RESUMEN
In this study, we investigate the reactions involving Atomic Layer Deposition (ALD) of 2D-MoS2 from the heteroleptic precursor Mo(NMe2)2(NtBu)2 and H2S as the co-reagent on a SiO2(0001) surface by means of density functional theory (DFT). All dominant reaction pathways from the early stage of adsorption of each ALD reagent to the formation of bulk-like Mo and S at the surface are identified. In the metal pulse, proton transfer from terminal OH groups on the SiO2 to the physisorbed metal precursor increases the Lewis acidity of Mo and Lewis basicity of O, which gives rise to the chemical adsorption of the metal precursor. Proton transfer from the surface to the dimethylamido ligands leads to the formation and desorption of dimethylamine. In contrast, the formation and desorption of tert-butylamine is not energetically favorable. The tert-butylimido ligand can only be partially protonated in the metal pulse. In the sulphur pulse, co-adsorption and dissociation of H2S molecules give rise to the formation and desorption of tert-butylamine. Through the calculated activation energies, the cooperation between H2S molecules ('cooperative' mechanism) is shown to have a profound influence on the formation and desorption of tert-butylamine, which are crucial steps in the initial ALD deposition of 2D-MoS2 on SiO2. The cyclic ALD reactions give rise to the formation of a buffer layer which might have important consequences for the electrical and optical properties on the 2D layer formed in the subsequent homodeposition.
RESUMEN
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.
RESUMEN
Atomic layer deposition (ALD) is a method that allows for the deposition of thin films with atomic level control of the thickness and an excellent conformality on 3-dimensional surfaces. In recent years, ALD has been implemented in many applications in microelectronics, for which often a patterned film instead of full area coverage is required. This article reviews several approaches for the patterning of ALD-grown films. In addition to conventional methods relying on etching, there has been much interest in nanopatterning by area-selective ALD. Area-selective approaches can eliminate compatibility issues associated with the use of etchants, lift-off chemicals, or resist films. Moreover, the use of ALD as an enabling technology in advanced nanopatterning methods such as spacer defined double patterning or block copolymer lithography is discussed, as well as the application of selective ALD in self-aligned fabrication schemes.