Controlled nanostructure fabrication using atomic force microscopy

Abstract

Scanning probe microscopy (SPM) nanolithography has been found to be a powerful and low-cost approach for sub-100 nm patterning. In this thesis, the possibility of using a state-of-the-art SPM system to controllably deposit nanoparticles on patterned Si substrates with high positional control has been explored. These nanoparticles have a range of interesting properties and have been characterised by electron microscopy and scanning probe microscopy. The influence of different deposition parameters on the nanoparticle properties was studied.

Contact mode atomic force microscopy (AFM)-based local oxidation nanolithography (LON) was used to oxidise sample surfaces. Two different substrates were studied which were native oxide silicon (Si) and molybdenum (Mo).

A number of factors that influence the height and width of the oxide features were investigated in order to achieve the optimal oxidation efficiency. The height and width of the oxide structures were found to be strongly dependent on the applied voltage and scan speed. The tunneling AFM (TUNA) technique was used to measure the ultralow currents flowing between the tip and the sample during the oxidation process. It was found that a threshold voltage for our oxidation experiments was -4.0 ± 1.6 V applied to the tip when fabricating geometric patterns as well as 2.9 ± 1.6 V and 2.8 ± 2.2 V applied to the substrate for nanodot fabrication. In addition, comparisons of nanodot-array patterns produced with different AFM tips were studied. The influence of applied voltage, type of AFM tip and substrate, humidity and ramping time has been studied for dot formation providing a comparison between native oxide Si and Mo surfaces. The nanodot sizes were found to be clearly dependent on the applied voltage, type of substrate, relative humidity and ramping time.

Dip-pen nanolithography (DPN) was used to study a direct deposition strategy for gold (Au) nanodot fabrication on a native oxide Si substrate. In this process, hydrogen tetrachloroaurate (HAuCl₄) molecules were deposited onto the substrate via a molecular diffusion process, in the absence of electrochemical reactions. This approach allowed for the generation of Au dots on the SiO2 substrate without the need for surface modification or additional electrode structures. The dependence of the size of the Au dots on different „scanning coating‟ (SC) times of AFM tips was studied. A thermal annealing process was used to decompose the generated HAuCl₄ molecular dots to leave Au (0) metal dots. A stereomicroscope has been used for preliminary observation of different steps of Au deposition treatments.

A scanning electron microscope (SEM) was used to characterise the SC AFM tips both before and after the DPN process. SEM energy-dispersive X-ray spectroscopy (EDS) has provided information about the elemental content of deposited particles for different annealing temperatures.

Fountain-pen nanolithography (FPN) has also been used to study nanowriting of HAuCl₄ salt and a variety of solvents on a native oxide Si surface. In this technique, a nanopipette was mounted within an AFM to deliver appropriate solutions to the silica substrate. We found that an aqueous Au salt solution was the most suitable ink for depositing gold using the FPN technique. In the case of solvents alone, ethanol and toluene were achieved with depositing onto a SiO₂ substrate using the FPN technique.