DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claim(s) 1-3, 9-13,15-20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Quick et al (US pub No. 20140027775), in view of Ruh et al (US Patent No. 4337239), in view of Frougier et al (US Patent No. 10388732), in view of Alaboson et al (PCT/US2017/061088, WO 2018/093679), in view of Bhattacherjee et al (US Pub No. 20180343006).
With respect to claim 1, Quick et al discloses method for depositing a transition metal chalcogenide film (para 32) on a substrate (102,Fig.1 by a cyclical deposition process (Para 30, ALD), the method comprising: contacting the substrate with at least one transition metal containing vapor phase reactant (Para 34) comprising at least one of a hafnium precursor and a zirconium precursor (Para 34); and contacting the substrate with at least one chalcogen containing vapor phase reactant (Para 34). However, Quick et al does not explicitly disclose that vapor phase was used during the ALD process, on the other hand, it would have been obvious to one of ordinary skill in the art at the time of filing of the invention to modify Quick et al such that vapor phase was to introduce the metal precursor in to the chamber in order to effectuate the ALD process.
However, Quick et al does not explicitly disclose wherein at least one of the hafnium precursor and the zirconium precursor comprises at least one of a halide precursor comprising at least one of hafnium tetrachloride (HfCl4) and zirconium tetrachloride (ZrCl4); or a metalorganic precursor comprising at least one of an alkylamide precursor or a cyclopentadienyl-ligand containing precursor. On the other hand, Ruh et al discloses titanium tetrachloride (titanium like zirconium is a transitional metal, Abstract) reacts with hydrogen disulfide (abstract) to form a titanium disulfide (Abstract). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify Quick et al according to the teachings of Ruhs et al such that one would be motivated to form ZrS2 by using zirconium tetrachloride and HS2, for semiconducting applications. However, the arts cited above do not explicitly disclose ALD process is used to ZrS2 or HFS2. On the other hand, Frougier et al discloses ALD is used to form a HfS2 and ZrS2 (Column 6). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above according to the teachings of the Frougier et al such that ALD is used to hafnium or zirconium disulfide using hafnium or zirconium tetrachloride and HS2, in order to form a high quality ZrS2 or HfS2 for semiconducting application.
Furthermore, the arts cited above do not explicitly disclose a metalorganic precursor comprising at least one of tetrakis(ethylmethylamido)hafnium (Hf(NEtMe),) or tetrakis(ethylmethylamido)zirconium (Zr(NEtMe)) a cyclopentadienyl-ligand containing precursor.
On the other hand, Alaboson et al discloses or a metalorganic precursor (Para 42) comprising at least one of tetrakis(ethylmethylamido)hafnium (Hf(NEtMe),) or tetrakis(ethylmethylamido)zirconium (Para 42) a cyclopentadienyl-ligand containing precursor (Para 42). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above according to the teachings of Alaboson such that tetrakis(ethylmethylamido)zirconium and sulfide agent are used in an ALD process to make a uniform film for semiconducting purposes. However, the arts cited above do not explicitly disclose depositing a capping layer over the transition metal chalcogenide film. On the other hand, Bhattacherjee et al discloses depositing a capping layer (122,Fig.1) over the transition metal chalcogenide film (106, Para 38). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above according to the teachings of the Bhattacherjee et al such that a capping layer is formed over the transition metal chalcogenide film, in order to make transistors which may be used in the logic devices.
With respect to claim 2, Quick et al discloses wherein the cyclical deposition process comprises atomic layer deposition (Para 30, Example 1).
With respect to claim 3, Quick et al discloses wherein the cyclical deposition process comprises cyclical chemical vapor deposition (Para 30). However, it does not explicitly discloses that the CVD was cyclical. On the other hand, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the art cited above such that cyclical CVD was used to deposit chalcogenide, in order to reach a desired thickness more accurately.
With respect to claim 9, Quick et al discloses wherein the at least one chalcogen containing vapor phase reactant comprises radicals formed from hydrogen sulfide (H2S), hydrogen selenide (H2Se), dimethyl sulfide ((CH3)2S), and dimethyl telluride (CH3)2Te (Para 10-34).
With respect to claim 10, Quick et al does not explicitly discloses further comprising flowing the chalcogen containing vapor phase reactant through a gas purifier prior to entering the reaction chamber to reduce a concentration of at least one of water and oxygen within the chalcogen containing vapor phase reactant. On the other hand ,it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify Quick et al such that a gas purifier prior to entering the reaction chamber to reduce a concentration of at least one of water and oxygen within the chalcogen containing vapor phase reactant, in order to make a make defect free chalcogenide material.
With respect to claim 11, Quick et al does not explicitly disclose wherein the concentration of at least one of water and oxygen within the chalcogen containing vapor phase reactant is reduced to less than 1 part per million. However, "[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation." In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
With respect to claim 12, Quick et al does not explicitly disclose further comprising flowing a carrier gas through a vessel containing a source of the transition metal containing vapor phase reactant to transport the transition metal containing vapor phase reactant to the reaction chamber and further comprising flowing the carrier gas through a gas purifier prior to entering the source of the transition metal containing vapor phase reactant to reduce a concentration of at least one of water and oxygen within the carrier gas. On the other hand, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify Quick et al such that it has the limitations cited in this claims to effectuate ALD process and produce a defect free film.
With respect to claim 13, Quick et al does not explicitly discloses, wherein the concentration of at least one of water and oxygen within the carrier gas is reduced to less than 1 part per million. However, "[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation." In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
With respect to claim 15, Quick et al disclose all the limitations of the claim 1, however, it does not explicitly disclose wherein the transition metal chalcogenide film comprises a predominant (001) crystallographic orientation. On the other hand, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify Quick et al such that metal chalcogenide film comprises a predominant (001) crystallographic is produced, since Quick et al discloses all the limitations of the claim 1.
With respect to claim 16, Quick et al does not explicitly discloses further comprising in-situ depositing a capping layer over the transition metal chalcogenide film. On the other hand, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above so the process of forming the capping layer on the metal chalcogen film is done in situ, in order to expedite the process.
With respect to claim 17, Quick et al does not explicitly disclose wherein in-situ depositing a capping layer over the transition metal chalcogenide film comprises depositing the capping layer utilizing non-oxidative precursors or non-oxygen reactants. On the other hand, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify Quick et al such that capping layer utilizing non-oxidative precursors or non-oxygen reactants in order to prevent it from harming the integrity of the chalcogenide layer.
With respect to claim 18, Quick et al does not explicitly discloses wherein the capping layer comprises a metal silicate film. On the other hand, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify Quick et al such that the capping layer comprises a metal silicate film, because of it’s desired dielectric value, which makes it ideal to use as a gate dielectric layer in some transistors.
With respect to claim 19, Quick et al does not explicitly disclose wherein the metal silicate film comprises an aluminum silicate film (AlxSiyOz). On the other hand, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify Quick et al such that Aluminum silicate is used as a gate dielectric layer as a design choice.
With respect to claim 20, Quick et al discloses a transition metal chalcogenide film deposited by the method of claim 1 (Para 34).
Claim(s) 21 is/are rejected under 35 U.S.C. 103 as being unpatentable over Quick et al (US pub No. 20140027775), in view of Ruh et al (US Patent No. 4337239), in view of Frougier et al (US Patent No. 10388732), in view of Alaboson et al (PCT/US2017/061088, WO 2018/093679), in view of Liu et al (ALD of Hafnium Oxide thin films from Tetrakis(ethylmethylamino)hafnium and Ozone, Journal of the Electrochemical Society,152 (3) G213-G219(2005))
With respect to claim 21, Alaboson et al discloses wherein at least one of the hafnium precursor and the zirconium precursor comprises tetrakis(diethylamido)hafnium and chalconegide agent is H2S (Para42), however, it does not explicitly disclose at least one of is selected from one or more of tetrakis(ethylmethylamido)hafnium (Hf(NEtMe)4) or tetrakis(ethylmethylamido)zirconium (Zr(NEtMe)4). On the other hand, Liu et al discloses tetrakis(ethylmethylamido)hafnium is used with water to form HfO2 (G213). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above according to the teachings of the Liu et al such that tetrakis(ethylmethylamido)hafnium is used instead of tetrakis(diethylamido)hafnium since in both cases hydrogen from water or chalcogen element to separate hydrocarbon from organo-metal material and the chalcogen element would attach to the hafnium, in order to form a HfS2 for microelectronic application.
Claim(s) 8, 23-24 is/are rejected under 35 U.S.C. 103 as being unpatentable over Quick et al (US pub No. 20140027775), in view of Ruh et al (US Patent No. 4337239), in view of Frougier et al (US Patent No. 10388732), in view of Breitung et al (EP 1930250A2), in view of Shin et al (US Pub No. 20180148334).
With respect to claim 8, Quick et al discloses method for depositing a transition metal chalcogenide film (para 32) on a substrate (102,Fig.1 by a cyclical deposition process (Para 30, ALD), the method comprising: contacting the substrate with at least one transition metal containing vapor phase reactant (Para 34) comprising at least one of a hafnium precursor and a zirconium precursor (Para 34); and contacting the substrate with at least one chalcogen containing vapor phase reactant (Para 34). However, Quick et al does not explicitly disclose that vapor phase was used during the ALD process, on the other hand, it would have been obvious to one of ordinary skill in the art at the time of filing of the invention to modify Quick et al such that vapor phase was to introduce the metal precursor in to the chamber in order to effectuate the ALD process.
However, Quick et al does not explicitly disclose wherein at least one of the hafnium precursor and the zirconium precursor comprises at least one of a halide precursor comprising at least one of hafnium tetrachloride (HfCl4) and zirconium tetrachloride (ZrCl4); or a metalorganic precursor comprising at least one of an alkylamide precursor or a cyclopentadienyl-ligand containing precursor. On the other hand, Ruh et al discloses titanium tetrachloride (titanium like zirconium is a transitional metal, Abstract) reacts with hydrogen disulfide (abstract) to form a titanium disulfide (Abstract). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify Quick et al according to the teachings of Ruhs et al such that one would be motivated to form ZrS2 by using zirconium tetrachloride and HS2, for semiconducting applications. However, the arts cited above do not explicitly disclose ALD process is used to ZrS2 or HFS2. On the other hand, Frougier et al discloses ALD is used to form a HfS2 and ZrS2 (Column 6). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above according to the teachings of the Frougier et al such that ALD is used to hafnium or zirconium disulfide using hafnium or zirconium tetrachloride and HS2, in order to form a high quality ZrS2 or HfS2 for semiconducting application.
However, the arts cited above do not explicitly disclose a metalorganic precursor comprising at least one of comprising at least one of an alkylamide precursor or tris(dimethylamido)cyclopentadienylhafnium (HfCp(NMez)s), bis(methylcyclopentadienyl)methoxymethylhafnium ((MeCp).Hf(CH)3(OCHs)), tris(dimethylamido)cyclopentadienylzirconium (ZrCp(NMez.)s3), or bis(methylcyclopentadienyl)methoxymethylzirconium ((MeCp)2Zr(CH)3(OCHs)). On the other hand, Breitung et al discloses a metalorganic precursor comprising at least one of comprising at least one of an alkylamide precursor (Para 33). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above such that Breitung et al uses alkylamide precursor in order to form a metal chalcogenide layer using ALD process, in order to be used in semiconducting applications. However, Chalcogen vapor comprises chalcogen radicals. On the other hand, Shin et al discloses chalcogen radicals are present in the chalcogen precursors (Para 72). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above according to the teachings of the Shin et al such that radicals are present in the chalcogen precursor in order to speed up the process to cut the fabrication time.
With respect to claim 23, further comprising in-situ depositing a capping layer over the transition metal chalcogenide film. However, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above such that metal chalcogenide has capping formed on it such as perovskite or electrodes for solar cell applications.
With respect to claim 24, the arts cited above dot not explicitly disclose further comprising pre-annealing the reaction chamber prior to film deposition. On the other hand, it would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above such that before the ALD process, the chamber is pre-annealed so the defect on the substrate where the metal chalcogenide is going to be formed would disappear, so better quality film would be deposited by the ALD process.
Claim(s) 22 is/are rejected under 35 U.S.C. 103 as being unpatentable over Quick et al (US pub No. 20140027775), in view of Ruh et al (US Patent No. 4337239), in view of Frougier et al (US Patent No. 10388732), in view of Breitung et al (EP 1930250A2), in view of Nikolaos et al (Solid-State Electronics 68 (2012) 38-47).
The claims cited above do not explicitly disclose wherein at least one of the hafnium precursor and the zirconium precursor comprises at least one of comprises at least one of tris(dimethylamido)cyclopentadienylhafnium (HfCp(NMez)s), bis(methylcyclopentadienyl)methoxymethylhafnium ((MeCp),Hf(CH)3(OCHsS)), tris(dimethylamido)cyclopentadienylzirconium (ZrCp(NMez)3), or bis(methylcyclopentadienyl)methoxymethylzirconium ((MeCp)2Zr(CH)3(OCHs)). On the other hand, Nikolaou discloses bis(methylcyclopentadienyl)methoxymethylhafnium as hafnium precursor to be used in order to make hafnium chalcogenide, since oxygen like sulfur would bind to hafnium and hydrocarbon would be released for semiconducting materials.
Claim(s) 14 is/are rejected under 35 U.S.C. 103 as being unpatentable over Quick et al (US pub No. 20140027775), in view of Ruh et al (US Patent No. 4337239), in view of Frougier et al (US Patent No. 10388732), in view of Alaboson et al (PCT/US2017/061088, WO 2018/093679), in view of Bhattacherjee et al (US Pub No. 20180343006).
With respect to claim 14, the arts cited above do not explicitly disclose annealing the transitional metal chalcogen film. On the other hand, Tang et al discloses annealing the transitional metal chalcogen film (Para 162). It would have been obvious to one of ordinary skill in the art at the time of the filing of the invention to modify the arts cited above according to the teachings of the Tang et al such that the metal chalcogen film is annealed in order to crystalized the channel region, thereby improve the electron mobility in the channel region.
Response to Arguments
Applicant’s arguments with respect to claim(s) 1-3,8-24 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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/ALI NARAGHI/Examiner, Art Unit 2817
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