DETAILED ACTION
Notice of Pre-AIA or AIA Status
1. 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 § 112
2. 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.
3. Claim 18 is 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.
The term “the metal” of Claim 18 lacks clarity since it is unclear if it is referring to “the first metal” or “the second metal” listed of Claim 1 from which Claim 18 depends. Correction is required.
Claim Rejections - 35 USC § 103
4 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.
5. 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.
6. Claims 1, 2, 3, 4, 5, 6, 9, 10, 11, 12, 13, 14, 15, 16, 17,18, and 19 are rejected under 35 U.S.C. 103 as being unpatentable over Amit et al. and Janz et al.
Amit et al. (“Electrochemical deposition of N-heterocyclic carbene monolayers on metal surfaces,” Nat. Comm. 2020, 11, article 5714, pg. 1-10) is directed toward the electrodeposition of NHCs on metal surfaces (pg. 1: title). Janz et al. (“The Silver-Silver Halide Electrodes,” Chem. Rev. 1953, 53(3), 397-437) is directed toward silver halide electrodes (pg. 397: title).
Regarding Claim 1, Amit et al. discloses a method of forming a coating on a metal surface of a substrate (pg. 1: abstract, pg. 2: Fig. 2, and pg. 8: methods – electrochemical deposition) using an electrochemical deposition setup consisting of a conventional three-electrode cell. The method of Amit et al. further describes applying a positive potential to a first metal surface on a substrate to form a working electrode (100 nm Au film that have been vapor-deposited onto an n-type silicon wafer) and applying a negative potential to a second metal surface or a conductive surface of a substrate to form a counter electrode (a platinum wire) as per pg. 8: methods – electrochemical deposition. Amit et al. teaches disposing the working electrode and counter electrode in a solution comprising a salt of a carbene (e.g.: 1,3-bis(2,4-dinitrophenyl)-imidazolium bromide salt or 1,3-dimethyl-benzimidazolium iodide), thus producing a coated metal surface after the application of voltage (pg. 8: methods – electrochemical deposition). Amit et al. indicates the electrodeposition of carbene films onto Si-coated with Ag, Pd, and Pt as the working electrode was also achieved (pg. 8: methods – electrochemical deposition).
[AltContent: textbox ([img-media_image1.png]
Fig. 2: Mechanism of Electrodeposition of Carbene Salt on Metallized Surface (pg. 2))]
Amit et al. discloses the use of a silver-based reference electrode in the form of Ag/AgBr. This differs from the limitations of Claim 1 which requires the use of a Ag/AgCl reference electrode. A reference electrode is simply use to provide a known potential to which the applied potentials in the electrochemical cell are compared/controlled. Since both silver-halide electrodes are for the purpose of a reference potential and both are based on the Ag0/Ag+ redox couple, they are recognized as equivalent in the art. In particular, Janz et al. teaches in the introduction that silver halide electrodes (e.g.: AgCl and AgBr) are reference standards with a number of advantages (pg. 397). Silver halide electrodes are easy to manufacture, have high reproducibility, are compact, offer direct use in an electrochemical cell, and avoid the uncertainty of liquid junction potentials (pg. 397: introduction). Silver halides are electrodes of the second kind having a solid phase in the form of a sparingly soluble salt (i.e.: AgBr or AgCl) in equilibrium with a saturated solution of this salt participating in the electrode process. A familiar example is the silver-silver chloride electrode (pg. 3978: introduction) and as explained on pg. 423 has similar properties to the silver bromide electrode regarding aging and exposure to oxygen. Therefore, it would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention in light of the disclosure in Janz et al. to substitute the Ag/AgCl reference electrode for the Ag/AgBr in Amit et al. The skilled artisan would reasonably expect facile deposition of the carbene film onto the substrate as the reference electrode swap is substitution of one known element for another known with the same purpose. See MPEP 2144.06.
Regarding Claim 2, Amit et al. and Janz et al. disclose the method of Claim 1, wherein the conductive surface comprises silicon as per pg. 2: Fig. 2, and pg. 8: methods – electrochemical deposition.
Regarding Claim 3, Amit et al. and Janz et al. disclose the method of Claim 1, wherein the second metal surface comprises a metal that is the same as the metal of the working electrode (i.e.: Pt) as evidenced by the deposition of a carbene film onto a silicon wafer coated with Pt (as the working electrode) and a platinum wire as the counter electrode (pg. 8: methods – electrochemical deposition).
Regarding Claim 4, Amit et al. and Janz et al. disclose the method of Claim 3, wherein the first metal surface comprises gold as evidenced by pg. 2: Fig. 2, and pg. 8: methods – electrochemical deposition.
Regarding Claim 5, Amit et al. and Janz et al. disclose the method of Claim 1, wherein the first metal surface is substantially unprotected as supported by pg. 8: methods – electrochemical deposition section, which described the vapor deposition of gold onto the silicon wafer occurring under a nitrogen atmosphere which would necessarily form metallic gold (which not protected by an oxide nor another coating layer). The term substantially unprotected is not considered a relative term since it is defined in ¶51 of the instant application (referenced from US Pub. No. 2024/0175164 A1).
Regarding Claim 6, Amit et al. and Janz et al. disclose the method of Claim 5, wherein substantially unprotected is substantially unoxidized as supported by pg. 8: methods – electrochemical deposition section, which described the vapor deposition of gold onto the silicon wafer occurring under a nitrogen atmosphere which would necessarily form metallic gold (which not protected by an oxide nor another coating layer).
Regarding Claim 9, Amit et al. and Janz et al. disclose the method of Claim 1, wherein the positive potential is in a range of 0.1 to 2.0 V as supported by Amit et al. which the generation of hydroxide under the positive applied potential deprotonates the carbene cation forming the free carbene which resulting in deposition of a free-carbene film onto the Au-coated silicon wafer (pg. 2: Fig. 2, and pg. 8: methods – electrochemical deposition) with an applied potential of 1 V.
Regarding Claim 10, Amit et al. and Janz et al. disclose the method of Claim 1, wherein the working electrode comprises gold (vapored deposited onto a silicon wafer) as supported by pg. 2: Fig. 2, and pg. 8: methods – electrochemical deposition.
Regarding Claim 11, Amit et al. and Janz et al. disclose the method of Claim 9, wherein the positive potential is in a range of 0.8 to 1.0 V as supported by Amit et al. which the generation of hydroxide under the positive applied potential deprotonates the carbene cation forming the free carbene which deposits onto the Au-coated silicon wafer (pg. 2: Fig. 2, and pg. 8: methods – electrochemical deposition) with an applied potential of 1V.
Regarding Claim 12, Amit et al. and Janz et al. disclose the method of Claim 1, wherein the coating is an electron passivation layer as supported by Amit et al. where the formation of a single monolayer of deprotonated NHC is discussed (pg. 8: EC deposition of a dimethyl-benzimidazole monolayer on Au film). The formation of a monolayer indicates that the reduction of water under applied voltage to form hydroxide is suppressed since no more NHC deposits on the gold surface. Suppression of the electro-reduction of water means the transfer of electrons is necessarily suppressed meaning electron passivation has occurred. Moreover, organic coatings deposited onto metal surface are known to increase the electrical resistivity of the coated metal article, which also is characterized as an electron passivation layer.
Regarding Claim 13,The method of Claim 1, wherein the coating prevents or reduces corrosion as supported by Amit et al. (and Janz et al.) where the formation of a single monolayer of deprotonated NHC is discussed (pg. 8: EC deposition of a dimethyl-benzimidazole monolayer on Au film). The formation of a monolayer indicates that the reduction of water under applied voltage to form hydroxide is suppressed since no more NHC deposits on the gold surface. Suppression of the electro-reduction of water means the transfer of electrons is necessarily suppressed indicating electron passivation has occurred. Moreover, organic coatings deposited onto metal surface are known to increase the electrical resistivity of the coated metal article, which also forms an electron passivation layer. The aforementioned properties of the deposited NHC layer onto the metal film would reduce corrosion since the coated metal article is resistant to both electron transfer and attack from corrosion species (that can potentially reach the bare metal surface) in the form of physical barrier.
Regarding Claim 14, Amit et al. and Janz et al. disclose the method of Claim 1, wherein once coated, the first metal surface has reduced reactivity relative to its uncoated form. In particular, Amit et al. indicates only a single monolayer of deprotonated NHC forms on the metallized surface (pg. 8: EC deposition of a dimethyl-benzimidazole monolayer on Au film). The formation of a monolayer indicates that the reduction of water under applied voltage to form hydroxide is suppressed since NHC deposition on the gold surface is self-limiting. Suppression of the electro-reduction of water indicates the transfer of electrons is necessarily suppressed meaning electron passivation has occurred and the reactivity relative to the uncoated metallized surface has been reduced.
Regarding Claim 15 and Claim 16, Amit et al. and Janz et al. disclose the method of Claim 1, wherein the disposing in the solution occurs for 5 minutes (pg. 8: methods – electrochemical deposition). A prima facie case of obviousness exists when the prior art discloses an example that falls within the claimed range (i.e.: 1 min to 5 h for Claim 15 and 1 minute to 5 h for Claim 16 for the disposing time). See MPEP 2144.05(I) - OVERLAPPING, APPROACHING, AND SIMILAR RANGES, AMOUNTS, AND PROPORTIONS.
Regarding Claim 17, Amit et al. and Janz et al. disclose the method of Claim 1, further comprising a reference electrode which is a Ag/AgBr electrode as indicated on pg. 8: methods – electrochemical deposition.
Regarding Claim 18, Amit et al. and Janz et al. disclose the method of Claim 1, wherein the metal is palladium, silver, platinum, or gold as indicated on pg. 8: methods – electrochemical deposition.
Regarding Claim 19, Amit et al. discloses the method of Claim 1, wherein the free carbene is a N-heterocyclic carbene benzimidazole as supported by Fig. 2 and Fig. 1b.[AltContent: textbox ([img-media_image2.png]
Fig. 1b: NHCs used in Amit et al. to make organic film on metal surface (pg. 2))]
7. Claims 7 and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Amit et al. AND Janz et al. as applied to Claim 1 above and further in view of Crudden-2019.
Amit et al. (“Electrochemical deposition of N-heterocyclic carbene monolayers on metal surfaces,” Nat. Comm. 2020, 11, article 5714, pg. 1-10) is directed toward the electrodeposition of NHCs on metal surfaces (pg. 1: title). Janz et al. (“The Silver-Silver Halide Electrodes,” Chem. Rev. 1953, 53(3), 397-437) is directed toward silver halide electrodes (pg. 397: title). Crudden-2019 (US Pub. No. 2019/0169132 A1) is directed toward a method of forming a carbene-functionalized composite material.
Regarding Claim 7, Amit et al. and Janz et al. disclose the method of Claim 1, but specifically discloses the where the counter ion of the NHC-cation is a halide. The two NHC cations taught in Amit et al. are depicted in Fig. 1b below from Amit et al., one of which is a heterocyclic carbene benzimidazolium species as required by Claim 7. However, Amit et al. is silent on the salt of the NHC-cation being a hydrogen carbonate salt.
[AltContent: textbox ([img-media_image2.png]
Fig. 1b: NHCs used in Amit et al. to make organic film on metal surface (pg. 2))]
One of ordinary skill in the art would reasonably expect that NHC-cations with different counter anions (halide vs. hydrogen carbonate) would behave similarly under an applied positive potential. One such reference Crudden-2019 offers support for this expectation. Crudden-2019 is directed toward methods of forming carbene-functionalized composite materials (title) meaning it is equivalent art to Amit et al. In particular, Crudden-2019 discloses the use of the hydrogen carbonate salts depicted in FIG. 1C (reproduced below). In ¶304, Crudden-2019 indicates that free NHCs are typically prepared by deprotonation of corresponding (benz)imidazolium salts with strong bases (e.g.: alkoxides, hydroxides, and amides). Crudden-2019 further explains in ¶368 that NHC hydrogen carbonate carbene precursors are capable of being deprotonated by the counter anion (i.e. HCO31-) resulting in solution which form self-assembled carbene monolayers on metal surfaces. In ¶31, Crudden-2019 disclose the use of the following examples of NHC-cation hydrogen carbonate: 1,3-Diisopropylbenzimidazolium hydrogen carbonate (3a), 1,3-Dimethylbenzimidazolium hydrogen carbonate (3b), 5-((12-(4-(Ferrocenyl)-1H-1,2,3-triazol-1-yl)dodecyl)oxy)-1,3-diisopropyl-1H-benzo[d]imidazol-3-ium hydrogen carbonate (3c), or 5-(Dodecyloxy)-1,3-diisopropyl-1H-benzo[d]imidazol-3-ium hydrogen carbonate (3d).
Prior to the effect filing date of the claimed invention, one of ordinary skill in the art would reasonably expect that substituting an NHC-cation with a halide counter anion with an NHC-cation with a hydrogen carbonate counter anion (of Crudden-2019) in the method of depositing taught by Amit et al. (and Janz et al.) would result in the deposition of a free-NHC film onto the gold coated silicon wafer (i.e.: the substrate).
[AltContent: textbox ([img-media_image3.png]
Fig. 1c: NHCs used in Crudden-2019)]
Regarding Claim 8, Amit et al. and Janz et al. in view of Crudden-2019 discloses the method of Claim 7, wherein the N-heterocyclic carbene benzimidazolium hydrogen carbonate salt is 5-(dodecyloxy)-1,3-diisopropyl-1H-benzo[d]imidazole-3-ium hydrogen carbonate (NHC-2·HCO3) as evidenced by the use of Ex. 3d (¶31 of Crudden-2019).
8. Claim 20 is rejected under 35 U.S.C. 103 as being unpatentable over Amit et al. and Janz et al. as applied to Claim 19 above and further in view of Crudden-2019.
Amit et al. (“Electrochemical deposition of N-heterocyclic carbene monolayers on metal surfaces,” Nat. Comm. 2020, 11, article 5714, pg. 1-10) is directed toward the electrodeposition of NHCs on metal surfaces (pg. 1: title). Janz et al. (“The Silver-Silver Halide Electrodes,” Chem. Rev. 1953, 53(3), 397-437) is directed toward silver halide electrodes (pg. 397: title). Crudden-2019 (US Pub. No. 2019/0169132 A1) is directed toward a method of forming a carbene-functionalized composite material.
Regarding Claim 20, Amit et al. and Janz et al. disclose the method of Claim 19, but are silent on where the N-heterocyclic carbene benzimidazole is 1,3-diisopropyl-5-(dodecyloxy)-1H-benzo[d]imidazole-2-ylidene (NHC-2).
One of ordinary skill in the art would reasonably expect that NHC-cations with different counter anions (halide vs. hydrogen carbonate) would behave similarly under an applied positive potential. One such reference Crudden-2019 offers support for this expectation. Crudden-2019 is directed toward methods of forming carbene-functionalized composite materials (title) meaning it is equivalent art to Amit et al. In particular, Crudden-2019 discloses the use of the hydrogen carbonate salts depicted in FIG. 1C (reproduced below). In ¶304, Crudden-2019 indicates that free NHCs are typically prepared by deprotonation of corresponding (benz)imidazolium salts with strong bases (e.g.: alkoxides, hydroxides, and amides). Crudden-2019 further explains in ¶368 that NHC hydrogen carbonate carbene precursors are capable of being deprotonated by the counter anion (i.e. HCO31-) resulting in solution which form self-assembled carbene monolayers on metal surfaces. In ¶31, Crudden-2019 disclose the use of the following examples of NHC-cation hydrogen carbonate: 1,3-Diisopropylbenzimidazolium hydrogen carbonate (3a), 1,3-Dimethylbenzimidazolium hydrogen carbonate (3b), 5-((12-(4-(Ferrocenyl)-1H-1,2,3-triazol-1-yl)dodecyl)oxy)-1,3-diisopropyl-1H-benzo[d]imidazol-3-ium hydrogen carbonate (3c), or 5-(Dodecyloxy)-1,3-diisopropyl-1H-benzo[d]imidazol-3-ium hydrogen carbonate (3d).
Prior to the effect filing date of the claimed invention, one of ordinary skill in the art would reasonably expect that substituting the benzimidazolium NHC-cation halide with the benzimidazolium NHC-cation with a hydrogen carbonate counter anion (of Crudden-2019) in the method of depositing taught by Amit et al. (and Janz et al.) would result in the deposition of a free-NHC film onto the gold coated silicon wafer (i.e.: the substrate).
Conclusion
9. The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Crudden-2016 (US Pub. No 2016/0199875 A1) is directed toward carbene-functionalized composite materials (title). Mariampilla et al. (US Pub. No. 2020/0283911 A1) is directed toward etching metal using NHCs (title)
10. Any inquiry concerning this communication or earlier communications from the examiner should be directed to KEVIN SYLVESTER whose telephone number is 703-756-5536. The examiner can normally be reached Mon - Fri 8:15 AM to 4:30 PM EST.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, James Lin can be reached at (571)272-8902. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
11. Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/KEVIN SYLVESTER/Examiner, Art Unit 1794
/JAMES LIN/Supervisory Patent Examiner, Art Unit 1794
Prosecution Insights