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 .
Status of the Claims
Claims 1-17 and 21-23 are pending and rejected. Claims 18-20 are cancelled.
Election/Restrictions
Applicant’s election without traverse of Group I, claims 1-17 in the reply filed on 6/12/2026 is acknowledged.
Claims 18-20 have been cancelled. Election was made without traverse in the reply filed on 6/12/2026.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-6 and 9 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Regarding claim 1, the term “super conformal” is a relative term which renders the claim indefinite. The term “super conformal” is not defined by the claim, the specification does not provide a standard for ascertaining the requisite degree, and one of ordinary skill in the art would not be reasonably apprised of the scope of the invention. The specification at [0033] indicates that an example of a super conformal profile includes a limited metal layer deposited on to the interior sidewalls of the cavity and substantially no metal layer deposition on the top surface of the substrate. For the purposes of examination, providing the metal fill layer such that substantially no metal is on the top surface of the substrate or using bottom-up filling is considered to meet the claimed super conformal profile. Since none of the dependent claims remedy the clarity of claim 1, they are also rendered indefinite. Appropriate action is required without adding new matter.
Regarding claim 2, TiCl5 is listed as a metal halide used for etching, however, TiCl4 is usually used because the maximum oxidation state of titanium with chloride under normal conditions is 4. Therefore, it is unclear whether this is a typographical error and TiCl4 was intended to be listed or whether TiCl5 is required. For the purposes of examination, either is considered to meet the claimed requirements. Appropriate action is required without adding new matter.
Regarding claim 9,the claim recites the limitation "the second metal layer" in line 2. There is insufficient antecedent basis for this limitation in the claim. The claim is dependent on claim 7 and indicates that the second processing operation comprises removing the second metal layer from the deposited metal layer, suggesting that the second processing operation removes the second metal layer from the metal layer that is deposited over the precleaned contact structure, however, claim 8 provides antecedent basis for “the second metal layer”, making it unclear from which claim the claim depends. The specification at [0034] indicates that operations 130 and 140 are cyclically performed to achieve a bottom-up metal fill provide where metal layer 216 is deposited and then etched. Therefore, the claim is being interpreted as though claim 9 is dependent on claim 8 to provide proper antecedent basis. Appropriate action is required without adding new matter.
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.
Claims 1-13, 16, 17, and 21-23 are rejected under 35 U.S.C. 103 as being unpatentable over Chang, US 2019/0355585 A1 in view of Lehn, US 2020/0283894 A1.
Regarding claims 1 and 4-6, Chang teaches a method of forming a contact structure (a method for fabricating a semiconductor structure including a contact region, abstract and 0042), the method comprising:
performing a preclean operation on a contact structure to form a precleaned contact structure (performing a pre-clean process on the substrate, 0073), the contact structure comprising:
a silicon-based portion exposed in a cavity of a substrate, the substrate comprising a bottom surface of the cavity, an interior sidewall of the cavity, and a top surface, and a liner layer disposed on the interior sidewall of the cavity (where the gate structures include and exposed S/D region that includes silicon so as to result in TiSi, such that the exposed portion is considered to be silicon-based, 0025, 0027, 0043, 0047, 0048, and Fig. 2, where the cavity has a bottom surface, a top surface, an interior sidewall, and a liner or spacer 116 disposed on the interior sidewall of the cavity, 0035 and Fig. 2);
depositing a metal layer over the precleaned contact structure to form a deposited contact structure (forming an initial titanium layer over the gate structures, 0043, 0074-0075, and Fig. 3), wherein:
a first layer is deposited on the bottom surface of the cavity, and a second layer is deposited onto the liner layer and the top surface (where the initial titanium layer is formed over the surfaces of the cavity while also being etched back, where the deposition rate can be higher than the etching rate, where the titanium layer is depicted as being formed over the surfaces of the cavity, 0043, 0047-0049, and Fig. 3);
introducing a metal halide precursor to the deposited contact structure to at least partially remove the second layer from the deposited contact structure to form an etched contact structure (where the precursor is TiCl4 which results in etching of the initial titanium layer 119 over the sidewalls of the gate structure, 0048 and Fig. 4, such that a portion of the second layer will be at least partially removed to form an etched contact structure); and
depositing a metal fill layer onto the first layer to form a filled contact structure, wherein the deposited metal fill layer comprises a super conformal profile (where the contact structure is filled with a metal interconnect, 0042, 0058, and Fig. 7).
They do not teach that depositing the metal fill layer comprises a super conformal profile.
Chang teaches that the fill metal layer may be tungsten (0030).
Lehn teaches methods of forming metal-containing films by ALD by delivering a metal-containing complex, a purge gas, and a co-reactant to a first substrate under sufficient conditions such that the metal-containing film selectively grows on at least a portion of the first substrate (abstract). They teach that the metal-containing complex may deposit a species (e.g., metal) on a substrate to form a film, and the metal-containing complex may also etch away the film already formed on the substrate, i.e., remove portions of previously deposited film (0087). They teach that by controlling or adjusting one or more of the rate at which the metal-containing complex deposits a species, rate at which the metal-containing complex etches the film, and the rate at which a species desorbs from the film, for example, by adjusting the conditions of the process and/or the metal-containing complex used, selective film growth may be achieved on one or more substrates (0087). They teach that the methods can achieve improved filling of a feature on or in a substrate including depositing a metal-containing film in a manner which substantially fills a feature without any voids of hollow seams (0087). They teach that features refer to contacts (0094). They teach that super-conformal growth refers to a deposition process wherein substantially more material may be deposited at a bottom or a lower portion of a feature, than compared to outside the feature and/or at the top or upper portion of the feature (0096). They teach that substantially more material is intended to encompass a thickness of material deposited at a bottom or a lower portion of a feature that is at least bout 100% greater, at least about 250% greater, at least about 1000% greater, etc. than a thickness of the material deposited within the top or upper portion of the feature and/or outside of the feature (0096). They teach that an example of super conformal growth includes substantially no material deposited outside the feature and/or at the top or upper portion of the feature or where about 100% of the feature may be filled with material and substantially no material may be deposited outside the feature (0096). They teach that a deposition cycle and an etching/desorbing cycle may be performed and/or alternated as needed to provide selective film growth on one or more substrates (0117). They teach that the super conformal growth cycle provides a deposition rate of the metal-containing complex higher in a lower portion of the feature than in an upper portion of the feature and/or an etching rate and/or a desorption rate of the metal-containing complex may be higher in an upper portion of the feature than in a lower portion of the feature (0122). They teach that the super conformal growth cycle comprises delivery of a metal-containing complex, delivery of a purge gas, delivery of a co-reactant, and delivery of a purge gas (0127-0131). They teach controlling the process conditions to achieve super-conformal growth (0132). They teach that the etch cycle includes that same steps where the conditions are controlled to achieve etching (0149-0154). They teach that a super cycle includes one or more super-conformal growth cycles, conformal growth cycles, sub-conformal growth cycles, and/or one or more etch cycles to achieve the desired growth (0156). They teach that the metal-containing complexes includes metals such as tungsten, where an example is WCl6 (0167-0170). They teach that co-reactants include hydrogen, DHP, etc. (0176-0180).
From the teachings of Lehn, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have deposited the tungsten filling material using the super conformal method of Lehn because Lehn teaches that their methods can achieve improved filling of a feature on or in a substrate including depositing a metal-containing film in a manner which substantially fills a feature without any voids of hollow seams, where the metal material can be tungsten such that it will be expected to fill the feature as desired. Therefore, the process will include depositing a metal fill layer, which is expected to have a super conformal profile (bottom-up deposition with substantially no metal on the top surface) as interpreted in the 112(b) rejection above. Further, since they indicate that the precursor can be WCl6, where the co-reactant include hydrogen or a reactant without fluorine, the resulting deposition process will be a FFW process in which a tungsten precursor (WCl6) is introduced to the etched contact structure in an ALD process.
Regarding claim 2, Chang in view of Lehn suggest the process of claim 1. Chang further teaches that the metal halide is titanium tetrachloride (0044), which is understood to meet the claimed requirements as discussed in the 112(b) rejection above.
Regarding claim 3, Chang in view of Lehn suggest the process of claim 1. Chang teaches that the titanium layer is used to form a titanium silicide layer 121 (0048 and Fig. 4), such that the first layer will comprise TiSi. They teach that the remaining layer of titanium 119’ is used to form a titanium nitride layer (0054 and Fig. 5). As depicted in Fig. 4, the TiSi layer 121 is also provided on the liner layer (Fig. 4). Therefore, the second layer after the nitridation process will comprise Ti, TiN, and TiSi.
Regarding claims 7-10, Chang in view of Lehn suggest the process of claim 7, wherein the cavity will include a volume defined by the silicon based portion exposed in the cavity of the substrate and the liner layer disposed on the interior sidewall of the cavity as in Fig. 2 of Chang. Further, by performing the process of Lehn, the filling will provide a cyclic processing operation to deposit a selective fill layer on the etched contact structure to form a bottom-up metal filled contact structure.
Further, as discussed above for claim 1, Lehn teaches performing a super cycle that includes one or more super-conformal growth cycles and one or more etch cycles to achieve the desired film growth, where the number and order of the various cycles can be varied (0156). They teach that super conformal growth includes various ranges where the thickness of the deposited at the bottom or lower power is at least about 20% or greater than the thickness at the top or upper portion of the feature, or about 50% greater, at least about 100% greater, etc., where the top or upper portion is intended to encompass the upper about 25% of the depth of the feature (0096). From this, the deposition process of Lehn is expected to include a range in which a first metal fill layer is formed to be on the bottom surface of the cavity an a second metal layer is disposed on the liner layer above the first metal layer because Lehn provides a bottom up process in which the thickness formed on the bottom is provided as having a thickness of at least about 20% greater, or about 50% greater, etc. indicating that a thickness on the upper 25% (upper portion) of the feature will also be provided, suggesting that a film or layer will also be provided on the sidewalls of the cavity as depicted in Fig. 2a-2d of Lehn. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have provided a second process (etching process) of removing the second metal layer on the liner layer so as to provide the super conformal bottom up growth because Lehn provides a super cycle including the super conformal growth cycle(s) and etching cycle(s) such that it will be expected to remove excess growth for providing the desired bottom up filling of the cavity. Therefore, Chang in view of Lehn suggest providing a first processing operation and a second processing operation as required by claims 7-9, where the first processing operation will be provided before the second processing operation as required by claim 10 such that the material will be deposited so as to be subsequently etched.
Regarding claims 11-13, Chang in view of Lehn suggest the process of claim 7, as noted above for claims 4-6, the process is understood to be a FFW process that includes introducing a tungsten precursor (WCl6) into the cavity in an ALD process.
Regarding claim 16, Chang in view of Lehn suggest the process of claim 7. Lehn teaches that the process comprises one or more cycles which may be adjusted as needed for film growth (0111). They teach that the super-cycle can includes one or more super-conformal growth cycles and/or one or more etch cycles to achieve the desired film growth (0156). They provide an example of a super cycle combining a first series of one or more of (i) a first series of one or more conformal growth cycles; (ii) a second series of one or more super-conformal growth cycles; (iii) a third series of one or more sub-conformal growth cycles; and (iv) a fourth series of one or more etch cycles (0157). They teach that the first series of conformal growth cycles can comprise from 1 to 10 cycles, 2 to 5 cycles, or 3 cycles, the second series of super conformal growth can comprise from 1 to 10 cycles, 1 to 5 cycles, or 1 cycle, the third series of sub-conformal growth cycles can comprise 1 to 10 cycles, 1 to 5 cycles, or 1 cycle, and the fourth series of etch cycles can comprise from 1 to 10 cycles, 1 to 5 cycles, or 1 cycle (0157). Therefore, the number of cycles in the cyclic processing operation will overlap or be within the claimed range when, for example, the super cycle includes 1 cycle of super conformal growth and 1 cycle of etching. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.”
Alternatively, since they teach providing the super cycle for achieving super conformal growth in filling the feature, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the number of cycles to be within the claimed range so as to provide the desired filling of the sized feature. According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[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).
Regarding claim 17, Chang in view of Lehn suggest the process of claim 7. Lehn further teaches that the super conformal growth cycles is used so that at least about 20%, 60%, or about 100% of the feature is filled (0126). They teach providing the super cycle so that the feature is substantially filled (0156). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have performed the cyclic processing operation for a number of cycles such that the metal fill layer occupies about 20%, 60%, or about 100% of the volume of the cavity because Chang teaches filling the feature and Lehn suggests performing the process until such a percentage of the cavity is filled, where the super cycles are provided so that the feature is substantially filled such that it will be expected to fill the feature as desired. Therefore, the process will be provided a number of cycles so that the volume of the cavity filled is within the claimed range. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.”
Regarding claims 21-23, Chang in view of Lehn suggest the process of claims 1 and 7. Chang teaches that the deposition of the titanium layer can be determined by a desired thickness of titanium silicide layer, where the desired thickness of titanium silicide is in the range of about 7 nm to about 10 nm (0044). They teach providing a second titanium layer and then nitriding, where the total thickness of the first and second titanium layers can result in longer nitridation times (0052, 0055, and Fig. 6). They teach that the thickness of the titanium nitride layer can be in the range of about 1 to about 4 nm on the spacer layers 116 (0055 and Fig. 6). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that the thicknesses of the first and second layers will be within the claimed range because Chang teaches that the thickness of the titanium nitride layer (comprising the second layer) is within the claimed range and the thickness of the titanium silicide layer is also within the claimed range, suggesting that the formed titanium layer will be within the range of 1000 nm or less so as to provide sufficient titanium for forming the layers without requiring removal. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.”
Claims 1, 2, 7, 10, 14, 15, and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Hsieh, WO 2023/164413 A1 (provided on the IDS of 7/15/2025) in view of Na, WO 2022/150270 A1.
Regarding claim 1, Hsieh teaches a method of forming a contact structure (methods of depositing Mo on S/D contacts, abstract and 0045), the method comprising:
performing a preclean operation on a contact structure to form a precleaned contact structure (pre-treating a conformal liner layer to clean it before depositing the metal film, 0017, 0106, and Fig. 3), the contact structure comprising:
a silicon-based portion in a cavity of a substrate, the substrate comprising a bottom surface of the cavity, an interior sidewall of the cavity, and a top surface, and a liner layer disposed on the interior sidewall of the cavity (where the feature has a bottom surface 405 and lined feature sidewalls surfaces 411, where the liner is TiN and the bottom surface includes a metal silicide nitride layer 408 and a metal silicide layer 407 connected to a semiconductor layer 406 such as silicon, 0105 and Fig. 4A, such that the silicon-based or silicide portion is at the bottom and the liner is on the interior sidewalls of the cavity);
depositing a metal layer over the precleaned contact structure to form a deposited contact structure (depositing a metal film base such as molybdenum layer 409 in the feature, 0107 and Fig. 4B), wherein:
a first layer is deposited on the bottom surface of the cavity, and a second layer is deposited onto the liner layer and the top surface (where Mo is formed on the bottom surface 405 and a thin conformal layer is deposited on the sidewalls, 0109 and Fig. 4B);
introducing a metal halide precursor to the deposited contact structure to at least partially remove the second layer from the deposited contact structure to form an etched contact structure (where in operation 304, part of the metal nitride layer or other conformal liner layer on the sidewalls is etched using the precursor used to deposit Mo as an etchant, where the precursor is a molybdenum halide precursor, and where MoCl5 etches away the Mo and the TiN liner layer on the sidewall surfaces in an upper portion of the feature, 0100, 0112, Fig. 3, and Fig. 4C, such that the halide precursor removes at least a portion of the second layer) ; and
depositing a metal fill layer onto the first layer to form a filled contact structure (where the feature is filled with a Mo fill 423 using a bottom-up fill, 0113). As noted above in the 112(b) rejection, the bottom-up filling is considered to provide a super conformal profile.
They do not teach that the silicon-based layer is exposed.
Na teaches depositing Mo using a MoClx precursor followed by depositing Mo to fill a feature using a molybdenum oxyhalide precursor (abstract). They teach that the protective Mo layer enables Mo fill using a molybdenum oxyhalide precursor without oxidation of the underlying surfaces (abstract). They teach that the method is used for S/D contact fill (0064). They teach providing a feature in a dielectric material to connect an underlying titanium silicide layer (0105 and Fig. 4A). They teach that the sidewall surfaces may be coated with a Ti liner layer and the top surface of the titanium silicide layer is oxidized (0105). They teach that the structure undergoes a preclean process to remove oxide from the silicide surface (0106 and Fig. 4B). They teach that the initial Mo layer is deposited using the MoClx precursor on the silicide and sidewalls surfaces (0107 and Fig. 4C). They teach that by using the non-oxygen containing precursor, there is no re-oxidation of the feature or the silicide (0107). They then teach filling the gap using ALD or CVD (0108 and Fig. 4D).
From the teachings of Na, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention that the silicide surface can be exposed in the feature because Na teaches that the oxide can be removed from the TiSix surface when molybdenum is deposited using MoClx without reoxidizing the silicide in forming a contact such that it will be expected to provide a desirable contact structure without resulting in oxidation.
Regarding claim 2, Hsieh in view of Na suggest the process of clam 1. Hsieh further teaches using MoCl5 as the precursor (0075, 0095, and 0101).
Regarding claims 7, 10, 14, and 15, Hsieh in view of Na suggest the features of claim 7, where a volume of the cavity will be defined by the silicon-based portion exposed in the cavity of the substrate and the liner layer disposed on the interior sidewall of the cavity as depicted in Fig. 4A of Hsieh and Fig. 5A of Na. In the process of Hsieh in view of Na the molybdenum layer will be deposited to form the first layer on the bottom surface of the cavity and the second layer will be formed on the liner layer and the top surface, where the metal halide precursor removes a portion of the second layer to form the etched contact surface. Hsieh further teaches that the feature may be filled with Mo by ALD, where in ALD one or more cycles of sequential doses of a Mo precursor and reactant may be used (0074-0075). They teach that MoCl5 may be used as a precursor and H2 may be used as a reducing agent or co-reagent (0075). They teach that the pulsing sequence is 1) introducing reducing agent; 2) optional Ar purge; 3) introducing molybdenum-containing precursor; and 4) optional Ar purge (0075-0076). They teach that the temperature and/or pressure may be used to control selectivity, where Mo is selectively deposited into the feature (0075 and 0079). They teach that the Mo is selectively deposited in a bottom-up process (0112-0113). Therefore, the filling process will be a cyclic processing operation to form a bottom-up metal filled contact structure, the cyclic processing operation comprising a first processing operation (reducing agent pulse) and a second processing operation (molybdenum precursor pulse), such that the second processing operation will be performed subsequent the first and it will comprise introducing a molybdenum halide compound, i.e., MoCl5, to the cavity as required by claims 10, 14 and 15.
Regarding claim 17, Hsieh in view of Na suggest the process of claim 7. Hsieh teaches filling the feature (0074 and Fig. 4D). From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the number of cycles such that the selective metal fill layer occupies about 100% of the volume of the cavity because they teach filling the feature such that it will be expected to provide the metal in the feature as desired. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[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).
Conclusion
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718
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