretreatment process to reduce, anneal, etc., 0030, and where the surface includes dielectric and a metal surface, 0016);
exposing a substrate surface to an organometallic precursor comprising a metal selected from the group consisting of molybdenum, tungsten, nickel, and ruthenium (where the substrate is exposed to a metal precursor, where the metal precursor includes ligands such as an optionally alkyl substituted cyclopentadiene ring, an optionally alkyl substituted benzene ring, a p-cymene ligand, an open or closed diene, an aromatic ligand, etc., where a specific example is bis(ethylbenzene)molybdenum, 0014 and 0101-0102, such that the metal precursor is organometallic since it includes organic ligands, i.e. has metal-organic bonds, and where the metal includes molybdenum, tungsten, nickel, and ruthenium, 0102-0103) ;
exposing the substrate surface to a first exposure of an iodine-containing reactant comprising a species having a formula RIx, where R is one or more of a C1-C10- alkyl, cycloalkyl, alkenyl, or alkynyl group and x is in a range of 1 to 4 to form a carbon-less iodine-containing metal film having a carbon content less than or equal to 20 atomic percent (where the substrate is exposed to an alkyl halide comprising iodine such as diiodomethane (CH2I2) or iodoethane (H5C2I), 0014 and 0091, such that the iodine-containing reactant comprises a species having a formula meeting the limitations of claim 1, where a metal film is formed that comprises less than or equal to about 20 atomic % carbon, abstract, 0014, and 0115, such that it is considered to be carbon-less because the carbon content is within the claimed range, and where the film comprises 0.02 to 5 atomic % iodine, 0114, indicating that the film will comprise iodine); and
exposing the carbon-less iodine-containing metal film to a second exposure of the iodine-containing reactant, hydrogen, hydrogen plasma, ammonia, a mixture of NH3/H2, or an alcohol having a general formula of R-OH, wherein R is an alkyl group having a in a range of from 1 to 20 carbon atoms to form a metal film having a resistivity less than or equal to 15 µΩ-com to form a metal film having a resistivity less than or equal to 15 µΩ-cm (annealing the metal film under a hydrogen atmosphere to reduce carbon and halogen impurities, 0118, such that after the exposure to the organometallic precursor and the iodine-containing precursor, the film will be exposed to hydrogen to form the metal film, and where the metal layer has a resistivity of less than or equal to about 20 µΩ=com, 0117, so as to overlap the claimed range).
Since the hydrogen anneal reduces carbon and halogen impurities, it is expected to reduce iodine and carbon amounts to provide a metal film, i.e., a film having more metallic character since it has fewer impurities. They teach that the metal layer has a resistivity of less than or equal to about 20 µohm-cm (0117), such that it overlaps the range of instant claim 38. While it is unclear whether this resistivity is determined before or after annealing with hydrogen, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that the resistivity would be expected to decrease after annealing with hydrogen because it removes impurities such as iodine in the metal film to increase the metallic character of the film and therefore increase the conductivity. Therefore, the resistivity of the film after being exposed to the reductant is considered to overlap the range of claim 38, i.e., be less than or equal to about 15 µohm-cm for forming the metal film. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
They do not teach pre-treating the substrate using a hydrogen anneal.
Cooper teaches cobalt compounds used as precursors for selectively depositing cobalt films (abstract). They teach providing a substrate to a reactor where the substrate comprises at least one patterned dielectric layer and at least one patterned conductive metal layer (0037). They teach performing a pre-treatment to remove contaminants from the surface of the substrate (0038). They teach pre-treating the conductive metal surface prior to deposition to remove contaminants such as organic impurities and metal oxides (0108). They teach that the pre-treatment process may comprise heating a structure comprising a conductive metal surface in the presence of a reducing gas such as hydrogen at 100-500°C (0108).
From the teachings of Cooper, 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 pre-treated the substrate surface by heating in hydrogen at 100-500°C because Cooper teaches that such a process removes contaminants and reduces oxides from a metal surface prior to deposition such that it will be expected to remove contaminants from the metal surface to provide a clean surface for deposition. Therefore, the pre-treatment will be a hydrogen anneal process performed at a temperature 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.” In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
They do not teach the flow rate of hydrogen or pressure during the reduction process.
As discussed above for claim 23, from the teachings of Kostamo, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have performed the hydrogen anneal process by flowing 500 sccm of hydrogen using a pressure in the range of about 0.375 to about 37.5 Torr because Kostamo teaches that such a flow rate and pressure are suitable for reducing oxides using hydrogen such that it will be expected to provide desirable conditions for the pre-treatment process for reducing oxides. Therefore, the flow rate is within the claimed range and the pressure overlaps the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.”
They do not teach sequentially exposing the substrate to a first exposure of an iodine-containing reactant and a second exposure of the iodine-containing reactant.
As discussed above for claim 23, from the teachings of Vayrynen, 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 Yu in view of Cooper and Kostamo to have exposed the substrate to the organometallic precursor, the first exposure of the iodine-containing reactant, and the second exposure of the iodine-containing reactant sequentially because Vayrynen teaches that it is known to expose a substrate to a precursor or reactant one or more times prior to exposing it to another precursor in a cyclical deposition which is indicated as being an ALD process such that it will be expected to provide a suitable sequence during the deposition while also ensuring the that self-limiting reaction has reached completion, i.e., it ensures that the surface is saturated with the reactant or precursor.
They do not teach using osmium, rhenium, or iridium. Yu teaches using metals such as molybdenum, ruthenium, nickel, tungsten, etc. (0103). They teach using metal precursors comprising at least one ligand comprising an optionally alkyl substituted cyclopentadiene ring (0102).
Sharma teaches methods for forming a rhenium-containing film on a substrate by a cyclical deposition method (abstract). They teach contacting the substrate with a first vapor phase reactant comprising a rhenium precursor; and contacting the substrate with a second vapor phase reactant (abstract). They teach that the cyclical deposition process can be ALD or cyclical chemical vapor deposition (0041). They teach that the metal precursor may be selected to deposit a metal and metal alloy by the selection of the second reactant and/or by changing the processing conditions (0069). They teach that the second reactant can be a hydrogen or a nitrogen containing precursor such as, for example, hydrogen gas, ammonia, a hydrogen plasma, an alkyl halide, etc. (0069). They teach that the rhenium precursor may comprise a cyclopentadienyl-based rhenium precursor such as ReHCp2 (0067). They teach that rhenium films may be used as a catalyst in high-temperature superalloys, in superconducting applications, in adhesion layer, in liners, in diffusion barriers, in seed layers to improve growth of other materials, and in microelectronic applications (0002).
From the teachings of Sharma, 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 Yu in view of Cooper, Kostamo, and Vayrynen to have used their method to deposit a rhenium film because Sharma teaches that it is desirable to deposit elemental, i.e. metallic, rhenium films by ALD using a cyclopentadienyl rhenium precursor and an alkyl halide co-reactant for use as catalyst in high-temperature superalloys, in superconducting applications, in adhesion layer, in liners, in diffusion barriers, in seed layers to improve growth of other materials, and in microelectronic applications and Yu provides a method of depositing metal films by ALD using an organometallic reactant comprising at least one cyclopentadiene ligand and an alkyl halide where they provide a high purity metal such that it will be expected to provide the desired and predictable result of depositing a rhenium metal film for the applications described by Sharma and further, since Yu teaches depositing molybdenum, tungsten, ruthenium, nickel, i.e. transition metal elements, the process is also expected to be applicable to rhenium films because it is also a transition element and because Sharma teaches using similar reactants (i.e., cyclopentadienyl ligands and reacting with alkyl halides).
Therefore, the process will result in exposing the substrate to an organometallic precursor comprising rhenium, exposing the substrate surface to an iodine-containing reactant meeting the claimed formula to form a carbon-less iodine-containing metal film and then exposing the iodine-containing metal film to a hydrogen anneal to provide a metal film due to the cyclical deposition process, where since it is done by the process of Yu it is also expected to provide the carbon-less iodine-containing metal film having a carbon content within the claimed range and a metal film having a resistivity overlapping the claimed range as described by Yu.
Regarding claim 40, Yu in view of Cooper, Kostamo, Vayrynen, and Sharma suggest the process of claim 38. Yu further teaches that the alkyl halide has the general formula R-X, where R is an alkyl, alkenyl, aryl, or other carbonaceous group (0090). They teach that R comprises on to two, one to four, or one to six carbon atoms (0091). They provide examples of iodoethane (H5C2I) or diiodomethane (CH2I2) (0091), indicating that the formula can be either RI or RI2. Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used a halide of RI or RI2 in which R is an alkenyl because Yu indicates that a suitable R group is an alkenyl, where the R group can be attached to one or two iodine atoms such that it will be expected to provide a suitable alkenyl halide for the process. Therefore, x will be within the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original).
Claims 43-47 and 49 are rejected under 35 U.S.C. 103 as being unpatentable over Yu, US 2019/0390340 A1 (provided on the IDS of 10/4/2021) in view of Cooper, US 2018/0122687 A1, Kostamo, US 2005/0208754 A1, Vayrynen, WO 2020/003000 A1, Heys, US 2013/0196065 A1 OR Vaartstra, US 6,281,124 OR Brand, US 2015/0262828 A1, OR Thompson, US 2008/0081127 A1.
Regarding claims 43-47 and 49, as discussed above for claims 23 and 38, Yu provides most of the features of claim 43, where the carbon-less iodine-containing metal film is exposed to hydrogen. They teach that the metal of the film can be molybdenum, where an example of the precursor is bis(ethylbenzene)molybdenum (0102-0103). They teach that in some embodiments the metal precursor comprises at least one ligand comprising an optionally alkyl substituted cyclopentadiene (Cp) ring (0102). They teach that in some embodiments the metal precursor comprises at least one ligand comprising an optionally alkyl substituted cyclopentadiene (Cp) ring (0102). They teach that in some embodiments, the metal precursor comprises at least one ligand comprising an open or closed diene such as 1,3-butadiene, 1,5-hexadiene (0102). They teach that the ligand may be an aromatic ligand such as benzene that comprises at least one organic substituent comprising in the range of 1 to 6 carbon atoms (0102). They teach that the metal precursor can be any suitable precursor with a decomposition temperature above the deposition temperature (0102). They teach that the substrate is maintained at a temperature less than or equal to about 400°C (0096).
As discussed above for claims 23 and 38, Cooper and Kostamo provide the suggestion of pre-treating the substrate surface in a hydrogen anneal at a temperature and pressure overlapping the claimed range and a flow rate within the claimed range so as to reduce the metal oxides on the metal surface. 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.”
Further, as discussed above for claims 23 and 38, from the teachings of Vayrynen, 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 Yu in view of Cooper and Kostamo to have exposed the substrate to the organometallic precursor, the first exposure of the iodine-containing reactant, and the second exposure of the iodine-containing reactant sequentially because Vayrynen teaches that it is known to expose a substrate to a precursor or reactant one or more times prior to exposing it to another precursor in a cyclical deposition which is indicated as being an ALD process such that it will be expected to provide a suitable sequence during the deposition while also ensuring the that self-limiting reaction has reached completion, i.e., it ensures that the surface is saturated with the reactant or precursor. Therefore, the process will consist of the claimed process steps which are either repeated or are performed singly when depositing a single cycle.
They do not teach using one of the claimed precursors.
For claims 43-45, Heys teaches molybdenum (IV) amide complexes corresponding in structure to Formula (I):
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142
412
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Greyscale
wherein L is -NR1R2, R1 and R2 are C1-C6 alkyl or hydrogen, R is C1-C6 alkyl, and n is 0, 1, 2, or 3 (abstract). They teach using the precursor for depositing a molybdenum-containing film by ALD (0009). They teach that the ALD growth conditions include a substrate temperature in the range of 160-300°C (0045-0046). They teach that the variation of the substitution of the Cp ring and three identical ligands attached to the metal center demonstrates useful and improved properties for ALD processes, such as increased thermal stability leading to improved product quality (0062). They teach that the use of Mo(IV) amide pianostool-type complexes enhances ALD performance by polarizing the molecule to allow reaction with the surface which can be saturative to self-limit film growth for excellent conformal control (0062). They teach that examples of the precursor include (methylcyclopentadienyl)Mo(NMe2)3 or (ethylcyclopentadienyl)Mo(NMe2)3 (0029 or 0030).
From the teachings of Heys, 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 Yu in view of Cooper, Kostamo, and Vayrynen to have used (methylcyclopentadienyl)Mo(NMe2)3 or (ethylcyclopentadienyl)Mo(NMe2)3 as the molybdenum precursor because Yu teaches that any suitable precursor can be used, where it may include an optionally alkyl substituted Cp ring, Hey teaches that the precursors can be used for ALD at a temperature within the range of Yu, and Heys teaches that the precursors provide benefits such as increase thermal stability, allow for saturative self-limiting film growth for excellent conformal control, etc. such that it will be expected to provide a desirable molybdenum precursor for the deposition process.
For claims 43 and 46, Vaartstra teaches a method of forming a film on a substrate using Group IVB, VB, or VIB metal complexes (abstract). They teach that Group VIB includes Mo (Col. 1, lines 39-52). They teach that the precursor composition comprises one or more complexes having the formula [(R1)NC(R2)C(R3)N(R4)]xMLy, wherein M is a Group IVB, VB, or VIB metal, each R1, R2, R3, and R4 group is independently H or an organic group, L is selected from the group including CO, NO, etc., x=1-4 and y=1 to 4 (Col. 2, lines 14-42). They teach forming a metal-containing film from the precursor composition on a surface of a substrate so that the complexes of Formula I are converted in some manner and deposited on a surface to form a metal-containing film (Col. 2, lines 14-42). They teach that methods of the invention are well suitable for forming films on a surface of a semiconductor substrate with or without layers or structures formed thereon (Col. 3, lines 4-26). They teach that the complexes can be used for CVD with assistance of plasmas or photolysis with substrate temperatures of about 100°C to about 400°C (Col. 4, lines 3-17). They teach that the precursor composition can be vaporized in the presence of a reaction gas to form a film, where the reaction gases include hydrogen, ammonia, etc. (Col. 4, lines 54-61). They teach that the metal-containing films can also be formed by subjecting a relatively pure metal film to subsequent processing (Col. 4, lines 54-67). They teach that the Group IVB, IV, or VIB metal complex is:
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where each R1-R4 is independently H or an organic group, L is selected from the group including CO, x=1-4, and y=1-4 (Col. 5, lines 12-42). They teach that the organic groups have 1-8 carbon atoms (Col. 5, lines 12-42). They teach that the organic group may be a t-butyl group (Col. 5, lines 43-59). They teach that the complexes are applicable in forming metal-containing films in a wide variety of film applications, including metallization layers (Col. 7, lines 22-32). They teach that such applications include multilevel interconnects in an integrated circuit structure (Col. 7, lines 22-32). They teach that the methods are not limited to any specific vapor deposition technique (Col. 9, lines 46-54). They provide an example of preparing Mo(CO)y(tBuN=CHCH=NtBu) (Col. 10, lines 30-40). Therefore, Vaartstra teaches using a complex meeting the formula of tBuDADMo(CO)4, where the complex is used for vapor deposition of metal films, including molybdenum, using a substrate temperature within the range of Yu.
From the teachings of Vaartstra, 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 tBuDADMo(CO)4 as the precursor in the deposition process because Yu teaches that any suitable precursor can be used, the precursors can be deposited by vapor deposition at a temperature overlapping the range of Yu for forming metal layers such that it will be expected to provide a desirable precursor for the deposition of the molybdenum film.
For claims 43 and 47, Brand teaches selectively depositing a first work function layer (abstract). They teach depositing the first work functional layer by CVD or ALD (0026). They teach exposing the precursor to a metal organic compound with a vapor pressure of greater than about 0.1 mTorr at about 200°C comprising Mo (0026). They teach that the precursor is one of Cp’Mo(CO)2NO, (RN)2(R’2N)2Mo, Cp’2MoH2, MoOCl4, etc., where R and R’ are each independently selected from H, alkyl (2-5), and where Cp’ is R1R2R3R4R5Cp, where each R is independently selected from H, alkyl, alkene, or the like (0026). Since they indicate that alkyl is (2-5), 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 also used a C2-C5 alkyl as the alkyl group of the Cp group because they indicate that such alkyl groups are understood to be defined as those having 2-5 carbon groups.
From the teachings of Brand, 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 Yu in view of Cooper, Kostamo, and Vayrynen to have used a molybdenum precursor such as bis(ethylcyclopentadienyl)MoH2 because Brand teaches using Cp’2MoH2, where they suggest that ethyl is a suitable group for the Cp ligand, indicating that such a precursor is capable of depositing a molybdenum film by ALD, and because Yu teaches that an alkyl-substituted Cp ligand can be used, such that it will be expected to provide a suitable precursor for deposition of molybdenum as a simple substitution of one known precursor for another.
For claims 43 and 49, Thompson teaches organometallic compounds represented by the formula (L1)yM(L)z-y, wherein M is a group 5 or 6 metal, L1 is a substituted or unsubstituted anionic 6 electron donor ligand, L2 is the same or different and is (i) a substituted or unsubstituted anionic 2 electron donor ligand, (ii) a substituted or unsubstituted cationic 2 electron donor ligand, or (iii) a substituted or unsubstituted neutral 2 electron donor ligand; y is an integer of 1, and z I s the valence of M; and wherein the sum of the oxidation number of M and the electric charges of L1 and L2 is equal to 0 (abstract). They teach a method for depositing a metal on a substrate by thermal or plasma enhanced dissociation of the organometallic precursor compounds by CVD or ALD techniques (abstract). They teach that the compound can be (L1)yM(CO)x’(L6)z-y-x’, wherein M is a group 5 to 6 metal, L1 is selected from substituted or unsubstituted ligands such as cyclopentadienyl, L6 is selected from groups including nitrosyl, x’ is an integer of from 0 to 3, y is an integer of 1, and z is the valence of M (0014). Therefore, they teach that the precursor can include CpMo(CO)2(NO), where the Cp group can be substituted. They provide examples of a tungsten compound where the cyclopentadienyl group is substituted with a methyl group (0063). 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 MeCpMo(CO)2(NO) is a suitable precursor because Thompson indicates that MeCp is an example of a suitable substituted Cp group. They teach that the presence of the anionic donor group enhance preferred physical properties, such as volatility, decrease in the temperature required to dissociate the precursor, and lower the boiling point of the precursor (0103).
From the teachings of Thompson, 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 Yu in view of Cooper, Kostamo, and Vayrynen to have used MeCpMo(CO)2(NO) as the precursor because Yu teaches that alkyl substituted Cp groups are desirable ligands, where any suitable precursor can be used and Thompson suggests that such a precursor is desirable in the deposition of a molybdenum film by ALD, where the precursors have desirable volatility, temperature for dissociation, and a lower boiling point such that it will be expected to provide a desirable molybdenum precursor.
Response to Arguments
Applicant's arguments filed 2/2/2026 have been fully considered.
In light of the amendments to the claims, the previous claim objection and 112(b) rejection is withdrawn.
Regarding Applicant’s argument that Cooper has absolutely nothing to do with deposition of molybdenum (Mo), tungsten (W), osmium (Os), rhenium (Re), iridium (Ir), nickel (Ni), or ruthenium (Ru), as claimed, the reference was relied upon for the teaching of a pre-treatment temperature using a hydrogen anneal which is required by the claims. In response to applicant's argument that Cooper is nonanalogous art, it has been held that a prior art reference must either be in the field of the inventor’s endeavor or, if not, then be reasonably pertinent to the particular problem with which the inventor was concerned, in order to be relied upon as a basis for rejection of the claimed invention. See In re Oetiker, 977 F.2d 1443, 24 USPQ2d 1443 (Fed. Cir. 1992). In this case, Cooper is in the field of vapor deposition and teaches performing a hydrogen anneal pre-treatment for a surface as is currently claimed. Therefore, Cooper is considered to be in Applicant’s field of endeavor, i.e., vapor deposition and hydrogen annealing pretreatments. Further, the hydrogen treatment is to reduce the oxides on the metal surface prior to deposition, which is indicated as being desirable by Yu, where Cooper teaches that the substrate includes metals (0034), suggesting that the hydrogen treatment is suitable for metals in general.
Regarding Applicant’s argument that Kostamo provides a post-deposition reduction process and not a pre-treatment process, it is noted that Yu teaches that the substrates can be exposed to pretreatments for reducing (0030). Further, Cooper was relied upon for the suggestion of performing a hydrogen anneal as a pretreatment process because they indicate that such a pretreatment removes contaminants such as organic impurities and metal oxides from a conductive metal surface prior to deposition. Therefore, Cooper suggests performing the hydrogen thermal treatment prior to deposition to clean the substrate at temperatures overlapping the claimed range. Kostamo teaches appropriate hydrogen flow rates and pressures for reducing metal oxides using temperatures overlapping the range of Cooper and the claimed range. Therefore, using the pressure and flowrate suggested by Kostamo is expected to also successfully reduce the metal oxides on the metal surface for pretreating the substrate or cleaning the surface prior to deposition.
Regarding Applicant’s arguments over claim 31, as discussed above, Yu is considered to suggest using an alkenyl group for R.
In light of the amendment to claim 38, the rejection has been modified to include the reference of Vayrynen.
In response to applicant's argument that the examiner's conclusion of obviousness is based upon improper hindsight reasoning, it must be recognized that any judgment on obviousness is in a sense necessarily a reconstruction based upon hindsight reasoning. But so long as it takes into account only knowledge which was within the level of ordinary skill at the time the claimed invention was made, and does not include knowledge gleaned only from the applicant's disclosure, such a reconstruction is proper. See In re McLaughlin, 443 F.2d 1392, 170 USPQ 209 (CCPA 1971). In the current case, while Sharma does not teach using an iodine-containing reactant, the reference indicates that it is desirable to form rhenium films using precursors similar to those of Yu. Therefore, the suggestion to form rhenium films using the process of Yu is because similar precursors are used, rhenium is a transition metal similar to those of Yu (molybdenum, ruthenium, etc.), and because it will be expected to provide a desirable film material for various applications.
As to Applicant’s argument that Sharma changes the operation of the prior art, while Sharma does not specifically teach using an iodine-containing reactant, they teach using an alkyl halide as the reactant and their process of deposition is very similar to that of Yu as discussed above. Therefore, the modification of Yu to deposit rhenium using a rhenium precursor and the iodine-containing reactant is expected to successfully deposit a rhenium film, where the iodine-containing reactant is an alkyl halide as disclosed by Sharma. Further, Yu teaches broadly depositing a metal film, suggesting that the process is not only limited to the specific embodiments of molybdenum, ruthenium, cobalt, copper, platinum, nickel, or tungsten (abstract, 0103, and claim 1). Specifically, Sharma indicates that rhenium is a desirable metal for deposition, where a reactant can be an alkyl halide and Yu provides a metal deposition method using an alkyl halide, i.e., RI, such that the use of a rhenium precursor is also expected to provide the predictable result of successfully depositing a desirable metal. Further, the principal of Yu is not changed, only a different metal precursor is used in combination with the alkyl iodide reactant.
Regarding Applicant’s arguments over the iodine-containing species, as noted above Yu is consider to suggest these features.
Regarding Applicant’s arguments over amended claim 43, the rejection has been modified to include Cooper, Kostamo, and Vayrynen as noted above.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718 /GORDON BALDWIN/Supervisory Patent Examiner, Art Unit 1718
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