Sub-nanometer dimensions control of core/shell nanoparticles prepared by atomic layer deposition.

Bimetallic core/shell nanoparticles (NPs) are the subject of intense research due to their unique electronic, optical and catalytic properties. Accurate and independent control over the dimensions of both core and shell would allow for unprecedented catalytic performance. Here, we demonstrate that both core and shell dimensions of Pd/Pt core/shell nanoparticles (NPs) supported on Al2O3 substrates can be controlled at the sub-nanometer level by using a novel strategy based on atomic layer deposition (ALD). From the results it is derived that the main conditions for accurate dimension control of these core/shell NPs are: (i) a difference in surface energy between the deposited core metal and the substrate to obtain island growth; (ii) a process yielding linear growth of the NP cores with ALD cycles to obtain monodispersed NPs with a narrow size distribution; (iii) a selective ALD process for the shell metal yielding a linearly increasing thickness to obtain controllable shell growth exclusively on the cores. For Pd/Pt core/shell NPs it is found that a minimum core diameter of 1 nm exists above which the NP cores are able to catalytically dissociate the precursor molecules for shell growth. In addition, initial studies on the stability of these core/shell NPs have been carried out, and it has been demonstrated that core/shell NPs can be deposited by ALD on high aspect ratio substrates such as nanowire arrays. These achievements show therefore that ALD has significant potential for the preparation of tuneable heterogeneous catalyst systems.