DETAILED ACTION
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 Rejections - 35 USC § 102
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claim(s) 1,5-9, 11-12, and 15 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Hock et al. (US 2023/0167548).
Regarding Claims 1-2,5-9, and 11-12, Hock et al. (US’548) teach a method of selectively depositing a metal-containing material (e.g. combination of gallium and aluminum, Fig. 7; [0023]) on a first surface of a semiconductor substrate relative to a second surface of the substrate (Figs. 6; [0067]), the method comprising providing the substrate in a reaction chamber; and depositing the metal-containing material on the first surface of the substrate by a cyclic vapor deposition process (ALD), wherein the cyclic vapor deposition process comprises providing a first metal precursor (e.g. Ga(amd)2Me,Ga(amd)Me2,Ga(amd)2Me, Ga(amd)(nBu)2,Ga(amd)(vinyl)2, Ga(amd)(NMe2)2), into the reaction chamber in a vapor phase (Fig. 5; [0058-0062]); and providing a reactant (e.g. oxygen source, water, hydrogen peroxide) into the reaction chamber in a vapor phase [0050, wherein the first metal precursor comprises a heteroleptic precursor (e.g. Ga(amd)2Me,Ga(amd)Me2,Ga(amd)2Me, Ga(amd)(nBu)2,Ga(amd)(vinyl)2, Ga(amd)(NMe2)2), comprising a group 13 metal atom (gallium), an amidinato ligand (diisopropylacetamidinato-group (-amd) and an alkyl ligand (Me) attached to the metal atom [0020-0021]. In addition, the metal-containing material includes aluminum [0023].
Regarding Claim 15, US’548 teaches performing the process of Claim 1 on a dielectric surface comprising a metal oxide, since the process includes additional sub-cycles and/ or cycles on a metal oxide layer, deposited by an earlier sub-cycle and/ or cycles, including a first ALD sub-cycle AFTER a second ALD sub-cycle (Fig. 5; [0063]).
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.
Claim(s) 2 is/are rejected under 35 U.S.C. 103 as being unpatentable over Hock et al. (US 2023/0167548) in view of Madia et al. (US 2021/0118672).
Regarding Claim 2, US’548 teaches aluminum as an example of a second metal in a ternary gallium oxide produced by thermal ALD (Abstract; [0050]), without excluding other metals. US’548 fails to teach indium. Madia et al. (US’672) suggest other ternary metal oxides of gallium, including indium zinc gallium oxide (IZGO) and indium gallium oxide (IGO), produced by ALD, in an analogous method, including depositing a metal containing material on a first surface of a substrate by a cyclic vapor deposition process, wherein the cyclic vapor deposition process comprises providing a first metal precursor, including a gallium precursor, and providing a reactant into the reaction chamber (Abstract;[0015,0054,0106]). Thus, it would have been obvious to a person of ordinary skill of art to modify the process of US’548 BY ANY OF substituting an indium for the aluminum precursor to form indium gallium oxide or indium gallium zinc oxide, by depositing both aluminum gallium oxide and either indium gallium oxide or indium gallium zinc oxide, or by substituting an aluminum precursor for a zinc precursor to deposit indium aluminum gallium oxide, thereby forming a metal-containing material, because US’672 suggests a method analogous to US’548 for depositing ternary and quaternary metal oxides.
Claim(s) 3-4 is/are rejected under 35 U.S.C. 103 as being unpatentable over Hock et al. (US 2023/0167548) in view of Gordon et al. (US 2006/0141155).
Regarding Claim 3, US’548 teaches depositing gallium oxide (gallium, a trivalent group 13 metal) from a precursor, including an amidinato ligand. US’548 also teaches depositing aluminum oxide with an organic aluminum precursor, and does not teach an organic aluminum precursor with an amidinato ligand [0022]. Gordon et al. (US’155) is analogous art in the field of ALD deposition of metal oxides and of precursors for ALD deposition and teaches organometallic precursors for ALD deposition of metal oxides, including metal amidinates (Abstract). US’155 suggests that not only gallium is a candidate as a trivalent metal for aminidato precursors, but also aluminum [0046]. It would have been obvious to a person of ordinary skill in the art at the time of invention to modify the process of US’548 by simple substitution of one group 13 trivalent metal for another (e.g. aluminum for gallium) to produce other heteroleptic precursors containing the same combination of ligands with a reasonable expectation of depositing oxides of the substituted group 13 trivalent metal. (i.e. aluminum oxide instead of gallium oxide).
Regarding Claim 4, US’548 teaches the deposition of gallium oxide by cycles of ALD, including sub-cycles of sequential pulses of a heteroleptic precursor comprising a group 13 metal atom (gallium), an amidinato ligand and an oxygen source (water), and an alkyl ligand attached to the group 13 metal atom (see rejection of Claim 1 above for citations). US’548 fails to teach deposition of a group 13 nitride. However, it was well-known in the art at the time of invention that a single organometallic precursor can be used to deposit either a metal oxide layer or a metal nitride layer by varying a reactant from an oxygen source to a nitrogen source. US’155 provides evidence of this, teaching that typical second reactants include hydrogen gas to deposit metal, ammonia gas to deposit a metal nitride, and water vapor to deposit metal oxide [0043]. Thus, it would have been obvious to a person of ordinary skill in the art to modify the process of US’548 with a simple substitution of a nitrogen reactant for an oxygen reactant (e.g. ammonia gas for water vapor) in order to deposit aluminum nitride instead of aluminum oxide, also a simple substitution in the prior art of a nitride for an oxide.
Claim(s) 10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Hock et al. (US 2023/0167548) in view of in view of Madia et al. (US 2021/0118672) as applied to Claim 2 above, and further in view of Gordon et al. (US 2006/0141155).
Regarding Claim 10, US’548 teaches the deposition of gallium oxide by cycles of ALD, including sub-cycles of sequential pulses of a heteroleptic precursor comprising a group 13 metal atom (gallium), an amidinato ligand and an oxygen source (water), and an alkyl ligand attached to the group 13 metal atom (see rejection of Claim 1 above for citations). Ligands for the group 13 metal atom include N,N’-diisopropylformamidinato, methyl, ethyl, propyl groups [0051,0021]. US’548 also teaches depositing aluminum oxide with an organic aluminum precursor. The combination of US’548 in view of US’672 fails to teach an organic aluminum precursor with an amidinato ligand [0022]. US’155 is analogous art in the field of ALD deposition of metal oxides and of precursors for ALD deposition and teaches organometallic precursors for ALD deposition of metal oxides, including metal amidinates (Abstract). US’548 suggests that not only gallium is a candidate as a trivalent metal for aminidato precursors, but also aluminum [0046]. It would have been obvious to a person of ordinary skill in the art at the time of invention to modify the process of US’548 in view of US’672 EITHER by simple substitution of one group 13 trivalent metal for another (e.g. aluminum for gallium) to produce other heteroleptic precursors containing the same combination of ligands with a reasonable expectation of depositing oxides of the substituted group 13 trivalent metal OR by substituting one aluminum precursor for another to deposit any of gallium aluminum oxide, aluminum oxide, indium aluminum oxide, indium gallium oxide, indium gallium zinc oxide, indium gallium aluminum oxide, or other combinations, and mixtures thereof, because US’155 suggests other precursors of aluminum, while the combination of US’548 in view of US’672 suggests the obviousness of binary, ternary, and higher metal oxides, including a variety of combinations of gallium, aluminum, and indium.
Claim(s) 13-14 is/are rejected under 35 U.S.C. 103 as being unpatentable over Fukase (US 5,384,287) in view of Gordon et al. (US 2006/0141155) and Hock et al. (US 2023/0167548).
Regarding Claims 13-14, Fukase (US’287) teach a now well-known semiconductor device, including stacked layers, including gate electrodes, a silicon oxide mask covering the gate electrodes, and an aluminum oxide layer covering the silicon oxide layer (Figs. 2A,12A; col. 8, lines 51-60; col. 11, lines 47-54).
US’287 fails to teach a method of selectively depositing a metal-containing material on a first surface of a semiconductor substrate relative to a second surface of the substrate; the method comprising providing the substrate in a reaction chamber; and depositing the metal-containing material on the first surface of the substrate by a cyclic vapor deposition process, wherein the cyclic vapor deposition process comprises providing a first metal precursor into the reaction chamber in a vapor phase; and providing a reactant into the reaction chamber in a vapor phase, wherein the first metal precursor comprises a heteroleptic precursor comprising a group 13 metal atom, an amidinato ligand and an alkyl ligand attached to the metal atom. Gordon et al. (US’155) is analogous art in the field of semiconductors and film deposition of metal oxides for semiconductor devices and is reasonably pertinent to Applicant’s problem of depositing a metal oxide film. US’548 suggests that aminidato precursors of trivalent metals can be used to deposit metal oxide films of the trivalent metal by ALD (Abstract; [0046]). Suitable trivalent metals, include gallium and aluminum [0046]. US’155 also teaches that trimethylaluminum is a precursor for aluminum oxide deposition [0073]. It would have been obvious to a person of ordinary skill in the art at the time of invention to deposit an aluminum oxide layer of US’287 by ALD using an aluminum precursor including an aminidato and/or methyl ligand to deposit an aluminum oxide film, because US’155 suggests aluminum precursors with these ligands.
The combination of US’287 in view of US’155 fails to teach a heteroleptic precursor comprising a group 13 metal atom, an amidinato ligand, and an alkyl ligand attached to the group 13 metal atom.
US’548 is analogous art in the field of deposition of metal oxide films by ALD and teach a method of selectively depositing a group 13 metal-containing material (gallium oxide) on a first surface of a semiconductor substrate relative to a second surface of the substrate (Fig. 6; [0067]), the method comprising providing the substrate in a reaction chamber; and depositing the metal-containing material on the first surface of the substrate by a cyclic vapor deposition process (ALD), wherein the cyclic vapor deposition process comprises providing a first metal precursor (e.g. Ga(amd)2Me,Ga(amd)Me2,Ga(amd)2Me, Ga(amd)(nBu)2,Ga(amd)(vinyl)2, Ga(amd)(NMe2)2), into the reaction chamber in a vapor phase (Fig. 5; [0058-0062]); and providing a reactant (e.g. oxygen source, water, hydrogen peroxide) into the reaction chamber in a vapor phase [0050, wherein the first metal precursor comprises a heteroleptic precursor (e.g. Ga(amd)2Me,Ga(amd)Me2,Ga(amd)2Me, Ga(amd)(nBu)2,Ga(amd)(vinyl)2, Ga(amd)(NMe2)2), comprising a group 13 metal atom (gallium), an amidinato ligand (diisopropylacetamidinato-group (-amd) and an alkyl ligand (Me) attached to the metal atom [0020-0021]. While US’548 fails to teach aluminum analogs of these gallium precursors, the teaching in US’155 that both gallium and aluminum are suitable trivalent metals for precursors including aminidato ligands, especially considering that both gallium and aluminum belong to group 13, would have suggested to a person of ordinary skill in the art the substitution of aluminum for gallium in the precursors of US’548 with the reasonable expectation of depositing aluminum oxide layers for the gate structure of US’287.
Claim(s) 16-19 and 21-22 is/are rejected under 35 U.S.C. 103 as being unpatentable over Kilkuchi (US 2008/0258216) in view of Gordon et al. (US 2006/0141155) and Hock et al. (US 2023/0167548).
Regarding Claims 16-19 and 21-22, Kilkuchi (US’216) teach a typical semiconductor device, including various material layers (second surfaces) deposited on a substrate, including layers comprising aluminum oxide or hafnium oxide, metal layers, and metal nitride layers (Fig. 1) [0074,0123]. US’216 fails to teach a method of selectively depositing a metal-containing material (e.g. aluminum oxide) on a first surface of a semiconductor substrate relative to a second surface of the substrate; the method comprising providing the substrate in a reaction chamber; and depositing the metal-containing material on the first surface of the substrate by a cyclic vapor deposition process, wherein the cyclic vapor deposition process comprises providing a first metal precursor into the reaction chamber in a vapor phase; and providing a reactant into the reaction chamber in a vapor phase, wherein the first metal precursor comprises a heteroleptic precursor comprising a group 13 metal atom, an amidinato ligand and an alkyl ligand attached to the metal atom.
US’216 fails to teach a method of selectively depositing a metal-containing material (e.g. aluminum oxide) on a first surface of a semiconductor substrate relative to a second surface of the substrate (other surfaces, comprising any of aluminum oxide, hafnium oxide, elemental metal, or metal nitride); the method comprising providing the substrate in a reaction chamber; and depositing the metal-containing material on the first surface of the substrate by a cyclic vapor deposition process, wherein the cyclic vapor deposition process comprises providing a first metal precursor into the reaction chamber in a vapor phase; and providing a reactant into the reaction chamber in a vapor phase, wherein the first metal precursor comprises a heteroleptic precursor comprising a group 13 metal atom, an amidinato ligand and an alkyl ligand attached to the metal atom. US’155 is analogous art in the field of semiconductors and film deposition of metal oxides for semiconductor devices and is reasonably pertinent to Applicant’s problem of depositing a metal oxide film. US’548 suggests that aminidato precursors of trivalent metals can be used to deposit metal oxide films of the trivalent metal by ALD (Abstract; [0046]). Suitable trivalent metals, include gallium and aluminum [0046]. US’155 also teaches that trimethylaluminum is a precursor for aluminum oxide deposition [0073]. It would have been obvious to a person of ordinary skill in the art at the time of invention to deposit an aluminum oxide layer of US’216 by ALD on a first surface of the semiconductor using an aluminum precursor including an aminidato and/or methyl ligand to deposit an aluminum oxide film, because US’155 suggests aluminum precursors with these ligands.
The combination of US’216 in view of US’155 fails to teach a heteroleptic precursor comprising a group 13 metal atom, an amidinato ligand, and an alkyl ligand attached to the group 13 metal atom.
US’548 is analogous art in the field of deposition of metal oxide films by ALD and teach a method of selectively depositing a group 13 metal-containing material (gallium oxide) on a first surface of a semiconductor substrate relative to a second surface of the substrate (Fig. 6; [0067]), the method comprising providing the substrate in a reaction chamber; and depositing the metal-containing material on the first surface of the substrate by a cyclic vapor deposition process (ALD), wherein the cyclic vapor deposition process comprises providing a first metal precursor (e.g. Ga(amd)2Me,Ga(amd)Me2,Ga(amd)2Me, Ga(amd)(nBu)2,Ga(amd)(vinyl)2, Ga(amd)(NMe2)2), into the reaction chamber in a vapor phase (Fig. 5; [0058-0062]); and providing a reactant (e.g. oxygen source, water, hydrogen peroxide) into the reaction chamber in a vapor phase [0050, wherein the first metal precursor comprises a heteroleptic precursor (e.g. Ga(amd)2Me,Ga(amd)Me2,Ga(amd)2Me, Ga(amd)(nBu)2,Ga(amd)(vinyl)2, Ga(amd)(NMe2)2), comprising a group 13 metal atom (gallium), an amidinato ligand (diisopropylacetamidinato-group (-amd) and an alkyl ligand (Me) attached to the metal atom [0020-0021]. While US’548 fails to teach aluminum analogs of these gallium precursors, the teaching in US’155 that both gallium and aluminum are suitable trivalent metals for precursors including aminidato ligands, especially considering that both gallium and aluminum belong to group 13, would have suggested to a person of ordinary skill in the art the substitution of aluminum for gallium in the precursors of US’548 with the reasonable expectation of depositing aluminum oxide layers for the gate structure of US’216.
Claim(s) 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Hock et al. (US 2023/0167548) in view of Illiberi et al. (US 2021/0301394).
Regarding Claim 20, US’548 fails to teach an inhibitor. Illiberi et al. (US’394) is analogous art in the field of deposition by ALD and teaches before providing the first metal precursor into the reaction chamber, treating the first surface with an inhibitor reactant and thereafter depositing an organic polymer on the second surface to passivate the second surface for selective deposition [0036]. It would have been obvious to a person of ordinary skill in the art at the time of invention to modify the process of US’548 by before providing the first metal precursor into the reaction chamber, treating the first surface with an inhibitor reactant and thereafter depositing an organic polymer on the second surface to passivate the second surface, because US’394 suggests these steps to enable selective deposition by ALD.
Response to Arguments
Applicant's arguments, filed 9 June 2026, have been fully considered but they are not persuasive.
In response to Applicant’s statement that the Office has not rejected the claimed method wherein the metal-containing material includes indium (Remarks, p. 5), no claim, previously examined, required a metal-containing material including indium, since the previously examined claims also recited gallium and aluminum as alternatives. Madia et al. (US’672) is now cited to show the obviousness of including indium in a metal-containing material, deposited by the claimed method.
In response to Applicant’s argument concerning the rejection of Claim 1 (Remarks, pp. 6-9) , the argument includes arguments about an aluminum precursor having an amidinato ligand (bottom, p. 6), which suggests that Applicant is conflating Claims 1 with other claims (perhaps Claim 10, which recites specific aluminum precursors). While US’548 uses aluminum, and certain aluminum precursors, as an example, it does not exclude other metals or aluminum precursors. Gordon suggests that amidinato precursors of metals, including aluminum, are available for ALD deposition, including for deposition of oxides and nitrides of those metals [0046]. While US’155 suggests that aluminum can be a metal of a metalamidinate precursor, including for the deposition of oxides and nitrides of those metals, Applicant has not given sufficient reasons to exclude other known aluminum ALD precursors, including amidinate precursors, as precursors for aluminum in the ALD process of US’548 or to substitute aluminum or indium for gallium to produce an aluminum oxide or indium oxide, since US’155 suggests that any of gallium, indium, or aluminum can be precursors for deposition.
In response to Applicant’s argument that Hock teaches only gallium (Remarks, p. 7), Gordon, on the other hand suggests that aluminum and indium can also be used instead of gallium (i.e. are simple substitutes for gallium ) [0046].
In response to Applicant’s argument concerning temperature and pressure considerations for the exemplar precursor in US’548 (Remarks, p. 8), it does not follow from the discussion of example precursors of an example metal in US’548 that it would not have been obvious to use other precursors, including of other metals, not studied in US’548, especially given that other prior art does suggest other precursors in analogous processes.
Conclusion
No claim is allowed.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure:
MELICALJUNAN et al. (CN 104284997 A) (depositing indium gallium zinc oxide, indium aluminum oxide and other ternary and quaternary oxides)
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.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ALEXANDER M WEDDLE whose telephone number is (571)270-5346. The examiner can normally be reached 9:30-6:30.
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ALEXANDER M WEDDLE
Examiner
Art Unit 1712
/ALEXANDER M WEDDLE/Primary Examiner, Art Unit 1712
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