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 .
Claims 24, 27-29, 32-34, 36 and 41-48 are pending
Claims 1-23, 25-26, 30-31, 35 and 37-40 have been canceled
Claims 24 and 34 are amended
Claims 41-48 are new
.
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) 24, 27-29 and 32-33 are rejected under 35 U.S.C. 103 as being unpatentable over Kiehlbauch et al. US 2009/0275205 (US’205) in view of Toda et al. US 2015/0380268 (US’268) and Visintin et al. US 2008/0125342 (US’342).
Regarding claims 24, US’205 teaches a composition comprising:
hydrogen fluoride vapor (a gaseous chemistry including HF to remove silicon oxide, para. 15);
a mixture, the mixture comprising and an additive consisting of a base (the gaseous mixture includes a volatile amine, volatile amine may be NH3 or an alkylated derivative or alkylated analog of NH3, such as methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, isopropyl amine, dipropyl amine, n-propyl amine, n-butyl amine, sec-butyl amine, t-butyl amine, or combinations thereof, para. 15);
and a carrier gas (The gaseous mixture may, optionally, include an inert carrier gas).
US’205 does not teach the based comprising a heteroaromatic cyclic compound the mixture comprises an alcohol and wherein the additive comprises 0.01 wt % to 1 wt % of the mixture of the alcohol and the additive.
US’268 teaches an etching composition for selectively etching silicon oxide including HF gas and an alcohol. a volume ratio (flow rate ratio) of the alcohol gas to the total sum of F2 gas+HF gas+alcohol gas may fall within a range from 10 to 85 volume %. The alcohol gas tends to increase the etching selectivity of the SiO2 film with respect to the SiN film (para. 44-53). Therefore, US’268 teaches adding an alcohol to a gaseous treatment composition for silicon oxide semiconductor processing for the purposes of controlling the selectivity of the treatment between silicon oxide and silicon nitride. US’205 further teaches by way of non-limiting example, a volumetric flow rate ratio of the HF to the volatile amine in the gaseous mixture may be within a range of from approximately 1/1 to approximately 1/2. The flow range of NH3 and HF may be in the range of approximately 20 sccm to approximately 50 sccm. If an inert carrier gas is present, the gaseous mixture of the HF and the volatile amine may account for from approximately 0.05% by volume to approximately 20% by volume of the total volume of the gaseous mixture and the inert carrier gas. The combination of amine and HF react with each other and the silicon oxide to breakdown the silicon oxide, thereby etching the silicon oxide to create a product that can be easily removed for the surface (para. 17-18.) Therefore, US’205 teaches using a relatively small amount of additive/amine relative to the composition as a whole and US’268 teaches using large amount of alcohol relative to the HF content. As a result, the combined teachings of US’205 and US’268 teach one of ordinary skill in the art to control the amount of amine additive to be relatively small compared to the amount of alcohol for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride. Too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the composition of US’205 to include the mixture comprises an alcohol because US’268 teaches it can be added for the purposes of providing etch electivity between silicon oxide and silicon nitride and combining prior art elements according to known methods to yield predictable results is obvious, see MPEP 2141 III (A).
Further, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the modified composition of US’205 to include wherein the additive comprises 0.01 wt % to 1 wt % of the mixture of the alcohol and the additive because the combination of US’205 and US’268 teaches to control the amount of amine additive to be relatively small compared to the amount of alcohol for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride, too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity and it is not inventive to discover the optimum or workable ranges by routine experimentation, see MPEP 2144.05.
The modified composition of US’205 does not teach the based comprising a heteroaromatic cyclic compound.
US’342 teaches a removal composition and process for removing silicon-containing layers from a microelectronic device. The removal composition selectively removes layers including, but not limited to, silicon oxide (abstract). Etchants are added to react with the silicon-containing material and assist in the removal of same from the microelectronic device. Etchants contemplated for use include fluorides and amines, not limited to: hydrogen fluoride (HF) an extensive list of amines. The amines listed include many of the same alkyl amine taught by US’205 as well as an extensive list of heteroaromatic cyclic amines for example pyrrole, triazoles and pyridine (para. 68). Amines may be added to increase the oxide etch rates in the presence of the fluoride etchant source. The speciation between the acid (A-H) and base (B) changes, depending on the amine basic strength. The intermediate complex A-H--B strongly influences the rate of various oxide materials. As such, we can selectively etch one oxide material over the other or adjust the amine concentration so that both or all of the oxide materials have similar etch rates. Preferably, the amine component comprises 1-methylimidazole (a heteroaromatic cyclic amine) (para. 71). Therefore, US’342 teaches that amines, including the category of heteroaromatic cyclic amines, are a well understood class of compounds, whose chemical reactions are well understood with regard to etching of oxides when combined with HF and that they can be selected from known alternatives to tune the etch selectivity.
It would have been obvious to one of ordinary skill in the art before the effective fling date of the claimed invention to modify the modified composition of US’205 to include the based comprising a heteroaromatic cyclic compound because US’342 teaches that amines, including the category of heteroaromatic cyclic amines, are a well understood class of compounds, whose chemical reactions are well understood with regard to etching of oxides when combined with HF and that they can be selected from known alternatives to tune the etch selectivity and simple substitution of one known element for another to obtain predictable results is obvious, see MPEP 2141 III (B).
Regarding claims 27-28, the modified composition of US’205 teaches the composition of claim 24. The modified composition further teaches wherein the heteroaromatic cyclic compound contains at least one nitrogen atom, with regard to claim 27 and wherein the heteroaromatic cyclic compound consists of pyridine, with regard to claim 28 (US’342 teaches pyridine as a known amine, para. 71).
Regarding claim 29, the modified composition of US’205 teaches the composition of claim 24. As discussed above US’205 teaches using a relatively small amount of additive/amine relative to the composition as a whole and US’268 teaches using large amount of alcohol relative to the HF content. As a result, the combined teachings of US’205 and US’268 teach one of ordinary skill in the art to control the amount of amine additive to be relatively small compared to the amount of alcohol and carrier gas for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride. Too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity.
it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the modified composition of US’205 to include wherein the additive is in a range from 0.1 parts per million (ppm) to 2000 ppm (mass) of the composition because the combination of US’205 and US’268 teaches to control the amount of amine additive to be relatively small compared to the amount of alcohol and carrier gas for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride, too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity and it is not inventive to discover the optimum or workable ranges by routine experimentation, see MPEP 2144.05.
Regarding claim 32, the modified composition of US’205 teaches the composition of claim 24. The modified composition further teaches wherein the alcohol is selected from a group consisting of methanol (US’268, para. 39, methanol may be used as the alcohol).
Regarding claim 33, the modified composition of US’205 teaches the composition of claim 24. US’268 further teaches e N2 gas, is a known inert gas such as an Ar gas or the like that may be used for HF gaseous etching (para. 22). US’205 teaches the gaseous mixture may, optionally, include an inert carrier gas, such as argon (para. 15).
It would have been obvious to one of ordinary skill in the art before the effective fling date of the claimed invention to modify the modified composition of US’205 to include wherein the carrier gas consists of molecular nitrogen because US’268 teaches it is a known alternative inert gas and simple substitution of one known element for another to obtain predictable results is obvious, see MPEP 2141 III (B).
Claim(s) 34, 36 and 43 are rejected under 35 U.S.C. 103 as being unpatentable over Kiehlbauch et al. US 2009/0275205 (US’205) in view of Toda et al. US 2015/0380268 (US’268).
Regarding claims 34, US’205 teaches a composition comprising:
hydrogen fluoride vapor (a gaseous chemistry including HF to remove silicon oxide, para. 15);
and a mixture comprising and an additive (the gaseous mixture includes a volatile amine, volatile amine may be NH3 or an alkylated derivative or alkylated analog of NH3, such as methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, isopropyl amine, dipropyl amine, n-propyl amine, n-butyl amine, sec-butyl amine, t-butyl amine, or combinations thereof, para. 15);
US’205 does not teach the mixture comprises an alcohol and wherein the additive comprises 0.01 wt % to 1 wt % of the mixture of the alcohol vapor and the additive.
US’268 teaches an etching composition for selectively etching silicon oxide including HF gas and an alcohol. a volume ratio (flow rate ratio) of the alcohol gas to the total sum of F2 gas+HF gas+alcohol gas may fall within a range from 10 to 85 volume %. The alcohol gas tends to increase the etching selectivity of the SiO2 film with respect to the SiN film (para. 44-53). Therefore, US’268 teaches adding an alcohol to a gaseous treatment composition for silicon oxide semiconductor processing for the purposes of controlling the selectivity of the treatment between silicon oxide and silicon nitride. US’205 further teaches by way of non-limiting example, a volumetric flow rate ratio of the HF to the volatile amine in the gaseous mixture may be within a range of from approximately 1/1 to approximately 1/2. The flow range of NH3 and HF may be in the range of approximately 20 sccm to approximately 50 sccm. If an inert carrier gas is present, the gaseous mixture of the HF and the volatile amine may account for from approximately 0.05% by volume to approximately 20% by volume of the total volume of the gaseous mixture and the inert carrier gas. The combination of amine and HF react with each other and the silicon oxide to breakdown the silicon oxide, thereby etching the silicon oxide to create a product that can be easily removed for the surface (para. 17-18.) Therefore, US’205 teaches using a relatively small amount of additive/amine relative to the composition as a whole and US’268 teaches using large amount of alcohol relative to the HF content. As a result, the combined teachings of US’205 and US’268 teach one of ordinary skill in the art to control the amount of amine additive to be relatively small compared to the amount of alcohol for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride. Too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the composition of US’205 to include the mixture comprises an alcohol because US’268 teaches it can be added for the purposes of providing etch electivity between silicon oxide and silicon nitride and combining prior art elements according to known methods to yield predictable results is obvious, see MPEP 2141 III (A).
Further, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the modified composition of US’205 to include wherein the additive comprises 0.01 wt % to 1 wt % of the mixture of the alcohol vapor and the additive because the combination of US’205 and US’268 teaches to control the amount of amine additive to be relatively small compared to the amount of alcohol for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride, too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity and it is not inventive to discover the optimum or workable ranges by routine experimentation, see MPEP 2144.05.
Regarding claim 36, the modified composition of US’205 teaches the composition of claim 34. US’205 further teaches if an inert carrier gas is present, the gaseous mixture of the HF and the volatile amine may account for from approximately 0.05% by volume to approximately 20% by volume of the total volume of the gaseous mixture and the inert carrier gas (para. 18). Therefore, the modified composition of US’205 includes a carrier gas having a gas vol% of 80 vol. % to 99.5 vol. %, which overlaps applicants claim range.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to select applicants claimed range of the carrier gas in a range from 92.5% to 99% volume of the composition because US’205 teaches overlapping ranges for amount of carrier gas, and in the case where the claimed ranges overlap or lie inside ranges disclosed by the prior art a prima facie case of obviousness exists, see MPEP 2144.05.
Regarding claim 43, the modified composition of US’205 teaches the composition of claim 34. The modified composition further teaches wherein the alcohol vapor is selected from a group consisting of methanol (US’268, para. 39, methanol may be used as the alcohol).
Claim(s) 44 is rejected under 35 U.S.C. 103 as being unpatentable over US’205 in view of US’268 as applied to claim 34 above, and further in view of Visintin et al. US 2008/0125342 (US’342).
Regarding claim 44, the modified composition of US’205 teaches the composition of claim 34.
The modified composition of US’205 does not teach wherein the additive comprises pyridine.
US’342 teaches a removal composition and process for removing silicon-containing layers from a microelectronic device. The removal composition selectively removes layers including, but not limited to, silicon oxide (abstract). Etchants are added to react with the silicon-containing material and assist in the removal of same from the microelectronic device. Etchants contemplated for use include fluorides and amines, not limited to: hydrogen fluoride (HF) an extensive list of amines. The amines listed include many of the same alkyl amine taught by US’205 as well as an extensive list of heteroaromatic cyclic amines for example pyrrole, triazoles and pyridine (para. 68). Amines may be added to increase the oxide etch rates in the presence of the fluoride etchant source. The speciation between the acid (A-H) and base (B) changes, depending on the amine basic strength. The intermediate complex A-H--B strongly influences the rate of various oxide materials. As such, we can selectively etch one oxide material over the other or adjust the amine concentration so that both or all of the oxide materials have similar etch rates. Preferably, the amine component comprises 1-methylimidazole (a heteroaromatic cyclic amine) (para. 71). Therefore, US’342 teaches that amines, including the category of heteroaromatic cyclic amines, are a well understood class of compounds, whose chemical reactions are well understood with regard to etching of oxides when combined with HF and that they can be selected from known alternatives to tune the etch selectivity.
It would have been obvious to one of ordinary skill in the art before the effective fling date of the claimed invention to modify the modified composition of US’205 to include wherein the additive comprises pyridine because US’342 teaches that amines, including the category of heteroaromatic cyclic amines which pyridine is an example of, are a well understood class of compounds, whose chemical reactions are well understood with regard to etching of oxides when combined with HF and that they can be selected from known alternatives to tune the etch selectivity and simple substitution of one known element for another to obtain predictable results is obvious, see MPEP 2141 III (B).
Claim(s) 41 and 45-46 are rejected under 35 U.S.C. 103 as being unpatentable over Kiehlbauch et al. US 2009/0275205 (US’205) in view of Toda et al. US 2015/0380268 (US’268) and Visintin et al. US 2008/0125342 (US’342).
Regarding claims 41, US’205 teaches a composition comprising:
hydrogen fluoride vapor (a gaseous chemistry including HF to remove silicon oxide, para. 15);
a mixture, the mixture comprising and an additive consisting of a base (the gaseous mixture includes a volatile amine, volatile amine may be NH3 or an alkylated derivative or alkylated analog of NH3, such as methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, isopropyl amine, dipropyl amine, n-propyl amine, n-butyl amine, sec-butyl amine, t-butyl amine, or combinations thereof, para. 15);
US’205 does not teach the based comprising a heteroaromatic cyclic compound the mixture comprises an alcohol vapor and wherein the additive is in a range from 0.1 parts per million (ppm) to 2000 ppm (mass) of the composition.
US’268 teaches an etching composition for selectively etching silicon oxide including HF gas and an alcohol. a volume ratio (flow rate ratio) of the alcohol gas to the total sum of F2 gas+HF gas+alcohol gas may fall within a range from 10 to 85 volume %. The alcohol gas tends to increase the etching selectivity of the SiO2 film with respect to the SiN film (para. 44-53). Therefore, US’268 teaches adding an alcohol to a gaseous treatment composition for silicon oxide semiconductor processing for the purposes of controlling the selectivity of the treatment between silicon oxide and silicon nitride. US’205 further teaches by way of non-limiting example, a volumetric flow rate ratio of the HF to the volatile amine in the gaseous mixture may be within a range of from approximately 1/1 to approximately 1/2. The flow range of NH3 and HF may be in the range of approximately 20 sccm to approximately 50 sccm. If an inert carrier gas is present, the gaseous mixture of the HF and the volatile amine may account for from approximately 0.05% by volume to approximately 20% by volume of the total volume of the gaseous mixture and the inert carrier gas. The combination of amine and HF react with each other and the silicon oxide to breakdown the silicon oxide, thereby etching the silicon oxide to create a product that can be easily removed for the surface (para. 17-18.) Therefore, US’205 teaches using a relatively small amount of additive/amine relative to the composition as a whole and US’268 teaches using large amount of alcohol relative to the HF content. As a result, the combined teachings of US’205 and US’268 teach one of ordinary skill in the art to control the amount of amine additive to be relatively small compared to the amount of alcohol for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride. Too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the composition of US’205 to include the mixture comprises an alcohol vapor because US’268 teaches it can be added for the purposes of providing etch electivity between silicon oxide and silicon nitride and combining prior art elements according to known methods to yield predictable results is obvious, see MPEP 2141 III (A).
Further, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the modified composition of US’205 to include wherein the additive is in a range from 0.1 parts per million (ppm) to 2000 ppm (mass) of the composition because the combination of US’205 and US’268 teaches to control the amount of amine additive to be relatively small compared to the amount of alcohol and other carrier gases present for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride, too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity and it is not inventive to discover the optimum or workable ranges by routine experimentation, see MPEP 2144.05.
The modified composition of US’205 does not teach the based comprising a heteroaromatic cyclic compound.
US’342 teaches a removal composition and process for removing silicon-containing layers from a microelectronic device. The removal composition selectively removes layers including, but not limited to, silicon oxide (abstract). Etchants are added to react with the silicon-containing material and assist in the removal of same from the microelectronic device. Etchants contemplated for use include fluorides and amines, not limited to: hydrogen fluoride (HF) an extensive list of amines. The amines listed include many of the same alkyl amine taught by US’205 as well as an extensive list of heteroaromatic cyclic amines for example pyrrole, triazoles and pyridine (para. 68). Amines may be added to increase the oxide etch rates in the presence of the fluoride etchant source. The speciation between the acid (A-H) and base (B) changes, depending on the amine basic strength. The intermediate complex A-H--B strongly influences the rate of various oxide materials. As such, we can selectively etch one oxide material over the other or adjust the amine concentration so that both or all of the oxide materials have similar etch rates. Preferably, the amine component comprises 1-methylimidazole (a heteroaromatic cyclic amine) (para. 71). Therefore, US’342 teaches that amines, including the category of heteroaromatic cyclic amines, are a well understood class of compounds, whose chemical reactions are well understood with regard to etching of oxides when combined with HF and that they can be selected from known alternatives to tune the etch selectivity.
It would have been obvious to one of ordinary skill in the art before the effective fling date of the claimed invention to modify the modified composition of US’205 to include the based comprising a heteroaromatic cyclic compound because US’342 teaches that amines, including the category of heteroaromatic cyclic amines, are a well understood class of compounds, whose chemical reactions are well understood with regard to etching of oxides when combined with HF and that they can be selected from known alternatives to tune the etch selectivity and simple substitution of one known element for another to obtain predictable results is obvious, see MPEP 2141 III (B).
Regarding claim 45, the modified composition of US’205 teaches the composition of claim 41. The modified composition further teaches wherein the alcohol is selected from a group consisting of methanol (US’268, para. 39, methanol may be used as the alcohol).
Regarding claim 46, the modified composition of US’205 teaches the composition of claim 41. The modified composition further teaches wherein the additive comprises pyridine (US’342 teaches pyridine as a known amine, para. 71).
Claim(s) 42 and 47 are rejected under 35 U.S.C. 103 as being unpatentable over Kiehlbauch et al. US 2009/0275205 (US’205) in view of Toda et al. US 2015/0380268 (US’268).
Regarding claims 42, US’205 teaches a composition comprising:
hydrogen fluoride vapor (a gaseous chemistry including HF to remove silicon oxide, para. 15);
and a mixture, the mixture comprising and an additive (the gaseous mixture includes a volatile amine, volatile amine may be NH3 or an alkylated derivative or alkylated analog of NH3, such as methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, isopropyl amine, dipropyl amine, n-propyl amine, n-butyl amine, sec-butyl amine, t-butyl amine, or combinations thereof, para. 15);
US’205 does not teach the mixture comprises an alcohol and wherein the additive comprises 0.01 wt % to 1 wt % of the mixture of the alcohol vapor and the additive.
US’268 teaches an etching composition for selectively etching silicon oxide including HF gas and an alcohol. a volume ratio (flow rate ratio) of the alcohol gas to the total sum of F2 gas+HF gas+alcohol gas may fall within a range from 10 to 85 volume %. The alcohol gas tends to increase the etching selectivity of the SiO2 film with respect to the SiN film (para. 44-53). Therefore, US’268 teaches adding an alcohol to a gaseous treatment composition for silicon oxide semiconductor processing for the purposes of controlling the selectivity of the treatment between silicon oxide and silicon nitride. US’205 further teaches by way of non-limiting example, a volumetric flow rate ratio of the HF to the volatile amine in the gaseous mixture may be within a range of from approximately 1/1 to approximately 1/2. The flow range of NH3 and HF may be in the range of approximately 20 sccm to approximately 50 sccm. If an inert carrier gas is present, the gaseous mixture of the HF and the volatile amine may account for from approximately 0.05% by volume to approximately 20% by volume of the total volume of the gaseous mixture and the inert carrier gas. The combination of amine and HF react with each other and the silicon oxide to breakdown the silicon oxide, thereby etching the silicon oxide to create a product that can be easily removed for the surface (para. 17-18.) Therefore, US’205 teaches using a relatively small amount of additive/amine relative to the composition as a whole and US’268 teaches using large amount of alcohol relative to the HF content. As a result, the combined teachings of US’205 and US’268 teach one of ordinary skill in the art to control the amount of amine additive to be relatively small compared to the amount of alcohol for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride. Too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the composition of US’205 to include the mixture comprises an alcohol because US’268 teaches it can be added for the purposes of providing etch electivity between silicon oxide and silicon nitride and combining prior art elements according to known methods to yield predictable results is obvious, see MPEP 2141 III (A).
Further, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify the modified composition of US’205 to include wherein the additive comprises 0.01 wt % to 1 wt % of the mixture of the alcohol vapor and the additive because the combination of US’205 and US’268 teaches to control the amount of amine additive to be relatively small compared to the amount of alcohol for the purposes of controlling the treatment of the SiO2 by controlling the breakdown of silicon oxide and the selectivity of the chemistry to silicon oxide vs other films present on the substrate including silicon nitride, too low an amount of amine would not provide a chemistry necessary to etch the silicon oxide and too high of an amount would inhibit the etch selectivity and it is not inventive to discover the optimum or workable ranges by routine experimentation, see MPEP 2144.05.
Regarding claim 47, the modified composition of US’205 teaches the composition of claim 42. The modified composition further teaches wherein the alcohol is selected from a group consisting of methanol (US’268, para. 39, methanol may be used as the alcohol).
Claim(s) 48 is rejected under 35 U.S.C. 103 as being unpatentable over US’205 in view of US’268 as applied to claim 42 above, and further in view of Visintin et al. US 2008/0125342 (US’342).
Regarding claim 48, the modified composition of US’205 teaches the composition of claim 42.
The modified composition of US’205 does not teach wherein the additive comprises pyridine.
US’342 teaches a removal composition and process for removing silicon-containing layers from a microelectronic device. The removal composition selectively removes layers including, but not limited to, silicon oxide (abstract). Etchants are added to react with the silicon-containing material and assist in the removal of same from the microelectronic device. Etchants contemplated for use include fluorides and amines, not limited to: hydrogen fluoride (HF) an extensive list of amines. The amines listed include many of the same alkyl amine taught by US’205 as well as an extensive list of heteroaromatic cyclic amines for example pyrrole, triazoles and pyridine (para. 68). Amines may be added to increase the oxide etch rates in the presence of the fluoride etchant source. The speciation between the acid (A-H) and base (B) changes, depending on the amine basic strength. The intermediate complex A-H--B strongly influences the rate of various oxide materials. As such, we can selectively etch one oxide material over the other or adjust the amine concentration so that both or all of the oxide materials have similar etch rates. Preferably, the amine component comprises 1-methylimidazole (a heteroaromatic cyclic amine) (para. 71). Therefore, US’342 teaches that amines, including the category of heteroaromatic cyclic amines, are a well understood class of compounds, whose chemical reactions are well understood with regard to etching of oxides when combined with HF and that they can be selected from known alternatives to tune the etch selectivity.
It would have been obvious to one of ordinary skill in the art before the effective fling date of the claimed invention to modify the modified composition of US’205 to include wherein the additive comprises pyridine because US’342 teaches that amines, including the category of heteroaromatic cyclic amines which pyridine is an example of, are a well understood class of compounds, whose chemical reactions are well understood with regard to etching of oxides when combined with HF and that they can be selected from known alternatives to tune the etch selectivity and simple substitution of one known element for another to obtain predictable results is obvious, see MPEP 2141 III (B).
Response to Amendment
Applicant’s amendments to independent claim 24 and 34 to broaden the scope of the composition and add limitations related to the amount of additive has changed the scope of claims 24 and 36. Upon further consideration, a new grounds of rejection is applied in the above final office action based on the teachings of US’205, US’268 and US’342.
Response to Arguments
Applicant's arguments filed 1-14-26 have been fully considered but they are not persuasive.
Regarding the Expert Declaration filed 1-14-26 that the inventors "invented the claimed compositions to overcome problems of wet etching and salt-based etching, and found a particular combination of gases including a particular amount of additive in the gas to be advantageous in a thermal, plasma-free vapor-based process, thereby enabling etching for semiconductor substrates.". The Expert Declaration is not found persuasive for showing unexpected results for overcoming the applied optimization rejection for the following reasons:
The claims are directed to a composition not a process of using the composition. Arguments directed solely to the use of the composition are not persuasive since the composition is independent of its intended use. Claim 34, a slightly broader version of claim 24 recite a generic additive having a concentration of 0.01wt% to 1wt% in relation to a generic alcohol. However, the declaration discussed how the composition is used to produce beneficial results, but does not presenting evidence to show that any combination of a generic additive and generic alcohol within the claimed range would produce a superior result. It is therefore unclear if the results applicants describe as being superior can solely be attributed to the makeup of the composition and not attributed to any of the operating conditions, i.e. process temperature, pressure, substrate properties.
Applicants’ specification discloses many other acceptable ranges for the additive including “in a range from 0.1 parts per million (ppm) to 2000 ppm (mass) of the gas mixture. In other features, the additive is in a range from 1 part per million (ppm) to 500 ppm (mass) of the gas mixture”, see pages 2-3 of the filed specification. The specification does not describe either of these ranges as equivalent ranges to the additive comprises 0.01 wt% to 1 wt% of the mixture of the additive and the alcohol. This undercut applicants’ assertions that the additive comprises 0.01 wt% to 1 wt% of the mixture of the additive and the alcohol is a particularly significant range resulting in unexpected results.
The Expert Declaration presents table 1 showing experimental results, however none of the process conditions are identified and critically what the wt% of the additive is for each process. As set forth in MPEP 716.02(d), Whether the unexpected results are the result of unexpectedly improved results or a property not taught by the prior art, the "objective evidence of nonobviousness must be commensurate in scope with the claims which the evidence is offered to support." In other words, the showing of unexpected results must be reviewed to see if the results occur over the entire claimed range. In re Clemens, 622 F.2d 1029, 1036, 206 USPQ 289, 296 (CCPA 1980) (Claims were directed to a process for removing corrosion at "elevated temperatures" using a certain ion exchange resin (with the exception of claim 8 which recited a temperature in excess of 100°C). Appellant demonstrated unexpected results via comparative tests with the prior art ion exchange resin at 110°C and 130°C. The court affirmed the rejection of claims 1-7 and 9-10 because the term "elevated temperatures" encompassed temperatures as low as 60°C where the prior art ion exchange resin was known to perform well. The rejection of claim 8, directed to a temperature in excess of 100°C, was reversed.). See also In re Peterson, 315 F.3d 1325, 1329-31, 65 USPQ2d 1379, 1382-85 (Fed. Cir. 2003) (data showing improved alloy strength with the addition of 2% rhenium did not evidence unexpected results for the entire claimed range of about 1-3% rhenium); In re Grasselli, 713 F.2d 731, 741, 218 USPQ 769, 777 (Fed. Cir. 1983) (Claims were directed to certain catalysts containing an alkali metal. Evidence presented to rebut an obviousness rejection compared catalysts containing sodium with the prior art. The court held this evidence insufficient to rebut the prima facie case because experiments limited to sodium were not commensurate in scope with the claims.). In re Lindner, 457 F.2d 506, 509, 173 USPQ 356, 359 (CCPA 1972) (Evidence of nonobviousness consisted of comparing a single composition within the broad scope of the claims with the prior art. The court did not find the evidence sufficient to rebut the prima facie case of obviousness because there was "no adequate basis for reasonably concluding that the great number and variety of compositions included in the claims would behave in the same manner as the tested composition.". To establish unexpected results over a claimed range, applicants should compare a sufficient number of tests both inside and outside the claimed range to show the criticality of the claimed range. In re Hill, 284 F.2d 955, 128 USPQ 197 (CCPA 1960). Applicants have not provided data to show that the unexpected results do in fact occur over the entire claimed range of 0.01 wt% to 1 wt% of a generic additive relative to a generic alcohol with any amount of HF in vapor form.
The conditions of the comparative examples are unclear and therefore it cannot be determined that the results are superior to the prior art combination applied in the instant or previous rejections.
Applicants’ arguments that the claimed composition addresses a problem not solved by the cited references, that the claimed composition achieves etching without performing a plasma removal or a steam clean operation, and combining the references as suggested by the Examiner would require a principle change of operation in US'205 has been considered but is not deemed persuasive. The arguments rely on the process of using the claimed composition and the end result of using the claimed composition is different that the combined teachings of KR’078, US’205 and US’035. However, claims 24 and 34 are directed to a composition which is independent of its intended use. As discussed above, Applicant has not shown sufficient evidence that the particular range of 0.01 wt% to 1 wt% of a generic additive relative to a generic alcohol with any amount of HF in vapor form produces unexpected results.
Applicants’ arguments that US'205 requires that the amine used react with HF to form a solid reaction product. It only suggests that alkylated ammonia derivatives, not heterocyclic aromatic derivatives has been considered but is not deemed persuasive. The examiner maintains that the list of alternatives presented by US’205 is not exclusionary for the volatile amine. US’035 further teaches solvents known for using in substrate treatments method include amines include triethylamine, pyridine, and the like (para. 133-145). Therefore, US’035 teaches that pyridine is in the amine class of compounds that can be used in semiconductor processing. Since, US’205 teaches the use of an amine, it would be understood by one of ordinary skill in the art that any amine that could be use in semiconductor processing could be used including pyridine which is taught by US’205. A reference that clearly names the claimed species, anticipates the claim, no matter how many other species are named (see MPEP 2131.02 II). The test for obviousness is not whether the features of a secondary reference may be bodily incorporated into the structure of the primary reference; nor is it that the claimed invention must be expressly suggested in any one or all of the references. Rather, the test is what the combined teachings of the references would have suggested to those of ordinary skill in the art. See In re Keller, 642 F.2d 413, 208 USPQ 871 (CCPA 1981). Further, as discussed above, US’342 teaches that amines, including the category of heteroaromatic cyclic amines, are a well understood class of compounds, whose chemical reactions are well understood with regard to etching of oxides when combined with HF and that they can be selected from known alternatives to tune the etch selectivity.
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.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ERIN FLANAGAN BERGNER whose telephone number is (571)270-1133. The examiner can normally be reached M-F 8:00-5:00.
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/ERIN F BERGNER/Primary Examiner, Art Unit 1713
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