Novel Chemical Route to Size-Controlled Ta(0) and Ru-Ta Nanoparticles in Ionic Liquids

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Novel Chemical Route to Size-Controlled Ta(0) and Ru-Ta Nanoparticles in Ionic Liquids

Inga S. Helgadottir 1, 2, Philippe P. Arquillière 1, 2, Paul S. Campbell 1, Catherine C. Santini *1, and P.-H. Haumesser 2

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CNRS-UMR 5265, 43 Bd du 11 Novembre 1918, 69616, Villeurbanne Cedex, France. CEA–LETI-Minatec Campus, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France. * [email protected] Fax: 33(0)472431795; Tel: 33(0)472431810 2

ABSTRACT Metallic nanoparticles under 10 nm are of particular interest for the microelectronics industry. However, there is a lack of convenient synthetic routes to control their size Oxophilic metals, such as Ta, are also of high interest, however, the high oxophilicity and melting point makes the synthesis of such nanoparticles challenging. Making use of imidazolium-based ionic liquids, monodisperse zero-valent tantalum nanoparticles (Ta(0)NPs) have been successfully synthesised at room temperature by reduction of tris(neopentyl)neopentylidenetantalum(V). Furthermore; well size-controlled bimetallic Ru-Ta NPs have also been synthesized. INTRODUCTION To meet the constant challenges of miniaturization in the microelectronics industry, traditional methodologies must be replaced by new innovative pathways to produce nanoobjects. Defined as particles, whose dimensions are on the nanoscale, they coincide with a transition between bulk and molecular states and exhibit unique characteristics related to the discontinuities and quantum effects of such a transition, e.g. enhanced magnetic and catalytic properties. [1, 2] Metallic nanoparticles (NPs) under 10 nm present unique properties between the bulk and the molecular species. These objects are of crucial importance for the development of various applications. In particular, they are relevant to face the challenges raised by the miniaturization in the microelectronics industry. For such applications, the precise synthesis of nanomaterials with tailored properties (size and structure) is a pre-requisite. However, there is a lack of convenient synthetic routes to control these properties. Tantalum is a metal of particular interest, e.g., due to its very high melting point and excellent corrosion resistance, high thermal conductivity, small work function, plasticity, and durability. It has very promising characteristics for use in solid electrolytic capacitors, better than other dielectrics, and metallic tantalum has been used in electronics, metallurgy industry, and chemical and mechanical engineering. [3, 4] The same properties that make Ta an interesting metal makes the synthesis of TaNPs difficult by conventional physical methods and the high oxophilicity of the metal means that making and stabilizing Ta(0)NPs is challenging. [5, 6] Unlike traditional solvents, ionic liquids (ILs) can be used to generate metallic NPs by several physical and chemical routes and stabilize them in the absence of further additives. [7] Using these specific solvation properties of ILs, we have demonstrated a general route for the

synthesis of mono- and bimetallic NPs b