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 .
Response to Amendment
Applicant’s amendments, filed 8/27/2026, have been fully considered and reviewed by the examiner. The examiner notes the amendment to claim 21. Claims 21-22, 25 and 27-32 are examined on the merits with claims 23-24 and 26 withdrawn.
Examiner notes the amendment to the title.
Response to Arguments
Applicant's arguments filed 8/27/2026 have been fully considered but they are not persuasive as they are directed towards newly added claim requirements that are addressed hereinafter.
Applicant’s arguments relative to the KR 370 and Kaufman-Osborn are noted, specifically arguing that the KR 370 reference discloses an oxidation prevention layer and the Kaufman reference discloses preforming an oxidation process and therefore each out contradict each other. The examiner disagrees with this analysis for the reasons set forth in the references. KR 370 discloses the oxidation protection layer is formed to prevent oxidation of the underlying Cu during other process steps and such needs to be removed prior to deposition on the Cu “a passivation layer on the Cu surface, such as a BTA layer, may have been deposited to protect the Cu surface from oxidation during other processing steps.” In addition, Kaufman-Osborn discloses preparing the substrate for the selective deposition, including removing e.g. various films. Kaufman-Osborn discloses exposing the substrate to the hydroxyl moiety (including air, water, oxygen) prior to SAM deposition for selective deposition (0038, 0041) and discloses the alternative for pulsing the oxidizer and SAM precursor (i.e. after removing the native oxide layer, oxidizing the surface) (0038). Kaufman-Osborn et al. discloses such providing the benefits of increasing the packed orientation of the SAM (0037) and having improved blocking properties (0049). Therefore, taking the references collectively, it would have been obvious to have modified Saly to use the oxidizing treatment to provide the benefits as outlined by Kaufman-Osborn et al., specifically, improved SAM blocking properties. The removal of the oxidation prevention layer that protects the underlying copper during other processes and prior to deposition and the oxidation of the underlying copper to enhance the blocking are not mutually exclusive and do not teach away from each other.
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.
Claim 21, 22, 25 and 28-32 recites the limitation "metal oxide" in second clause lacks antecedent basis in the claims as the claims require an undefined first material and oxidizing the surface “form a metal oxide”; however the claims fail to require any previously recited metal and therefore the metes and bounds of this claim are unknown (i.e. first material can be non-metal and it is unclear how oxidizing any first material as claimed can “form a metal oxide film”). There is insufficient antecedent basis for this limitation in the claim.
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.
Claim(s) 21, 22, 25, 27-32 is/are rejected under 35 U.S.C. 103 as being unpatentable over US Patent 11164745 by Saly taken with KR 20180136730, hereinafter KR 370 and US Patent Application Publication 20170256402 by Kaufman-Osborn et al. as evidenced by or further in view of Hashemi et al. (Selective Deposition of Dielectrics: Limits and Advantages of Alkanethiol Blocking Agents on Metal−Dielectric Patterns).
Claim 1: Saly discloses a film forming method for forming an object film on a substrate (Figure and accompanying text), the method comprising: providing the substrate including an a first material formed on a surface of a first area (column 4, lines 54-65), and a layer of a second material formed on a surface of a second area, the second material being different from the first material (column 4, lines 54-65), forming an SAM on the first surface relative to the second surface by supplying a SAM precursor (column 4, lines 12-50).
Saly discloses a metal layer and dielectric layer and selective blocking and discloses the substrate can be subject to a pretreatment process including reduction (column 3, lines 118-22); however, fails to disclose the oxidation prevention layer as claimed and removal of such. However, KR 370 discloses for selective deposition of surfaces that include Cu, including a oxidation prevention layer to protect the Cu and removing the oxidation prevention layer prior to selective deposition (“the treatment process may remove native oxide layers present on the first metal-based surface”, “ the treatment may remove a passivation layer or hydrocarbon layer that may be present on the second metal-based surface, for example, the treatment may remove the BTA layer present on the Cu surface . In some embodiments, a passivation layer on the Cu surface, such as a BTA layer, may have been deposited to protect the Cu surface from oxidation during other processing steps”) and therefore having a BTA/native oxide layer on the Cu layer would have been obvious to one of ordinary skill in the art to protect the Cu surface during other process steps as suggested by KR 370. KR 370 explicitly discloses the protective oxidation prevention layer must be removed prior to selective deposition (“a passivation layer must be removed prior to the selective deposition process.”) and therefore removing of such would have been obvious to provide a surface for selective deposition.
As for oxidizing the surface, Kaufman-Osborn et al. discloses exposing the substrate to the hydroxyl moiety (including air, water, oxygen) prior to SAM deposition for selective deposition (0038, 0041) and discloses the alternative for pulsing the oxidizer and SAM precursor (i.e. after removing the native oxide layer, oxidizing the surface) (0038). Kaufman-Osborn et al. discloses such providing the benefits of increasing the packed orientation of the SAM (0037) and having improved blocking properties (0049). Therefore, taking the references collectively, it would have been obvious to have modified Saly to use the oxidizing treatment to provide the benefits as outlined by Kaufman-Osborn et al., specifically, improved SAM blocking properties.
As for the gaseous SAM, Kaufman-Osborn et al. discloses liquid or gas SAM deposition (0034) and using gas would have been obvious as predictable.
As for the requirement of forming the metal oxide by oxidizing the layer of the first material, the examiner notes that Kaufman-Osborn et al. discloses exposing the substrate to the hydroxyl moiety (including air, water, oxygen) prior to SAM deposition for selective deposition (0038, 0041) and discloses the alternative for pulsing the oxidizer and SAM precursor (i.e. after removing the native oxide layer, oxidizing the surface) (0038) and selective deposition on metal versus dielectric (“SAM will selectively attach to one material over another material (e.g., metal vs. dielectric) and if of sufficient density, can successfully operation subsequent deposition allowing for selective deposition on materials not coated with the SAM.”). Similarly, Saly discloses selective deposition onto a first surface versus a second surface, wherein the first surface can be metal and second surface can be dielectric, including silicon oxide (column 4, lines 60-64) and discloses blocking deposition onto the first surface (i.e. metal) and thereafter depositing a material onto the second surface (i.e. SiO2-). Saly discloses the metal can be copper (column 4, lines 5-10) and therefore using copper and blocking such would have been obvious as Saly discloses blocking a metal and also discloses metals include copper. Therefore taken with Saly, such a process would have resulted in a metal oxide film as instantly claimed.
As for the reduction of the metal oxide using the SAM, Saly discloses using known SAM compounds and selecting such based-on head and tail groups with affinity for the blocked surface (column 2, lines 12-35). Kaufman-Osborn et al. discloses thiol (0029) and using the known SAM compound would have been obvious as predictable in the process of Saly. Additionally, as noted by the prior art Hashemi, also in the art of selective deposition via blocking with a SAM, the exposure of the copper oxide to the thiol will result in the reduction of the metal oxide as claimed ( “Cu oxide has been displaced by S−Cu on the surface, showing reduced Cu (Cu(0) or Cu(I), which have similar binding energies) after the samples are treated with thiols.”)
Alternatively, and at the very least, Hashemi disclose area selective deposition by using a SAM between copper and dielectric and discloses a thiol based SAM to reduce the metal oxide and bond the SAM to the copper for blocking and therefore taking the references collectively it would have been obvious to one of ordinary skill in the art at the time of the invention to have modified the cited prior art to use the thiol SAM to reduce the copper oxide layer and block deposition thereon for selective area deposition.
Claim 22: KR 370 discloses removing the oxidation prevention layer via a hydrogen gas treatment (“gas comprising H .sub.2 may be used in the first surface treatment process”) and discloses such heating to a temperature (“The temperature during the surface treatment is, for example, from about room temperature to about 400”). Kaufman-Osborn et al. discloses hydroxyl moiety treatment and heating to a temperature (“ temperature of between about 25° C. and about 400° C.”, 0043). Therefore, taking the references collectively it would have been obvious to have removed the antioxidation layer and form the hydroxyl moieties at a first and second temperature respectively with a reasonable expectation of predictable results as both are taught as being performed at a heated temperature. The examiner notes the collection of prior art fails to explicitly disclose the second temperature is less then the first temperature; however, the temperature is taught as a result effective variable directly affecting the treatment and it would have been obvious to have determined the optimum temperature through routine experimentation to reap the benefits of removal of the oxidation prevention layer and the hydroxyl moiety treatment. 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). Additionally, the ranges of the treatment overlap the claimed relationship and therefore make obvious such. Finally, the first and second temperature relationship is a selection of a finite number of predictable solution (first and second temperature are equal, first temperature is higher, second temperature is higher) and the claim would have been obvious because “a person of ordinary skill has good reason to pursue the known options with his or her technical grasp. If this leads to the anticipated success, it is likely the product not of innovation but of ordinary skill and common sense.”
Claim 25: As noted with respect to claim 22, KR 370 discloses removing the oxidation prevention layer using hydrogen atmosphere at a temperature. Additionally, Kaufman-Osborn et al. discloses using hydrogen atmosphere for the formation of the oxide layer (“Hydrogen gas and oxygen gas may also be utilized in combination to form hydroxyl moieties”) and therefore using a hydrogen atmosphere for the removal and the oxidation would have been obvious to one of ordinary skill in the art. Additionally, the temperature is a made obvious for the reasons set forth above with respect to claim 22.
Claim 27: Saly discloses selective deposition onto a first surface versus a second surface, wherein the first surface can be metal and second surface can be dielectric, including silicon oxide (column 4, lines 60-64) and discloses blocking deposition onto the first surface (i.e. metal) and thereafter depositing a material onto the second surface (i.e. SiO2-). Saly discloses the metal can be copper (column 4, lines 5-10) and therefore using copper and blocking such would have been obvious as Saly discloses blocking a metal and also discloses metals include copper.
Claim 28 Saly discloses silicon included materials (column 4, lines 60-64). Kaufman-Osborn et al. discloses silicon (0022, 0023).
Claim 29: Saly discloses using known SAM compounds and selecting such based-on head and tail groups with affinity for the blocked surface (column 2, lines 12-35). Kaufman-Osborn et al. discloses thiol (0029) and using the known SAM compound would have been obvious as predictable in the process of Saly.
Claim 30: Saly discloses deposition onto the second layer (column 7, line 64 to Column 8, line 5). Kaufman-Osborn et al. discloses forming a film on the surface of the second layer (0036).
Claim 31-32: KR 370 discloses the oxidation prevention layer, including BTA, or native oxide layer, prior to selective deposition (“the treatment process may remove native oxide layers present on the first metal-based surface”, “ the treatment may remove a passivation layer or hydrocarbon layer that may be present on the second metal-based surface, for example, the treatment may remove the BTA layer present on the Cu surface . In some embodiments, a passivation layer on the Cu surface, such as a BTA layer, may have been deposited to protect the Cu surface from oxidation during other processing steps”) and therefore having a BTA/native oxide layer on the Cu layer would have been obvious to one of ordinary skill in the art to protect the Cu surface during other process steps as suggested by KR 370.
Claim(s) 21, 22, 25, 27-32 is/are rejected under 35 U.S.C. 103 as being unpatentable over US Patent Application Publication US 20200043776 A1, hereinafter USPP 776 taken with KR 20180136730, hereinafter KR 370 as evidenced by or further in view of Hashemi et al. (Selective Deposition of Dielectrics: Limits and Advantages of Alkanethiol Blocking Agents on Metal−Dielectric Patterns).
Claim 1: USPP 776 discloses a film forming method for forming an object film on a substrate (Figure 1 and accompanying text), the method comprising: providing the substrate including an a first material formed on a surface of a first area (column 4, lines 54-65), and a layer of a second material formed on a surface of a second area, the second material being different from the first material (0020) forming an SAM on the first surface relative to the second surface by supplying a SAM precursor (0008 related to thiol molecules). USPP 776 discloses removing the material from the copper surface and thereafter oxidizing the copper to form a metal oxide to be more selective for the thiol deposition (0017-0018).
USPP 776 discloses a metal layer and dielectric layer and selective blocking and discloses the substrate can be subject to a pretreatment process including reduction (column 3, lines 118-22); however, fails to disclose the oxidation prevention layer as claimed and removal of such. However, KR 370 discloses for selective deposition of surfaces that include Cu, including a oxidation prevention layer to protect the Cu and removing the oxidation prevention layer prior to selective deposition (“the treatment process may remove native oxide layers present on the first metal-based surface”, “ the treatment may remove a passivation layer or hydrocarbon layer that may be present on the second metal-based surface, for example, the treatment may remove the BTA layer present on the Cu surface . In some embodiments, a passivation layer on the Cu surface, such as a BTA layer, may have been deposited to protect the Cu surface from oxidation during other processing steps”) and therefore having a BTA/native oxide layer on the Cu layer would have been obvious to one of ordinary skill in the art to protect the Cu surface during other process steps as suggested by KR 370. KR 370 explicitly discloses the protective oxidation prevention layer must be removed prior to selective deposition (“a passivation layer must be removed prior to the selective deposition process.”) and therefore providing such on the copper and thereafter removing of such would have been obvious to provide a surface for selective deposition.
As for the gaseous SAM, USPP 776 discloses “Thiols, on the other hand, are volatile, so wet chemistry is not necessary when using thiols as the inhibitor.”
As for the reduction of the metal oxide using the SAM, additionally, as noted by the prior art Hashemi, also in the art of selective deposition via blocking with a SAM, the exposure of the copper oxide to the thiol will result in the reduction of the metal oxide as claimed ( “Cu oxide has been displaced by S−Cu on the surface, showing reduced Cu (Cu(0) or Cu(I), which have similar binding energies) after the samples are treated with thiols.”)
Alternatively, and at the very least, Hashemi disclose area selective deposition by using a SAM between copper and dielectric and discloses a thiol based SAM to reduce the metal oxide and bond the SAM to the copper for blocking and therefore taking the references collectively it would have been obvious to one of ordinary skill in the art at the time of the invention to have modified the cited prior art to use the thiol SAM to reduce the copper oxide layer and block deposition thereon for selective area deposition.
Claim 22: KR 370 discloses removing the oxidation prevention layer via a hydrogen gas treatment (“gas comprising H .sub.2 may be used in the first surface treatment process”) and discloses such heating to a temperature (“The temperature during the surface treatment is, for example, from about room temperature to about 400”). Therefore, taking the references collectively it would have been obvious to have removed the antioxidation layer and form the hydroxyl moieties at a first and second temperature respectively with a reasonable expectation of predictable results as both are taught as being performed at a heated temperature. The examiner notes the collection of prior art fails to explicitly disclose the second temperature is less then the first temperature; however, the temperature is taught as a result effective variable directly affecting the treatment and it would have been obvious to have determined the optimum temperature through routine experimentation to reap the benefits of removal of the oxidation prevention layer and the hydroxyl moiety treatment. 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). Additionally, the ranges of the treatment overlap the claimed relationship and therefore make obvious such. Finally, the first and second temperature relationship is a selection of a finite number of predictable solution (first and second temperature are equal, first temperature is higher, second temperature is higher) and the claim would have been obvious because “a person of ordinary skill has good reason to pursue the known options with his or her technical grasp. If this leads to the anticipated success, it is likely the product not of innovation but of ordinary skill and common sense.”
Claim 27: USPP 776 discloses selective deposition onto a first surface versus a second surface, wherein the first surface is copper and second surface can be dielectric, including silicon oxide and discloses blocking deposition onto the first surface (i.e. metal) and thereafter depositing a material onto the second surface (i.e. 0020, Figure 3 and accompanying text).
Claim 28 USPP 776 discloses silicon included materials (0020, Figure 3 and accompanying text)
Claim 29: USPP 776 discloses thiol (0024) and using the known SAM compound would have been obvious as predictable in the process of Saly.
Claim 30: USPP discloses deposition onto the second layer (Figure 3 and accompanying text)
Claim 31-32: KR 370 discloses the oxidation prevention layer, including BTA, or native oxide layer, prior to selective deposition (“the treatment process may remove native oxide layers present on the first metal-based surface”, “ the treatment may remove a passivation layer or hydrocarbon layer that may be present on the second metal-based surface, for example, the treatment may remove the BTA layer present on the Cu surface . In some embodiments, a passivation layer on the Cu surface, such as a BTA layer, may have been deposited to protect the Cu surface from oxidation during other processing steps”) and therefore having a BTA/native oxide layer on the Cu layer would have been obvious to one of ordinary skill in the art to protect the Cu surface during other process steps as suggested by KR 370.
Claim(s) 25 is/are rejected under 35 U.S.C. 103 as being unpatentable over US Patent Application Publication US 20200043776 A1, hereinafter USPP 776 taken with KR 20180136730, hereinafter KR 370 as evidenced by or further in view of Hashemi et al. as applied above and further with Kaufman-Osborn et al.
As noted with respect to claim 22, KR 370 discloses removing the oxidation prevention layer using hydrogen atmosphere at a temperature. Additionally, the temperature is made obvious for the reasons set forth above with respect to claim 22. Additionally, Kaufman-Osborn et al. discloses hydroxyl moiety treatment and heating to a temperature (“ temperature of between about 25° C. and about 400° C.”, 0043). As for the requirement of oxidizing in a hydrogen atmosphere, Kaufman-Osborn et al. discloses using hydrogen atmosphere for the formation of the oxide layer (“Hydrogen gas and oxygen gas may also be utilized in combination to form hydroxyl moieties”) and therefore using a hydrogen atmosphere for the removal and the oxidation would have been obvious to one of ordinary skill in the art.
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 DAVID P TUROCY whose telephone number is (571)272-2940. The examiner can normally be reached Mon, Tues, Thurs, and Friday, 7:00 a.m. to 5:30 p.m.
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/DAVID P TUROCY/ Primary Examiner, Art Unit 1718
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