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 § 103
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.
Claims 1, 2, 4-6, 10-12, 14-18, 20, 21 and 23 are rejected under 35 U.S.C. 103 as being unpatentable over Yu et al (US Patent Application Publication 2020/0343136) and Curtin et al (US Patent Application Publication 2023/0087976).
Regarding claim 1, Yu et al disclose a method of forming a metal layer, the method comprising:
(a) providing a semiconductor substrate 212 having a recessed feature 202 [see Fig. 2A];
(b) exposing the semiconductor substrate to a halogen-containing compound [see paragraphs 0009 and 0025];
(c) exposing the semiconductor substrate to a metal precursor and a reducing agent to form a metal layer at least within the recessed feature on the semiconductor substrate [see paragraph 0030].
Yu et al do not disclose wherein the halogen-containing compound represents a deposition inhibitor, and wherein the deposition inhibitor modifies a surface of the semiconductor substrate to make the surface more resistant to metal deposition than the surface was before modification, nor specifically wherein the metal precursor and the halogen-containing compound are different. One such as Curtin et al disclose exposing a substrate to a halogen-containing compound specifically for the purpose of acting as an inhibitor of ALD deposition [see paragraphs 0049-0050]. Furthermore, the halogen-containing compound taught by Curtin et al is definitively different than the metal precursor of Yu et al. It would have been obvious to one of ordinary skill in the art at the time of invention to perform the pretreatment disclosed by Yu et al to have the effect of Curtin et al in order to control the deposition of the metal layer.
Regarding claim 2, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein the semiconductor substrate is exposed to the deposition inhibitor prior to exposure to the metal precursor [see paragraphs 0025-0030].
Regarding claim 4, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein the halogen-containing compound is an iodine-containing compound [see paragraph 0036].
Regarding claim 5, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein the metal layer comprises a molybdenum layer, or a cobalt layer, or a ruthenium layer, or any combination thereof [see paragraphs 0026].
Regarding claim 6, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore to the deposition inhibitor comprising a halogen-containing compound, Curtin et al disclose wherein the halogen-containing compound is selected from the group consisting of I2 (diiodine), HI (hydrogen iodide), CH3I (methyl iodide), C2H5I (ethyl iodide), 1-iodopropane, 2-iodopropane, 1-iodobutane, sec-butyl iodide, t-butyl iodide, iodocyclopentane, iodocyclohexane, diiodomethane, 1,2-diiodoethane, 1,1-diiodopropane, 1,2-diiodopropane, 1,3-diiodopropane, 2,2-diiodopropane, 1,1-diiodobutane, 1,2-diiodobutane, 1,3-diiodobutane, 2,2- diiodobutane, 2,3-diiodobutane, 1,2-diiodo-2-methylpropane, 2,3-diiodo-2,3-dimethylbutane, 1,1,2,2- tetraiodoethane, 2,2,3,3-tetraiodobutane, 1,1,1,2,2,2-hexaiodoethane, 1,2-diiodocyclopentane, 1,2- diiodocyclohexane, iodobenzene, diiodobenzene, 2-iodopyridine, 3-iodopyridine, 4-iodopyridine, 3- iodo-1-nitrobenzene, 3-iodo-1-trifluoromethylbenzene, 4-iodoaniline, 4-iodo-1-dimethylaminobenzene, 4-iodophenol, (trimethylsilyl)methyl iodide, (trimethylsilyl)methyl diiodide, (trimethylsilyl)methyl triiodide, bis(trimethylsilyl)methyl iodide, bis(trimethylsilyl)methyl diiodide, tris(trimethylsilyl)methyl iodide, 1-(trimethylsilyl)-1-iodoethane, 1-(trimethylsilyl)-1,2-diiodoethane, 1,1 -bis(trimethylsilyl)- 1,2-diiodoethane, 1,2-bis(trimethylsilyl)-1,2-diiodoethane, CHI3 (triiodomethane), CI4 (carbon tetraiodide), 1-iodoethene, 1-iodopropene, 2-iodopropene, 1-iodo-1- butene, 1-iodo-2-butene, 2-iodo-1-butene, 2-iodo-2-butene, iodoacetylene, 3,3-dimethyl-1-iodo-but- 1-yne, 1,1-diiodoethene, 1,2-diiodoethene, 1,2-diiodopropene, 1,2-diiodo-2-propene, 1,2-diiodobutene, 1,2-diiodo-2-butene, 1,2-diiodo-3-butene, 3,4-diiodocyclohexene, 4,5-diiodocyclohexadiene, 1,2-diiodoacetylene, 1,1,2,2-tetraiodoethene, SiI4 (silicon tetraiodide), SiHI3 (triiodosilane), SiH2I2 (dioiodosilane), SiH3I (iodosilane), Si(CH3)I3 (methylsilyl triiodide), Si(CH3)2I2 (dimethylsilyl diiodide), Si(CH3)3I (trimethylsilyl iodide), Si(CH3)HI2 (diiodomethylsilane), Si(CH3)2HI (iododimethylsilane), Si(CH3)H2I (methyliodosilane), Si2I6 (hexaiododisilane), GeI4 (germanium tetraiodide), GeHI3 (triiodogermane), GeH2I2 (diiodogermane), GeH3I (iodogermane), A1I3 (aluminum triiodide), BI3 (boron triiodide), TiI4 (titanium tetraiodide), SnI4 (tin tetraiodide), N-iodosuccinimide, 1,3-diiodo-5,5-dimethylhydantoin, N-iodophthalimide, N- iodosaccharin, 1-chloro-2-iodoethane, iodinechloride (ICl), and combinations thereof [see paragraph 0050].
Regarding claim 10, the prior art of Yu et al and Curtin et al disclose the method of claim 1. While neither Yu et al nor Curtin et al specifically disclose wherein the deposition inhibitor modifies the surface of the semiconductor substrate by at least one of physisorption or chemisorption, one of ordinary skill in the art would recognize that physisorption and/or chemisorption are the primary mechanism by which a halogen deposition inhibitor is reversibly provided to modify a surface.
Regarding claim 11, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein the deposition inhibitor modifies the surface of the semiconductor substrate by halogenating the surface of the substrate [see paragraph 0025].
Regarding claim 12, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein the metal layer is deposited at a temperature of between about 250ºC and about 600ºC and a pressure of less than about 300 torr [see paragraph 0030].
Regarding claims 14 and 15, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein the semiconductor substrate provided in (a) comprises exposed metal nitride 216, wherein the exposed metal nitride lines sidewalls of the recessed feature and a bottom of the recessed feature, and in particular titanium nitride [see Fig. 2A; see also paragraph 0026].
Regarding claim 16, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein the semiconductor substrate provided in (a) comprises an exposed silicon-containing dielectric 212 and an exposed metal 220, wherein the exposed silicon-containing dielectric is exposed at sidewalls of the recessed feature, and the exposed metal is exposed at a bottom of the recessed feature [see Fig. 2A; see also paragraph 0023].
Regarding claim 17, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein (c) comprises sequentially exposing the semiconductor substrate to the metal precursor and a reducing agent, and repeating the sequential exposure to perform at least 10 inhibitor-free deposition cycles [see paragraph 0030].
Regarding claim 18, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein the method comprises:
(i) exposing the semiconductor substrate to the deposition inhibitor [see paragraph 0025];
(ii) after (i), exposing the semiconductor substrate to the metal precursor;
(iii) after (ii) exposing the semiconductor substrate to a reducing agent to reduce the metal precursor to metal; and
(iv) repeating steps (i)-(iii) to perform at least 10 inhibitor-assisted deposition cycles [see paragraph 0030].
Regarding claims 20 and 21, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Furthermore, Yu et al disclose wherein the metal layer is deposited conformally, which would include depositing the metal layer in a bottom-up deposition mode to fill the recessed feature [see Figs. 2B-2D; see also paragraph 0029].
Regarding claim 23, Yu et al disclose an apparatus for processing a substrate, the apparatus comprising:
(a) a process chamber 500, having a substrate holder 538 for holding a semiconductor substrate, and one or more inlets for introduction of reactants to the process chamber [see Fig. 5; see also paragraphs 0048-0054]; and
(b) a controller 554 comprising program instructions for:
(i) causing contact of a semiconductor substrate having a recessed feature with a halogen-containing compound [see Fig. 2A; see also paragraphs 0009 and 0025]; and
(ii) causing contact of the semiconductor substrate with a metal precursor, and causing a reduction of the metal precursor to form a metal layer at least within the recessed feature on the semiconductor substrate [see paragraph 0030].
Yu et al do not disclose wherein the halogen-containing compound represents a deposition inhibitor, and wherein the deposition inhibitor modifies a surface of the semiconductor substrate to make the surface more resistant to metal deposition than the surface was before modification, nor specifically wherein the metal precursor and the halogen-containing compound are different. One such as Curtin et al disclose exposing a substrate to a halogen-containing compound specifically for the purpose of acting as an inhibitor of ALD deposition [see paragraphs 0049-0050]. Furthermore, the halogen-containing compound taught by Curtin et al is definitively different than the metal precursor of Yu et al. It would have been obvious to one of ordinary skill in the art at the time of invention to perform the pretreatment disclosed by Yu et al to have the effect of Curtin et al in order to control the deposition of the metal layer.
Claims 7 and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Yu et al (US Patent Application Publication 2020/0343136) and Curtin et al (US Patent Application Publication 2023/0087976) as applied to claim 1 above, and further in view of Cen et al (US Patent Application Publication 2022/0372617).
Regarding claim 7, the prior art of Yu et al and Curtin et al disclose the method of claim 1. Neither Yu et al nor Curtin et al disclose wherein the metal layer is a molybdenum layer, and the metal precursor is a molybdenum precursor. One such as Cen et al disclose a substantially similar method of forming a metal layer on a halogen-treated surface, including a ruthenium layer as disclosed by Yu et al, wherein a molybdenum layer, formed with a molybdenum precursor, is an alternative metal [see paragraphs 0046-0048]. It would have been obvious to one of ordinary skill in the art at the time of invention to use a molybdenum precursor to form a molybdenum layer because they are disclosed by Cen et al to be alternatives in the art for the purpose of forming a metal layer for electrical contact in a semiconductor structure, as they are both low-resistance metals.
Regarding claim 8, the prior art of Yu et al, Curtin et al and Cen et al disclose the method of claim 7. Furthermore to the molybdenum precursor, Cen et al disclose wherein the molybdenum precursor comprises MoCl5, Mo2Cl10, MoO2Cl2, MoOCl4, bis(ethylbenzene)molybdenum or any combination thereof [see paragraph 0005; while Cen et al teach that they prefer molybdenum precursors that do not comprise chlorine, a teaching that a material is non-preferred is not a teaching away, and in fact is a teaching that these precursors are known and used in the art].
Allowable Subject Matter
Claims 9 and 22 are objected to as being dependent upon a rejected base claim, but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
The following is a statement of reasons for the indication of allowable subject matter: regarding dependent claim 9, the prior art of record fails to teach or make reasonably obvious, in combination with the other claimed elements and with sufficient specificity, wherein the deposition inhibitor modifies a surface on a field region and near an opening of the recessed feature to a greater degree than a surface of a bottom of the recessed feature; regarding dependent claim 22, the prior art of record fails to teach or make reasonably obvious, in combination with the other claimed elements and with sufficient specificity, wherein the method comprises delivering the deposition inhibitor and the metal precursor to a process chamber contemporaneously.
Conclusion
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/C.E.S./Examiner, Art Unit 2899 /VICTOR A MANDALA/Primary Examiner, Art Unit 2899
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