DETAILED ACTION
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on March 9, 2026 has been entered.
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
In the amendment filed on March 9, 2026, claims 1 – 9 are pending. Claims 1 and 10 have been amended. Claim 10 has been withdrawn from consideration.
Election/Restrictions
Claim 10 is withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on May 23, 2025.
Claim Rejections - 35 USC § 102
The rejections of the claims under 35 USC § 102 in the previous Office Action are withdrawn due to Applicant amendment.
Claim Rejections - 35 USC § 103
The rejections of the claims under 35 USC § 103 in the previous Office Action are withdrawn due to Applicant amendment.
Claim(s) 1 – 9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Wade et al. US 20030129306 A1 (hereafter “Wade”) in view of either Hämäläinen et al. “Atomic Layer Deposition of Noble Metals and Their Oxides”. Chemistry of Materials (2014), 26, 786 – 801 or Park et al. “Metallorganic Chemical Vapor Deposition of Ru and RuO2 Using Ruthenocene Precursor and Oxygen Gas”. (2000) J. Electrochem. Soc. 147 203 (hereafter “Park”).
Regarding claims 1, 2, 3, 4, 5, 6, 7, 8, 9:
Wade is directed to a method of depositing ruthenium films on substrates by liquid source chemical vapor deposition (CVD) (Abstract; [0002]). Wade discloses that their CVD method comprises: supplying a liquid ruthenium film precursor, e.g. Ru(Cp)2 or Ru(EtCp)2 [meeting claims 2, 3, 4] and an oxygen source gas, e.g. O2 ([0040], [0050], [0090], [0057] – [0072]) to a substrate inside a chamber with a pressure of 8 Torr [under vacuum, meeting in part claim 9], wherein the substrate temperature is within a range between 100°C to 500°C; and forming a ruthenium film from the supplied ruthenium film precursor and oxygen source ([0012], [0039], [0090], [0057] – [0072]). The substrate may be e.g. a thermal oxide substrate, seeded with a tantalum pentoxide or ruthenium oxide layer [metal oxide] ([0039]).
Wade discloses that the process is intended to be limited to a kinetic-limited temperature regime characterized by relatively low temperatures (Abstract; [0002], ) in contrast to a mass-transfer limited regime ([0009]). When deposited under kinetic-limited temperature and using a liquid precursor, Wade indicates that relatively pure and thin ruthenium films can be deposited ([0010], [0039]).
While Wade does not expressly teach an embodiment of their method that sets a temperature of the substrate less than 150°C, Wade discloses an overlapping range. In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990); In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d 1362, 1365-66(Fed. Cir. 1997). See MPEP 2144.05.
Wade does not expressly teach that the supply of the metal complex compound having the cyclopentadienyl ligand removes metal oxide.
As noted above, Wade discloses that ruthenium film is deposited under conditions falling within a kinetic-limited temperature regime. Wade further discloses that the precursor is vaporized to a temperature of about 100 – 300°C to form the CVD material source gas for processing ([0012]); and that kinetic-limited temperature regime is characterized by the chemical reactions at the substrate surface being determinative of the deposition rate of the ruthenium film ([0043]). In other words, the CVD reaction is surface-mediated.
Hämäläinen is directed to review of atomic layer deposition methods for depositing noble metals and their oxides (Abstract). As depicted in Fig. 9, reproduced below with annotations, Hämäläinen discloses a layer-by-layer deposition of a noble metal film, where preceding metal atomic has a surface metal oxide layer that is subsequently removed by supplied metal organic complexes (page 792 – 795). In Fig. 9 as reproduced below, the step corresponds to the picture depicted in the upper left corner of the figure to the upper right corner of the figure. Hämäläinen also specifically discusses an ALD process of depositing ruthenium metal using oxygen and Ru(Cp)(CO)2Et [ruthenium with a cyclopentadienyl ligand “Cp”] and another of depositing ruthenium metal using oxygen and RuCp2 (page 793; Table 4). As clearly depicted within Figure 9, the underlying ruthenium layer has the metal of the Ru-ligand complex absorbed onto the metal oxide layer and the oxygen present on the surface released with carbon as carbon dioxide and water.
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While ALD is a type of chemical vapor deposition technique distinct from the concurrent flow chemical vapor deposition as taught by Wade, ALD is characterized by surface-mediated half reactions; ALD’s characterization is known to those of ordinary skill in the art as well as implied by Hämäläinen.
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have recognized that the formation of a ruthenium film under kinetic limited conditions as taught by Wade would also remove metal oxides, such as from a ruthenium oxide seed-layered substrate or a substrate defined by the growing film of ruthenium metal with surface oxygen because Wade teaches that the reaction of the ruthenium precursor having a cyclopentadienyl group is surface-mediated, and Hämäläinen discloses that the formation of noble metal films entails the reaction of surface oxygen atoms with the ruthenium precursor in order to form ruthenium metal. Alternatively, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the conditions of the method of Wade to remove metal oxides in order to form pure ruthenium films, as taught by Wade and Hämäläinen.
Alternatively Park, directed to the deposition of ruthenium and ruthenium dioxide films by CVD under a surface-mediated temperature regime (Abstract, page 207 1st col ) discloses that surface-mediated CVD of ruthenium films require surface-absorbed oxygen (page 208 2nd col). In the ruthenium-forward reaction, the absorbed oxygen is reacted with the cyclopentadienyl ligand to form organic byproducts. Park discloses that a surface-mediated temperature regime may be deposition by CVD at temperatures less than 275°C.
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have recognized that the formation of a ruthenium film under kinetic limited conditions as taught by Wade would also remove metal oxides, such as from a ruthenium oxide seed-layered substrate or a substrate defined by the growing film of ruthenium metal with surface oxygen because Wade teaches that the reaction of the ruthenium precursor having a cyclopentadienyl group is surface-mediated, and Park discloses that the formation of noble metal films entails the reaction of surface oxygen atoms with the ruthenium precursor in order to form ruthenium metal. Alternatively, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the conditions of the method of Wade to remove metal oxides in order to form pure ruthenium films, as taught by Wade and Park.
Response to Arguments
Applicant’s arguments, filed March 9, 2026, with respect to the rejection(s) of the claim(s) under 35 USC 103 have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Wade.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to JOSE I HERNANDEZ-KENNEY whose telephone number is (571)270-5979. The examiner can normally be reached M-F 6:30-3:30.
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/JOSE I HERNANDEZ-KENNEY/
Primary Examiner
Art Unit 1717