Rohm and Haas Electronic Materials LLCDownload PDFPatent Trials and Appeals BoardNov 12, 20202019006826 (P.T.A.B. Nov. 12, 2020) Copy Citation UNITED STATES PATENT AND TRADEMARK OFFICE UNITED STATES DEPARTMENT OF COMMERCE United States Patent and Trademark Office Address: COMMISSIONER FOR PATENTS P.O. Box 1450 Alexandria, Virginia 22313-1450 www.uspto.gov APPLICATION NO. FILING DATE FIRST NAMED INVENTOR ATTORNEY DOCKET NO. CONFIRMATION NO. 15/212,713 07/18/2016 Yi Qin 79353-US-NP 2053 53884 7590 11/12/2020 ROHM AND HAAS ELECTRONIC MATERIALS LLC c/o DUPONT SPECIALTY PRODUCTS USA, LLC P. O. Box 2915 974 Centre Road, Chestnut Run Plaza 721-2342 Wilmington, DE 19805 EXAMINER WONG, EDNA ART UNIT PAPER NUMBER 1795 NOTIFICATION DATE DELIVERY MODE 11/12/2020 ELECTRONIC Please find below and/or attached an Office communication concerning this application or proceeding. The time period for reply, if any, is set in the attached communication. Notice of the Office communication was sent electronically on above-indicated "Notification Date" to the following e-mail address(es): PTO-Legal.PRC@dupont.com PTOL-90A (Rev. 04/07) UNITED STATES PATENT AND TRADEMARK OFFICE BEFORE THE PATENT TRIAL AND APPEAL BOARD Ex parte YI QIN, KRISTEN FLAJSLIK, and MARK LEFEBVRE Appeal 2019-006826 Application 15/212,713 Technology Center 1700 Before ADRIENE LEPIANE HANLON, LINDA M. GAUDETTE, and JAMES C. HOUSEL, Administrative Patent Judges. HOUSEL, Administrative Patent Judge. DECISION ON APPEAL STATEMENT OF THE CASE Pursuant to 35 U.S.C. § 134(a), Appellant1 appeals from the Examiner’s decision to reject claims 2, 3, 6–8, 10–12, 15, 16, and 18 under 35 U.S.C. § 103 as unpatentable over Lu (US 7,023,089 B1, iss. Apr. 4, 2006) in view of Kazarov (Characteristics of Cathodic Deposition of Indium from Electrolytes Containing Compounds with a Thione Group, 7 1 We use the word “Appellant” to refer to “applicant” as defined in 37 C.F.R. § 1.42. Appellant identifies the real party in interest as DuPont de Nemours, Inc., through its wholly owned subsidiary, Rohm and Haas Electronic Materials, LLC. Appeal Brief (“Appeal Br.”) filed May 31, 2019, 2. Appeal 2019-006826 Application 15/212,713 2 Khimcheskaya Tekhnologiya 108–115 (1967)) and Szocs (US 2011/0103022 A1, pub. May 5, 2011). We have jurisdiction under 35 U.S.C. § 6(b). We AFFIRM.2 CLAIMED SUBJECT MATTER The invention relates to a method for electroplating indium (“In”) on metal layers. Specification (“Spec.”) filed July 18, 2016, 1:4–5. Appellant discloses that it is challenging to reproducibly plate void-free, uniform In of target thickness and smooth surface morphology onto metal. Id. at 1:10–11. According to Appellant, because In reduction potentials are more negative than proton reduction potentials, significant hydrogen bubbling at the cathode causes increased surface roughness. Id. at 1:11–13. Also, in the absence of a complexing agent, In ions begin to precipitate from solutions having a pH > 3. Id. at 1:15–16. Moreover, Appellant discloses that metals such as nickel, tin, copper, and gold are good catalysts for proton reduction and are more noble than In, thus leading to In corrosion and intermetallic compounds. Id. at 1:16–20. As such, “conventional indium electroplating baths have not been able to electroplate indium with high coplanarity and high surface planarity on substrates which include nickel.” Id. at 1:24–26. To address these issues, Appellant discloses In plating compositions including a source of In ions, at least one thiourea or derivative thereof, and citric acid or salts or mixtures thereof. Id. at 2:20–32. 2 This Decision also cites the Final Office Action (“Final Act.”) dated January 3, 2019, the Examiner’s Answer (“Ans.”) dated July 25, 2019, and the Reply Brief (“Reply Br.”) filed September 19, 2019. Appeal 2019-006826 Application 15/212,713 3 Claim 10, reproduced below from the Claims Appendix to the Appeal Brief, is illustrative of the claimed subject matter: 10. A method comprising: a) providing a substrate comprising a nickel layer; b) contacting the substrate with an indium electroplating composition comprising one or more sources of indium ions, wherein the one or more sources of indium ions are chosen from indium salts of alkane sulfonic acids, indium salts of aromatic sulfonic acids, indium salts of sulfamic acid, sulfate salts of indium, nitrate salts of indium, hydroxide salts of indium, indium oxides, fluoroborate salts of indium, indium salts of carboxylic acids and indium salts of amino acids, one or more thiourea derivatives and 50 g/L to 300 g/L citric acid, salt of citric acid or mixtures thereof, wherein the indium electroplating composition is free of alloying metals and free of hydrogen suppressors chosen from epihalohydrin copolymers, and, wherein a pH of the indium electroplating composition is 1-4; and c) electroplating an indium metal layer on the nickel layer of the substrate with the indium electroplating composition. OPINION We review the appealed rejection for error based upon the issues Appellant identifies, and in light of the arguments and evidence produced thereon. Ex parte Frye, 94 USPQ2d 1072, 1075 (BPAI 2010) (precedential) (cited with approval in In re Jung, 637 F.3d 1356, 1365 (Fed. Cir. 2011) (“[I]t has long been the Board’s practice to require an applicant to identify the alleged error in the examiner’s rejections.”). After considering the argued claims and each of Appellant’s arguments, we are not persuaded of Appeal 2019-006826 Application 15/212,713 4 reversible error in the pending rejection. We offer the following for emphasis only. The Examiner finds that Lu teaches a method comprising providing a substrate having a nickel (“Ni”) layer, contacting the substrate with an In composition, and plating an In metal layer onto the Ni layer with the In composition. Ans. 3–4. The Examiner acknowledges that Lu fails to teach that the In composition includes: 1) a source of In ions chosen from indium salts of alkane sulfonic acids, indium salts of aromatic sulfonic acids, indium salts of sulfamic acid, sulfate salts of indium, nitrate salts of indium, hydroxide salts of indium, indium oxides, fluoroborate salts of indium, indium salts of carboxylic acids and indium salts of amino acids; 2) one or more thiourea derivatives; and 3) 50 g/L to 300 g/L citric acid, salt of citric acid or mixtures thereof; but is free of alloying metals and epihalohydrin copolymer hydrogen suppressors. Id. at 4–5, 7. For these features, the Examiner turns to Kazarov’s teaching of a method of electrodepositing In using an In(SO4)3 solution containing thiourea or derivatives thereof to accelerate In ionization and deposition and Szocs’ teaching of a method of In electrochemical deposition onto a nickel coated substrate using chelating agents such as citric acid and salts thereof to control the amount of In ions available for electroplating. Id. at 5–6, 7. The Examiner, therefore, concludes that it would have been obvious to have modified Lu’s process to electroplate an In layer from a composition comprising In(SO4)3, a thiourea derivative for accelerating In ionization and deposition, and citric acid chelating agent to control the amount of In ions available for electroplating. Id. at 6, 8. Appeal 2019-006826 Application 15/212,713 5 Appellant argues that Kazarov fails to remedy deficiencies in Lu’s method because Kazarov teaches cathodic separation rather than cathodic deposition. Appeal Br. 4–5, citing Kazarov 1, ¶ 4.3 In addition, Appellant argues that Szocs fails to remedy the deficiencies in Lu and Kazarov because Szocs requires the presence of epihalohydrin copolymer in the In plating composition for suppressing hydrogen gas formation to enable a smooth and uniform In deposit. Id. at 5, citing Szocs ¶ 68 and Fig. 2. Appellant contends that Szocs teaches that excluding epihalohydrin copolymer from the In plating composition results in a spongy, non-uniform In deposit. Id., citing Szocs ¶ 64 and Fig. 1. As such, Appellant asserts that Szocs teaches away from the claimed method which excludes epihalohydrin copolymer as a hydrogen suppressor. Id. at 6. Appellant’s arguments fail to persuade us of reversible error. Initially, we note that Appellant’s argument regarding Kazarov is based on a different translation than relied on by the Examiner. Appellant relies on a different translation of Kazaraov than the Examiner. The Examiner relies on a July 2019 English-language translation prepared for the United States Patent and Trademark Office by Schreiber Translations, Inc. Kazarov Translation 2 (“Trans. 2”) mailed July 25, 2019. A review of the two translations relied on by Appeallant and the Examiner reveals that they are substantially the same except in one significant aspect—Appellant translates the Russian word, 3 Appellant’s citation of Kazarov is from an undated English-language translation prepared by the Republican Inter-Institutional Scientific and Technical Reports. Kazarov Translation 1 (“Trans. 1”) filed August 27, 2018. Appeal 2019-006826 Application 15/212,713 6 Выделения, as “separation,” whereas the Examiner’s translates this word as “deposition.” Compare the titles of Trans. 1 with Trans. 2. We note that the Examiner provided Translation 2 with the Examiner’s Answer and Appellant fails to dispute or otherwise address this translation in the Reply Brief. Compare Ans. 16 with Reply Br. 2–3. Moreover, a careful review of each translation indicates that those skilled in this art would understand that the original Russian-language version of Kazarov is directed to the cathodic deposition of In separated from an acidic In(SO4)3 electrolyte solution containing thiourea or derivatives thereof. For example, Translation 1 states that “[t]he process of cathodic separation of indium appeared to be very convenient for studying a depolarizing effect of the certain additives, since it proceeds at a high degree of irreversibility in acid electrolytes even in the absence of other additives.” Trans. 1, p. 2. As Appellant discloses (and Szocs confirms), electrochemical deposition of In occurs when an electrolytic current is applied to an acidic In source. Compare Spec. 5:23 with Szocs ¶ 20. Further, Translation 1 discloses that the experiments used mercury or mercury-indium amalgam electrodes with an electrolyte solution containing In(SO4)3. Trans. 1, p. 2, Experimental procedure. Cathodic separation using mercury electrodes in such an electrolyte solution logically can only refer to In separation from the electrolyte solution onto the electrodes, i.e., deposition of In onto the cathode. Additionally, Translation 1 specifically states that “Figure 1 shows the kinetic curves of cathodic separation of indium on the mercury dropping electrode from a pure sulfuric acid electrolyte (dashed line) and electrolyte with additives.” Trans. 1, p. 2, Results and discussion, first sentence (emphasis added). This sentence clearly states that the cathodic separation of Appeal 2019-006826 Application 15/212,713 7 In refers to the separation of In from the electrolyte solution on (onto) the cathode. Thus, although Appellant’s Translation 1 superficially appears to be in conflict with the Examiner’s Translation 2, we find a preponderance of the evidence supports the view that these translations are directed to the same concept—electrochemical deposition of In. As such, we are not persuaded that the Examiner erred in relying on Kazarov’s teaching regarding the use of thiourea for accelerating In ionization and deposition. We turn next to Appellant’s argument that Szocs teaches away from an In electrolyte solution free of epihalohydrin copolymer for use as a hydrogen suppressor. Teaching away requires a reference to actually criticize, discredit, or otherwise discourage the claimed solution. See In re Fulton, 391 F.3d 1195, 1201 (Fed. Cir. 2004). However, “[a] teaching that a composition may be optimal or standard does not criticize, discredit, or otherwise discourage investigation into other compositions.” Galderma Labs., LP v. Tolmar, Inc., 737 F.3d 731, 738–39 (Fed. Cir. 2013). In determining obviousness, “[a] reference must be considered for everything that it teaches, not simply the described invention or a preferred embodiment.” In re Applied Materials Inc., 692 F.3d 1289, 1298 (Fed. Cir. 2012). “Although a reference that teaches away is a significant factor to be considered in determining unobviousness, the nature of the teaching is highly relevant, and must be weighed in substance.” In re Gurley, 27 F.3d 551, 553 (Fed. Cir. 1994). For instance, when there is nothing within the reference teaching that the claimed element should not, or cannot, be used, and further cited prior art teaches the propriety of employing the missing element, the teachings of both reference must be weighed together. Para- Appeal 2019-006826 Application 15/212,713 8 Ordnance Mfg., Inc. v. SGS Importers Int'l, Inc., 73 F.3d 1085, 1090 (Fed. Cir. 1995). Here, we note (as did the Examiner, Ans. 16) that Kazarov’s In electrolyte solution is free of epihalohydrin copolymer. Kazarov 10, Table 2. Further Szocs, particularly as relied on by the Examiner, does not teach away from the use of citric acid in the absence of epihalohydrin copolymer hydrogen suppressors. Instead, Appellant points to paragraphs 64 and 68 as teaching away from the exclusion per se of epihalohydrin copolymers from In electrochemical plating compositions. In paragraph 64, Szocs states that the In deposit as shown in Figure 1 was spongy in appearance and was non- uniform. Szocs ¶ 64. Szocs speculates that “[t]he spongy and non-uniform surface was . . . caused by the evolution of hydrogen gas during indium metal deposition and the decomposition of organic additives in the indium composition.” Id. In paragraph 68, Szocs states that “the indium electrochemical composition with the imidazole-epichlorohydrin copolymer had an improved indium metal deposit in contrast to the comparative indium composition.” Id. ¶ 68. However, Szocs’ comparison is not a direct comparison between In compositions with and without epihalohydrin copolymers. Szocs’ Figure 1 result was obtained with an aqueous composition comprising 30 g/l indium sulfate, 70 g/l ammonium hydroxide, 80 g/l boric acid, 300 g/l tartaric acid, and 0.5 g/l “[c]onventional indium electroplating bath additives” at a pH of 3. Szocs ¶ 61. In contrast, Szocs’ Figure 2 result was obtained with an aqueous composition comprising twice the amount of indium sulfate, 30 g/l methane sulfonic acid, and 100 g/l imidazole-epichlorohydrin copolymer at a pH of 1–1.2. Furthermore, Figure 2 is the result after deposition continued Appeal 2019-006826 Application 15/212,713 9 until an In layer thickness of 200 µm was obtained, which is about 10 times the likely layer thickness of Figure 1. These substantial differences in conditions render the comparison between Figures 1 and 2 of little probative value, especially with regard to whether Szocs teaches away from use of citric acid in the absence of epihalohydrin copolymer. As such, those skilled in the art would have understood Szocs as teaching that epihalohydrin copolymer is a preferred or optimal component of In electrochemical compositions, and not as a teaching away from In compositions with citric acid chelator and without this component. Accordingly, as Appellant fails to identify reversible error, we sustain the Examiner’s obviousness rejection of claim 10. Also because Appellant does not separately argue dependent claims 2, 3, 6–8, 11, 12, 15, 16, and 18, we likewise sustain the Examiner’s obviousness rejection of these claims. See 37 C.F.R. § 41.37(c)(1)(iv) (2018). CONCLUSION Upon consideration of the record and for the reasons set forth above and in the Examiner’s Answer, the Examiner’s decision to reject claims 2, 3, 6–8, 10–12, 15, 16, and 18 under 35 U.S.C. § 103 as unpatentable over Lu in view of Kazarov and Szocs is affirmed. DECISION SUMMARY In summary: Claims Rejected 35 U.S.C. § Reference(s)/Basis Affirmed Reversed 2, 3, 6–8, 10–12, 15, 16, 18 103 Lu, Kazarov, Szocs 2, 3, 6–8, 10–12, 15, 16, 18 Appeal 2019-006826 Application 15/212,713 10 TIME PERIOD FOR RESPONSE No time period for taking any subsequent action in connection with this appeal may be extended under 37 C.F.R. § 1.136(a). See 37 C.F.R. § 1.136(a)(1)(iv). AFFIRMED Copy with citationCopy as parenthetical citation