Ab-initio Simulations and Structure Fabrication at Atomic and Close-to-atomic Scale using Atomic Force Microscopy

To increase the number of electronic components in a single integrated circuit chip, the functional feature size should be reduced to the atomic and close-to-atomic scale (ACS). For this, the application of molecules could be utilised as a channel for current conduction. This thesis focuses on the fundamental aspects of this theme to help us achieve atomic scale device fabrication in the future. A literature review on advances in moletronics and atomic and close-to-atomic scale manufacturing (ACSM) research with the application of atomic force microscopy (AFM) is given in chapter 1. ACS device manufacturing using molecules as the building block requires to overcome mainly three fundamental problems. Firstly the orientation of the molecule when placed between the electrodes plays a critical role in electronic transport. This is explained in chapter 2, which gives a detailed ab-initio simulation studies of current flow in inorganic molecule, such as polyoxometalates (POMs) and organic molecules such as phthalocyanines (Pc) and porphyrins (Pr), by incorporating them between gold electrodes. For the POM molecule, longitudinal orientation showed better conduction than lateral orientation, whereas for Pc and Pr molecules, the geometrically optimised orientation displayed better electronic transport properties than the tautomerized structure. Secondly, the bonding interaction between the electrode and the molecular terminal atoms helps us to determine the rate of electronic transport at the junction. Chapter 3 inspects this interaction through a periodic energy decomposition analysis on Pc and Pr derivatives. The attractive and repulsive energy terms of the bonding interactions proved that Pr molecules are better interactive over the gold substrate in comparison to Pc molecules. Electronic transport studies performed on their derivatives with and without thiol linkers further supported this result. Thus, a link between these two studies were established. This paves path for future work to select appropriate molecules and electrodes to demonstrate transistor actions for atomic scale device fabrication. Finally, the possibility of the fabrication of ACS electrodes with a single atomic protrusion for the attachment of molecules needs to be experimentally validated. As a first step towards this, fundamental studies using AFM to achieve atomic layer removal were carried out taking into account different machining parameters. This is given in chapter 4 and chapter 5. In chapter 4, mechanical AFM-based scratching techniques over gold and silicon using diamond tips were performed. In silicon substrate, material removal having a minimum depth of 3.2Å which is close to about 3 silicon atom thickness, has been achieved. On gold, a minimum depth of 9.7Å, close to 7 atom thickness has been achieved. In chapter 5, electrochemical AFM-based lithography over HOPG and silicon using platinum coated tips were carried out. Results showed that in bare silicon local anodic oxidation took place instead of material removal. Even in hydrofluoric (HF) treated silicon, oxidation occurred but in a controlled and well defined manner. From this, it can be deduced that HF treated silicon is better suited for structure fabrication than bare silicon. In the case of HOPG, different patterns such as nano-holes, nanolines and intrinsic patterns were machined and material removal close-to-a single atomic layer, ~3.35Å was achieved. Results from chapter 4 and 5 reveal that controlled AFM-based scratching techniques can ensure the fabrication of well-defined atomic structures for the application of molecular devices. Since ACSM represents the next phase of manufacturing, this thesis proposes some of the primary works required to realise ACSM using the currently available techniques and simulation methodologies to bring us one step closer in achieving considerable advancements in this field in the near future.