DETAILED ACTION
This is in response to communication received on 5/5/26
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
The text of those sections of AIA 35 U.S.C. code not present in this action can be found in previous office actions dated 2/9/26.
Claim Rejections - 35 USC § 102
The claim rejection(s) under 35. U.S.C. 102(a)(1) as being anticipated by Zope et al. US PGPub 201310260555 hereinafter ZOPE on claims 1-3 and 11-12 are withdrawn because the independent claim 1 has been amended and claim 12 is cancelled.
Claim Rejections - 35 USC § 103
The claim rejection(s) under AIA 35 U.S.C. 103 as being obvious over Zope et al. US PGPub 201310260555 hereinafter ZOPE on claim 4-9 and 14-19 are withdrawn because the independent claim 1 has been amended, and claim 14 is cancelled.
The claim rejection(s) under AIA 35 U.S.C. 103 as being obvious over Zope et al. US PGPub 01310260555 hereinafter ZOPE as applied to claim 1, 2, 3, 4 and 10 above, and further in view of Mani et al. US PG Pub 200910233453 hereinafter MANI on claim 10 and 20 are withdrawn because the independent claim 1 has been amended.
Claim(s) 1-2, 4-9, and 21-23 are rejected under 35 U.S.C. 103 as being unpatentable over by Zope et al. US PGPub 201310260555 hereinafter ZOPE further in view of Lubomirsky et al. US PGPub2014/0227881 hereinafter LUBOMIRSKY and Shankar et al. US Patent Number 7,727,906 hereinafter SHANKAR.
As for claim 1, ZOPE teaches "Methods for depositing a contact metal layer in contact structures of a semiconductor device are provided" (abstract, lines 1-2) and "Embodiments of the present invention provide gapfill utilizing metallic CVD processes (e.g., cobalt CVD processes) resulting in a potential low contact resistance (Re) onematerial solution for contact fill" (paragraph 22, lines 1-4), i.e. A method of depositing a gap-fill material on a semiconductor substrate.
ZOPE further teaches "In one or more embodiments, the deposition method passivates dangling silicon bonds" (paragraph 60, lines 4-5), i.e. forming a passivation layer.
ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5), and "The pretreatment gas mixture may be supplied from a remote plasma source, such as the remote plasma source 141 coupled to the metal deposition processing chamber 150" (paragraph 54), i.e. by introducing a hydrogen gas and an oxygen gas from a remote plasma source to a processing chamber.
SHANKAR teaches “This invention relates to electronic device fabrication for making devices such as semiconductor wafers and resolves the detrimental fluorine loading effect on deposition in the reaction chamber of a HDP CVD apparatus used for forming dielectric layers in high aspect ratio, narrow width recessed features with a repeating dep/etch/dep process” (abstract, lines 1-6).
SHANKAR teaches “In a preferred embodiment, hydrogen and oxygen gas is introduced to the reactor to create the plasma-containing hydrogen and oxygen gas and comprises substantially molecular hydrogen and molecular oxygen. In other embodiments, the gas may comprise a combination of hydrogen, oxygen, steam (H2O), hydrogen peroxide (H2O2) , among others. He or other inert gas may be used as a diluent” (column 7, lines 8-14), i.e. wherein an oxygen gas and a hydrogen gas combination is a known equivalent to H2O2 in CVD processes.
It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results. In this case, the H2O2 of ZOPE being replaced with the hydrogen gas and oxygen gas of SHANKAR to obtain the predictable result of hydrogen and oxygen ions being applied to the surface.
ZOPE is silent on through an ion filter.
LUBOMIRSKY teaches “An exemplary system may include a chamber configured to contain a semiconductor substrate in a processing region of the chamber. The system may include a first remote plasma unit fluidly coupled with a first access of the chamber and configured to deliver a first precursor into the chamber through the first access” (abstract, lines 1-6) and “Each substrate processing chamber 108-fj; can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, preclean, degas, orientation, and other substrate processes” (paragraph 31, lines 11-17).
LUBOMIRSKY teaches “An ion suppressor may be used to filter ions from the plasma effluents during transit from the remote plasma region to the substrate processing region in embodiments of the technology. The ion suppressor functions to reduce or eliminate ionically charged species traveling from the plasma generation region to the substrate. Uncharged neutral and radical species may pass through the openings in the ion suppressor to react at the substrate. It should be noted that complete elimination of ionically charged species in the reaction region surrounding the substrate is not always the desired goal. In many instances, ionic species are required to reach the substrate in order to perform the etch and/or deposition process. In these instances, the ion suppressor helps control the concentration of ionic species in the reaction region at a level that assists the process. In disclosed embodiments the upper plate of the gas distribution assembly may include an ion suppressor.” (paragraph 111), i.e. providing precursors through an ion filter.
It would have been obvious to one of ordinary skill in the art to include through an ion filter in the process of ZOPE because LUBOMIRSKY teaches the ion filters controls the concentration of ionic species in a deposition process to a specific level to assist the process.
ZOPE shows in Fig. 7 A and teaches "A silicon containing layer 404 is formed on the substrate 402 having openings 406 formed therein with high aspect ratios, such as aspect ratios greater than 10: 1, for example about greater than 20: 1. The openings 406 (which may be a contact opening, contact via, contact trench, contact channel or the like) are formed in the device structure 408 and have sidewalls 412 and a bottom 414 which form an open channel to expose the underlying silicon containing layer 404. The silicon containing layer 404 may include any suitable layers such as a single silicon layer or a multiple layer film stack having at least one silicon containing layer formed therein" (paragraph 44, lines 1-12) i.e. which is a range that includes the contact structure comprises a feature formed over a surface of the semiconductor substrate; the feature comprises an opening that is defined by a surface of a substrate, a surface of a lower dielectric material disposed over the substrate, and a surface of an upper dielectric material disposed over the lower dielectric material. Examiner notes that as currently written the claims do not distinguish between a substrate made of a singular material or a substrate made of multiple layers.
ZOPE teaches "At block 320, prior to deposition of a contact metal layer on the substrate 402, but after the substrate 402 is provided in the metal deposition processing chamber 150 at block 310, a pretreatment process may be performed to pretreat the substrate surface 411, thus, forming a treated surface region 410 on the surface 411, sidewalls 412 and bottoms 414 of the openings 406 in the silicon containing layer 404, as shown in FIG. 4B" (paragraph 52, lines 1-8), i.e. the passivation layer is formed over the surface of the substrate, the surface of the lower dielectric material, and the surface of the upper dielectric material.
ZOPE teaches "The contact metal layer 420 may be deposited using a multi-step deposition process comprising multiple cycles of performing a cyclic metal deposition process to deposit the contact metal layer 420 followed by annealing the contact metal layer 420. In certain embodiments, the thickness of the contact metal layer 420 should be less than 50% of the feature diameter (critical dimension) of the smallest feature to be filled. For example, the cyclic metal deposition process is performed to partially fill a feature to less than half of the feature diameter followed by an anneal process. The cyclic deposition process followed by an anneal would then be repeated to deposit until the contact metal layer 420 achieved a predetermined thickness. In an alternative embodiment, the contact metal layer 420 may be deposited to completely fill the feature in a single, non-cyclic deposition process" (paragraph 59, lines 1-15), i.e. depositing a metal gap-fill material over a portion of the passivation layer to fill the feature formed in the surface of the semiconductor substrate.
As for claim 2, ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5), i.e. wherein the hydrogen gas comprises hydrogen or water.
As for claim 4, ZOPE is silent on a hydrogen gas to an oxygen gas.
SHANKAR teaches “The hydrogen and oxygen gas in the desired ratio may be introduced to the chamber at any suitable flow rate. In a preferred embodiment for both 200 and 300 mm wafers, the flow rates of hydrogen ranges between about 100 sccm and 2000 sccm while the flow rate of oxygen varies between 50 sccm and 500 sccm” (column 7, lines 16-21). It is expected that a person of ordinary skill in the art at the time of the invention could have converted the volumetric flow rates to a volumetric ratio, which overlap with the instant claimed range of wherein a ratio of the hydrogen gas to the oxygen [[gas]] is about 1 vol. % to about 100 vol.% of the hydrogen gas to the oxygen [[gas]]. 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, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results. In this case, the H2O2 of ZOPE being replaced with the hydrogen gas and oxygen gas of SHANKAR to obtain the predictable result of hydrogen and oxygen ions being applied to the surface.
As for claim 5, ZOPE is silent on a hydrogen gas to an oxygen gas.
SHANKAR teaches “The hydrogen and oxygen gas in the desired ratio may be introduced to the chamber at any suitable flow rate. In a preferred embodiment for both 200 and 300 mm wafers, the flow rates of hydrogen ranges between about 100 sccm and 2000 sccm while the flow rate of oxygen varies between 50 sccm and 500 sccm” (column 7, lines 16-21). It is expected that a person of ordinary skill in the art at the time of the invention could have converted the volumetric flow rates to a volumetric ratio, which overlap with the instant claimed range of wherein the ratio of the hydrogen gas to the oxygen [[gas]] is about 1 vol. % to about 90 vol.% of the hydrogen gas to the oxygen [[gas]]. 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, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results. In this case, the H2O2 of ZOPE being replaced with the hydrogen gas and oxygen gas of SHANKAR to obtain the predictable result of hydrogen and oxygen ions being applied to the surface.
As for claim 6, ZOPE is silent on an oxygen gas, however, when combined with SHANKAR as shown in the rejection of claim 1 and 4, it would be obvious to use a mixture of hydrogen and oxygen.
ZOPE further teaches a "mixture may include at least a hydrogen containing gas" implies that there can be multiple hydrogen containing gases, such as H2 and H2O, provided in any mixture and producing a plasma from those gases inherently produces radicals such that wherein introducing the hydrogen gas and the oxygen gas from the remote plasma source to the processing chamber comprises introducing a treatment radical comprising a hydrogen radical, an oxygen radical, a hydroxide radical, or a combination thereof from the remote plasma source to the processing chamber. A reference which is silent about a claimed invention's features is inherently anticipatory if the missing feature is necessarily present in that which is described in the reference. lnherency is not established by probabilities or possibilities. In re Robertson, 49 USPQ2d 1949 (1999).
As for claim 7, ZOPE is silent on an oxygen gas, however, when combined with SHANKAR as shown in the rejection of claim 1 and 4, it would be obvious to use a mixture of hydrogen and oxygen.
ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5) and "The pre-treatment gas mixture may be supplied from a remote plasma source, such as the remote plasma source 141 coupled to the metal deposition processing chamber 150" (paragraph 54). A "mixture may include at least a hydrogen containing gas" implies that there can be multiple hydrogen containing gases, such as H2 and H2O, provided in any mixture and producing a plasma from those gases inherently produces radicals such that wherein the treatment radical comprises the hydrogen radical. A reference which is silent about a claimed invention's features is inherently anticipatory if the missing feature is necessarily present in that which is described in the reference. lnherency is not established by probabilities or possibilities. In re Robertson, 49 USPQ2d 1949 (1999).
As for claim 8, ZOPE is silent on an oxygen gas, however, when combined with SHANKAR as shown in the rejection of claim 1 and 4, it would be obvious to use a mixture of hydrogen and oxygen.
ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5) and "The pre-treatment gas mixture may be supplied from a remote plasma source, such as the remote plasma source 141 coupled to the metal deposition processing chamber 150" (paragraph 54). A "mixture may include at least a hydrogen containing gas" implies that there can be multiple hydrogen containing gases, such as H2 and H2O, provided in any mixture and producing a plasma from those gases inherently produces radicals such that wherein the treatment radical comprises the oxygen radical. A reference which is silent about a claimed invention's features is inherently anticipatory if the missing feature is necessarily present in that which is described in the reference. lnherency is not established by probabilities or possibilities. In re Robertson, 49 USPQ2d 1949 (1999).
As for claim 9, ZOPE is silent on an oxygen gas, however, when combined with SHANKAR as shown in the rejection of claim 1 and 4, it would be obvious to use a mixture of hydrogen and oxygen.
ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5) and "The pre-treatment gas mixture may be supplied from a remote plasma source, such as the remote plasma source 141 coupled to the metal deposition processing chamber 150" (paragraph 54). A "mixture may include at least a hydrogen containing gas" implies that there can be multiple hydrogen containing gases, such as H2 and H2O, provided in any mixture and producing a plasma from those gases inherently produces radicals such that wherein the treatment radical comprises the hydroxide radical. A reference which is silent about a claimed invention's features is inherently anticipatory if the missing feature is necessarily present in that which is described in the reference. lnherency is not established by probabilities or possibilities. In re Robertson, 49 USPQ2d 1949 (1999).
As for claim 21, ZOPE teaches “The deposition process may efficiently improve deposited film step coverage, conformality, and continuity and uniformity across the substrate, thereby improving the overall film properties formed across the substrate” (paragraph 28, lines 3-7), i.e. wherein the passivation layer is formed conformally over the surface of the substrate, the surface of the lower dielectric material, and the surface of the upper dielectric material.
As for claim 22, ZOPE teaches “Further, the substrate can include any other materials such as metal nitrides and metal alloys, depending on the application” (paragraph 24, lines 18-19), i.e. wherein the surface of the substrate comprises a metal material.
As for claim 23, ZOPE is silent on wherein the remote plasma source comprises a first radical generator and a second radical generator, and wherein the hydrogen gas is provided through the first radical generator and the oxygen is provided through the second radical generator.
LUBOMIRSKY teaches “One or more remote plasma system (RPS) units 201 may optionally be included in the system, and may process a first and second gas which then may travel through gas inlet assembly 205… The process gases may be excited within the RPS units 201 prior to entering the first plasma region 215.” (paragraph 33, lines 8-21), i.e. wherein multiple RPS units for each precursor gas, i.e. radical generators, are a known alternative to a single radical generator.
It is a prima facie case of obviousness to substitute one known element for another to obtain predictable results. In this case, the single radical generator, i.e. plasma generator of ZOPE being replaced with the hydrogen gas and oxygen gas RPS units of LUBOMIRKSY such that it includes wherein the remote plasma source comprises a first radical generator and a second radical generator, and wherein the hydrogen gas is provided through the first radical generator and the oxygen is provided through the second radical generator to obtain the predictable result of hydrogen and oxygen ions being applied to the surface.
Claim(s) 11, 15-16, 18-19 are rejected under 35 U.S.C. 103 as being unpatentable over by Zope et al. US PGPub 201310260555 hereinafter ZOPE further in view of Shankar et al. US Patent Number 7,727,906 hereinafter SHANKAR.
As for claim 11, ZOPE teaches "Methods for depositing a contact metal layer in contact structures of a semiconductor device are provided" (abstract, lines 1-2) and "Embodiments of the present invention provide gapfill utilizing metallic CVD processes (e.g., cobalt CVD processes) resulting in a potential low contact resistance (Re) onematerial solution for contact fill" (paragraph 22, lines 1-4), i.e. A method of depositing a gap-fill material on a semiconductor substrate.
ZOPE teaches "Prior to transferring the substrate 402 into the metal deposition processing chamber described at block 310, a pre-cleaning process is optionally performed to treat the substrate surfaces 411, sidewalls 412 and bottoms 414 of the openings 406 to remove native oxides or other sources of contaminants. Removal of native oxides or other sources of contaminants from the substrate 402 may provide a low contact resistance surface to form a good contact surface for forming a contact metal layer" (paragraph 46), i.e. performing a preclean process on a surface of a contact structure.
ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5), and "The pretreatment gas mixture may be supplied from a remote plasma source, such as the remote plasma source 141 coupled to the metal deposition processing chamber 150" (paragraph 54), i.e. by introducing a hydrogen gas and an oxygen gas from a remote plasma source to a processing chamber.
ZOPE shows in Fig. 7 A and teaches "A silicon containing layer 404 is formed on the substrate 402 having openings 406 formed therein with high aspect ratios, such as aspect ratios greater than 10: 1, for example about greater than 20: 1. The openings 406 (which may be a contact opening, contact via, contact trench, contact channel or the like) are formed in the device structure 408 and have sidewalls 412 and a bottom 414 which form an open channel to expose the underlying silicon containing layer 404. The silicon containing layer 404 may include any suitable layers such as a single silicon layer or a multiple layer film stack having at least one silicon containing layer formed therein" (paragraph 44, lines 1-12) i.e. which is a range that includes the contact structure comprises a feature formed in a surface of the semiconductor substrate; the feature comprises an opening that is defined by a substrate, a lower dielectric material disposed over the substrate, and an upper dielectric material disposed over the lower dielectric material; and the passivation layer is formed over the substrate, the lower dielectric material, and the upper dielectric material. Examiner notes that as currently written the claims do not distinguish between a substrate made of a singular material or a substrate made of multiple layers.
ZOPE further teaches "In one or more embodiments, the deposition method passivates dangling silicon bonds" (paragraph 60, lines 4-5), i.e. forming a passivation layer.
ZOPE teaches "At block 320, prior to deposition of a contact metal layer on the substrate 402, but after the substrate 402 is provided in the metal deposition processing chamber 150 at block 310, a pretreatment process may be performed to pretreat the substrate surface 411, thus, forming a treated surface region 410 on the surface 411, sidewalls 412 and bottoms 414 of the openings 406 in the silicon containing layer 404, as shown in FIG. 4B" (paragraph 52, lines 1-8), i.e. the passivation layer on the surface of the contact structure.
ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5), and "The pretreatment gas mixture may be supplied from a remote plasma source, such as the remote plasma source 141 coupled to the metal deposition processing chamber 150" (paragraph 54), i.e. by introducing a first gas comprising hydrogen gas or an oxygen gas and a second gas comprising water from a remote plasma source to a processing chamber.
ZOPE teaches "The contact metal layer 420 may be deposited using a multi-step deposition process comprising multiple cycles of performing a cyclic metal deposition process to deposit the contact metal layer 420 followed by annealing the contact metal layer 420. In certain embodiments, the thickness of the contact metal layer 420 should be less than 50% of the feature diameter (critical dimension) of the smallest feature to be filled. For example, the cyclic metal deposition process is performed to partially fill a feature to less than half of the feature diameter followed by an anneal process. The cyclic deposition process followed by an anneal would then be repeated to deposit until the contact metal layer 420 achieved a predetermined thickness. In an alternative embodiment, the contact metal layer 420 may be deposited to completely fill the feature in a single, non-cyclic deposition process" (paragraph 59, lines 1-15), i.e. depositing a metal gap-fill material over a portion of the passivation layer to fill the feature formed in the surface of the semiconductor substrate.
As for claim 15, ZOPE is silent on an oxygen gas, however, when combined with SHANKAR as shown in the rejection of claim 1 and 4, it would be obvious to use a mixture of hydrogen and oxygen.
ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5). A "mixture may include at least a hydrogen containing gas" implies that there can be multiple hydrogen containing gases, such as H2 and H2O, provided in any mixture such that it overlaps with wherein the ratio of the first gas to the second gas is about 1 vol. % to about 90 vol.% of the first gas to the second gas. 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); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
As for claim 16, ZOPE is silent on an oxygen gas, however, when combined with SHANKAR as shown in the rejection of claim 1 and 4, it would be obvious to use a mixture of hydrogen and oxygen.
ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5) and "The pre-treatment gas mixture may be supplied from a remote plasma source, such as the remote plasma source 141 coupled to the metal deposition processing chamber 150" (paragraph 54). A "mixture may include at least a hydrogen containing gas" implies that there can be multiple hydrogen containing gases, such as H2 and H2O, provided in any mixture and producing a plasma from those gases inherently produces radicals such that wherein introducing the first gas and the second gas from the remote plasma source to the processing chamber comprises introducing a treatment radical comprising a hydrogen radical, an oxygen radical, a hydroxide radical, or a combination thereof from the remote plasma source to the processing chamber. A reference which is silent about a claimed invention's features is inherently anticipatory if the missing feature is necessarily present in that which is described in the reference. lnherency is not established by probabilities or possibilities. In re Robertson, 49 USPQ2d 1949 (1999).
As for claim 18, ZOPE is silent on an oxygen gas, however, when combined with SHANKAR as shown in the rejection of claim 1 and 4, it would be obvious to use a mixture of hydrogen and oxygen.
ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5) and "The pre-treatment gas mixture may be supplied from a remote plasma source, such as the remote plasma source 141 coupled to the metal deposition processing chamber 150" (paragraph 54). A "mixture may include at least a hydrogen containing gas" implies that there can be multiple hydrogen containing gases, such as H2 and H2O, provided in any mixture and producing a plasma from those gases inherently produces radicals such that wherein the treatment radical comprises the oxygen radical. A reference which is silent about a claimed invention's features is inherently anticipatory if the missing feature is necessarily present in that which is described in the reference. lnherency is not established by probabilities or possibilities. In re Robertson, 49 USPQ2d 1949 (1999).
As for claim 19, ZOPE further teaches "In one embodiment, a pre-treatment gas mixture may be supplied into the metal deposition processing chamber 150 to alter the surface properties of the substrate 402 prior to the contact metal deposition process. In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2, H2O, H2O2 or the like" (paragraph 53, lines 1-5) and "The pre-treatment gas mixture may be supplied from a remote plasma source, such as the remote plasma source 141 coupled to the metal deposition processing chamber 150" (paragraph 54). A "mixture may include at least a hydrogen containing gas" implies that there can be multiple hydrogen containing gases, such as H2 and H2O, provided in any mixture and producing a plasma from those gases inherently produces radicals such that wherein the treatment radical comprises the hydroxide radical. A reference which is silent about a claimed invention's features is inherently anticipatory if the missing feature is necessarily present in that which is described in the reference. lnherency is not established by probabilities or possibilities. In re Robertson, 49 USPQ2d 1949 (1999).
“In one embodiment, the pre-treatment gas mixture may include at least a hydrogen containing gas, such as H2 , H2O, H2O2 , or the like. An inert gas, such as Ar, He, Kr, and the like, may also be supplied into the pre-treatment gas mixture” (paragraph 53, lines 4-8) and “The hydrogen containing gas supplied in the pretreatment gas mixture may be flowed into the processing chamber 150 at a rate between about 400 sccm to about 4000 sccm and the inert gas supplied in the pretreatment gas mixture may be flowed at a rate between about 200 sccm and about 2000 sccm” (paragraph 55, lines 11-15), i.e. a range that overlaps with wherein the second gas is a mixture further comprising an inert carrier gas, and wherein the mixture is between about 0.5 vol. % and about 30 vol. % water.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); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
Claim(s) 10 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Zope et al. US PGPub 201310260555 hereinafter ZOPE further in view of Lubomirsky et al. US PGPub2014/0227881 hereinafter LUBOMIRSKY and Shankar et al. US Patent Number 7,727,906 hereinafter SHANKAR as applied to claim 1 above, and further in view of Mani et al. US PG Pub 200910233453 hereinafter MANI.
As for claim 10, ZOPE is silent on the thickness of the passivation layer.
ZOPE does teach "In certain embodiments, the substrate surface 411 may have some weak or residual dangling bonding structures of Si-F, N-F, H-F, and Si-N on the substrate surface left from the optional pre-cleaning process previously performed on the substrate 402. The dangling bonds may undesirably and adversely obstruct absorption or adherence of metallic atoms deposited on the substrate surface in the subsequent contact metal deposition process. Thus, the pretreatment process at block 320 may be performed to efficiently alter the surface bonding structure of the surface 411 of the silicon containing layer 404, thereby providing a surface having a good absorption ability to promote adherence of metallic atoms provided from the subsequent contact metal deposition process" (paragraph 52, lines 8-21 ), i.e. where the pretreatment layer serves to cover the surface of the substrate.
MANI teaches "Methods of fabricating an oxide layer on a semiconductor substrate are provided herein. The oxide layer may be formed over an entire structure disposed on the substrate, or selectively formed on a non-metal containing layer with little or no oxidation of an exposed metal-containing layer" (abstract, lines 1-5).
MANI teaches "The methods disclosed herein may be performed in a variety of process chambers, including but not limited to decoupled plasma oxidation chambers, rapid and/or remote plasma oxidation chambers, and/or plasma immersion ion implantation chambers" (paragraph 9, lines 7-11) and "In some embodiments, a method of forming an oxide layer on a semiconductor substrate includes providing a substrate to be oxidized on a substrate support in a process chamber; and forming a plasma in the process chamber from a process gas to form an oxide layer on the substrate, the process gas comprising a hydrogen-containing gas, an oxygen- containing gas, and at least one of a nitridizing gas ( e.g., a nitrogen-containing gas) or a supplemental oxidizing gas (e.g., a supplemental oxygen-containing gas)" (paragraph 10), i.e. a remote plasma process of applying a coating from hydrogen containing gas and oxygen containing gas on a semiconductor substrate to form a conformal coating on the desired surfaces.
MANI further teaches "The hydrogen-containing gas may include hydrogen (H2) and/or water vapor (H2O). The oxidizing gas may include oxygen (O2) and/or water vapor (H2O) ... The supplemental oxidizing gas may include ozone (O3) and hydrogen peroxide (H2O2), and combinations thereof. In the embodiments described herein, water vapor (H2O) may be used as either the hydrogen-containing gas or the oxidizing gas, but not both" (paragraph 33, lines 9-18).
MANI further teaches "The oxide layer (e.g., 230, 330) may be formed to a thickness of between about 5-100 Angstroms. The process 100 may provide growth rates of oxide films between about 7-50 Angstroms per minute, or at least about 25 Angstroms per minute" (paragraph 42, lines 1-5), i.e. a range that overlaps with forming the passivation layer on the surface of the contact structure comprises forming a thickness of about 10 A to about 20 A. 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); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
MANI teaches "Upon forming the oxide layer (e.g., 230, 330) to a desired thickness over the film stack (e.g., 240, 340), the process 100 ends" (paragraph 43, lines 1-3).
It would have been obvious to one of ordinary skill in the art before the effective filing date to include a range that overlaps with forming the passivation layer on the surface of the contact structure comprises forming a thickness of about 10 A to about 20 A in the process of ZOPE because MANI teaches that such a thickness can form a conformal layer over an underlying structure.
In the alternative, it would have been obvious to one of ordinary skill in the art before the effective filing date to design the thickness such that the desired layer of material is applied over the dangling bonds is achieved. Discovery of optimum value of result effective variable in known process is ordinarily within the skill of the art. In re Boesch, CCPA 1980, 617 F.2d 272, 205 USPQ215.
As for claim 20, ZOPE is silent on the thickness of the passivation layer.
ZOPE does teach "In certain embodiments, the substrate surface 411 may have some weak or residual dangling bonding structures of Si-F, N-F, H-F, and Si-N on the substrate surface left from the optional pre-cleaning process previously performed on the substrate 402. The dangling bonds may undesirably and adversely obstruct absorption or adherence of metallic atoms deposited on the substrate surface in the subsequent contact metal deposition process. Thus, the pretreatment process at block 320 may be performed to efficiently alter the surface bonding structure of the surface 411 of the silicon containing layer 404, thereby providing a surface having a good absorption ability to promote adherence of metallic atoms provided from the subsequent contact metal deposition process" (paragraph 52, lines 8-21 ), i.e. where the pretreatment layer serves to cover the surface of the substrate.
MANI teaches "Methods of fabricating an oxide layer on a semiconductor substrate are provided herein. The oxide layer may be formed over an entire structure disposed on the substrate, or selectively formed on a non-metal containing layer with little or no oxidation of an exposed metal-containing layer" (abstract, lines 1-5).
MANI teaches "The methods disclosed herein may be performed in a variety of process chambers, including but not limited to decoupled plasma oxidation chambers, rapid and/or remote plasma oxidation chambers, and/or plasma immersion ion implantation chambers" (paragraph 9, lines 7-11) and "In some embodiments, a method of forming an oxide layer on a semiconductor substrate includes providing a substrate to be oxidized on a substrate support in a process chamber; and forming a plasma in the process chamber from a process gas to form an oxide layer on the substrate, the process gas comprising a hydrogen-containing gas, an oxygen- containing gas, and at least one of a nitridizing gas ( e.g., a nitrogen-containing gas) or a supplemental oxidizing gas (e.g., a supplemental oxygen-containing gas)" (paragraph 10), i.e. a remote plasma process of applying a coating from hydrogen containing gas and oxygen containing gas on a semiconductor substrate to form a conformal coating on the desired surfaces.
MANI further teaches "The hydrogen-containing gas may include hydrogen (H2) and/or water vapor (H2O). The oxidizing gas may include oxygen (O2) and/or water vapor (H2O) ... The supplemental oxidizing gas may include ozone (O3) and hydrogen peroxide (H2O2), and combinations thereof. In the embodiments described herein, water vapor (H2O) may be used as either the hydrogen-containing gas or the oxidizing gas, but not both" (paragraph 33, lines 9-18).
MANI further teaches "The oxide layer (e.g., 230, 330) may be formed to a thickness of between about 5-100 Angstroms. The process 100 may provide growth rates of oxide films between about 7-50 Angstroms per minute, or at least about 25 Angstroms per minute" (paragraph 42, lines 1-5), i.e. a range that overlaps with forming the passivation layer on the surface of the contact structure comprises forming a thickness of about 10 A to about 20 A. 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); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d, 1362, 1365-66 (Fed. Cir. 1997). See MPEP 2144.05.
MANI teaches "Upon forming the oxide layer (e.g., 230, 330) to a desired thickness over the film stack (e.g., 240, 340), the process 100 ends" (paragraph 43, lines 1-3).
It would have been obvious to one of ordinary skill in the art before the effective filing date to include a range that overlaps with forming the passivation layer on the surface of the contact structure comprises forming a thickness of about 10 A to about 20 A in the process of ZOPE because MANI teaches that such a thickness can form a conformal layer over an underlying structure.
In the alternative, it would have been obvious to one of ordinary skill in the art before the effective filing date to design the thickness such that the desired layer of material is applied over the dangling bonds is achieved. Discovery of optimum value of result effective variable in known process is ordinarily within the skill of the art. In re Boesch, CCPA 1980, 617 F.2d 272, 205 USPQ215.
Claim(s) 24 is rejected under 35 U.S.C. 103 as being unpatentable over Zope et al. US PGPub 201310260555 hereinafter ZOPE further in view of Lubomirsky et al. US PGPub2014/0227881 hereinafter LUBOMIRSKY and Shankar et al. US Patent Number 7,727,906 hereinafter SHANKAR as applied to claim 1 above, and further in view of Chinn et al. US PGPub 2003/0166342 hereinafter CHINN.
As for claim 24, ZOPE, LUBOMIRSKY and SHANKAR are silent on the plasma density.
CHINN teaches “The treatment oxidizes the surfaces, which are then reacted with hydrogen to form bonded OH groups on the surfaces. The hydrogen source may be present as part of the plasma source gas, so that the bonded OH groups are created during treatment of the surfaces with the plasma” (abstract, lines 6-11).
CHINN teaches “Typically, the plasma used to treat the MEMS structure surfaces is an externally generated plasma. The use of an external plasma generation source provides the ability to control the plasma to exhibit a low, yet uniform, ion density, preventing undesirable etching and/or ion bombardment of the MEMS structure surface during oxidation of the surface. The plasma typically has an ion density of about 1x1011 e-/cm3 to about 1x1012 e-/cm3 at the plasma generation source; however, the ion density of the plasma is permitted to drop off to about 1x107 e-/cm3 to about 1x108 e-/cm3 by the time the plasma reaches the substrate surface. One skilled in the art to which the present invention belongs will be able to control the holding time or stabilization time of the plasma prior to contacting the substrate surface in order to ensure that the plasma density at the substrate surface is within a desired range” (paragraph 66).
It would have been obvious to one of ordinary skill in the art before the effective filing date to design the plasma density in the remote plasma source such that the desired ion density at the substrate is achieved. Discovery of optimum value of result effective variable in known process is ordinarily within the skill of the art. In re Boesch, CCPA 1980, 617 F.2d 272, 205 USPQ215.
Claim(s) 25 are rejected under 35 U.S.C. 103 as being unpatentable over by Zope et al. US PGPub 201310260555 hereinafter ZOPE and of Shankar et al. US Patent Number 7,727,906 hereinafter SHANKAR as applied to claim 11, further in view of Lubomirsky et al. US PGPub2014/0227881 hereinafter LUBOMIRSKY.
As for claim 25, ZOPE is silent on through an ion filter.
LUBOMIRSKY teaches “An exemplary system may include a chamber configured to contain a semiconductor substrate in a processing region of the chamber. The system may include a first remote plasma unit fluidly coupled with a first access of the chamber and configured to deliver a first precursor into the chamber through the first access” (abstract, lines 1-6) and “Each substrate processing chamber 108-fj; can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, preclean, degas, orientation, and other substrate processes” (paragraph 31, lines 11-17).
LUBOMIRSKY teaches “An ion suppressor may be used to filter ions from the plasma effluents during transit from the remote plasma region to the substrate processing region in embodiments of the technology. The ion suppressor functions to reduce or eliminate ionically charged species traveling from the plasma generation region to the substrate. Uncharged neutral and radical species may pass through the openings in the ion suppressor to react at the substrate. It should be noted that complete elimination of ionically charged species in the reaction region surrounding the substrate is not always the desired goal. In many instances, ionic species are required to reach the substrate in order to perform the etch and/or deposition process. In these instances, the ion suppressor helps control the concentration of ionic species in the reaction region at a level that assists the process. In disclosed embodiments the upper plate of the gas distribution assembly may include an ion suppressor.” (paragraph 111), i.e. providing precursors through an ion filter.
It would have been obvious to one of ordinary skill in the art to include wherein introducing the first gas and the second gas from a remote plasma source further comprises flowing the first gas and the second gas through an ion filter in the process of ZOPE because LUBOMIRSKY teaches the ion filters controls the concentration of ionic species in a deposition process to a specific level to assist the process.
Response to Arguments
Applicant’s arguments with respect to claim(s) 1-2, 4-11, 15-16, 18-19, and 21-26 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
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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/KRISTEN A DAGENAIS/Examiner, Art Unit 1717
/Dah-Wei D. Yuan/Supervisory Patent Examiner, Art Unit 1717
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