Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation

Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O-2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO2, Al2O3, Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe2O3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth.The authors would like to thank Dr. Beatriz Barcones Campo (TU/e) for cross-sectional TEM sample preparation and Dr. Marcel Verheijen (TU/e) for TEM analysis. We acknowledge financial support from the U.S. Department of Energy, Office of Basic Energy Sciences, to the SUNCAT Center for Interface Science and Catalysis (J.A.S.) and from the U.S. Department of Energy under Award No. DE-SC0004782 (W.-H.K. and S.F.B.). This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-114747. The work of A.J.M.M. at Stanford was supported by The Netherlands Organization for Scientific Research (NWO-Rubicon 680-50-1309). The work at TU/e was financially supported by NWO and the Technology Foundation STW through the VIDI program on "Novel bottom-up nanofabrication techniques for future carbon-nanoelectronics" (VIDI 12379), and by Toyota Motor Europe. The authors gratefully acknowledge the use of the Stanford Nano Shared Facilities (SNSF) of Stanford University for sample characterization. Solliance and the Dutch province of Noord-Brabant are acknowledged for funding the TEM facility