Nanoscale electronic properties of conjugated polymers and nanocrystals

The objective of this thesis is the exploration and characterisation of the nanoscale electronic properties of conjugated polymers and nanocrystals. In Chapter 2, the first application of conducting-probe atomic force microscopy (CP-AFM)-based displacement-voltage (z-V) spectroscopy to local measurement of electronic properties of conjugated polymer thin films is reported. Charge injection thresholds along with corresponding single particle gap and exciton binding energies are determined for a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] thin film. By performing measurements across a grid of locations on the film, a series of exciton binding energy distributions are identified. The variation in measured exciton binding energies is in contrast to the smoothness of the film suggesting that the variation may be attributable to differences in the nano-environment of the polymer molecules within the film at each measurement location. In Chapter 3, the CP-AFM-based z-V spectroscopy method is extended for the first time to local, room temperature measurements of the Coulomb blockade voltage thresholds arising from sequential single electron charging of 28 kDa Au nanocrystal arrays. The fluid-like properties of the nanocrystal arrays enable reproducible formation of nanoscale probe-array-substrate junctions, allowing the influence of background charge on the electronic properties of the array to be identified. CP-AFM also allows complementary topography and phase data to be acquired before and after spectroscopy measurements, enabling comparison of local array morphology with local measurements of the Coulomb blockade thresholds. In Chapter 4, melt-assisted template wetting is applied for the first time to massively parallel fabrication of poly-(3-hexylthiophene) nanowires. The structural characteristics of the wires are first presented. Two-terminal electrical measurements of individual nanowires, utilising a CP-AFM tip as the source electrode, are then used to obtain the intrinsic nanowire resistivity and the total nanowire-electrode contact resistance subsequently allowing single nanowire hole mobility and mean nanowire-electrode barrier height values to be estimated. In Chapter 5, solution-assisted template wetting is used for fabrication of fluorene-dithiophene co-polymer nanowires. The structural characteristics of these wires are also presented. Two-terminal electrical measurements of individual nanowires indicate barrier formation at the nanowire-electrode interfaces and measured resistivity values suggest doping of the nanowires, possibly due to air exposure. The first report of single conjugated polymer nanowires as ultra-miniature photodetectors is presented, with single wire devices yielding external quantum efficiencies ~ 0.1 % and responsivities ~ 0.4 mA/W under monochromatic illumination.

Pyramidal quantum dots: single and entangled photon sources and correlation studies

Practical realisation of quantum information science is a challenge being addressed by researchers employing various technologies. One of them is based on quantum dots (QD), usually referred to as artificial atoms. Being capable to emit single and polarization entangled photons, they are attractive as sources of quantum bits (qubits) which can be relatively easily integrated into photonic circuits using conventional semiconductor technologies. However, the dominant self-assembled QD systems suffer from asymmetry related problems which modify the energetic structure. The main issue is the degeneracy lifting (the fine-structure splitting, FSS) of an optically allowed neutral exciton state which participates in a polarization-entanglement realisation scheme. The FSS complicates polarization-entanglement detection unless a particular FSS manipulation technique is utilized to reduce it to vanishing values, or a careful selection of intrinsically good candidates from the vast number of QDs is carried out, preventing the possibility of constructing vast arrays of emitters on the same sample. In this work, site-controlled InGaAs QDs grown on (111)B oriented GaAs substrates prepatterned with 7.5 μm pitch tetrahedrons were studied in order to overcome QD asymmetry related problems. By exploiting an intrinsically high rotational symmetry, pyramidal QDs were shown as polarization-entangled photon sources emitting photons with the fidelity of the expected maximally entangled state as high as 0.721. It is the first site-controlled QD system of entangled photon emitters. Moreover, the density of such emitters was found to be as high as 15% in some areas: the density much higher than in any other QD system. The associated physical phenomena (e.g., carrier dynamic, QD energetic structure) were studied, as well, by different techniques: photon correlation spectroscopy, polarization-resolved microphotoluminescence and magneto-photoluminescence.

Synthesis, functionalisation and characterisation of germanium nanocrystals & their applications

In the last two decades, semiconductor nanocrystals have been the focus of intense research due to their size dependant optical and electrical properties. Much is now known about how to control their size, shape, composition and surface chemistry, allowing fine control of their photophysical and electronic properties. However, genuine concerns have been raised regarding the heavy metal content of these materials, which is toxic even at relatively low concentrations and may limit their wide scale use. These concerns have driven the development of heavy metal free alternatives. In recent years, germanium nanocrystals (Ge NCs) have emerged as environmentally friendlier alternatives to II-VI and IV-VI semiconductor materials as they are nontoxic, biocompatible and electrochemically stable. This thesis reports the synthesis and characterisation of Ge NCs and their application as fluorescence probes for the detection of metal ions. A room-temperature method for the synthesis of size monodisperse Ge NCs within inverse micelles is reported, with well-defined core diameters that may be tuned from 3.5 to 4.5 nm. The Ge NCs are chemically passivated with amine ligands, minimising surface oxidation while rendering the NCs dispersible in a range of polar solvents. Regulation of the Ge NCs size is achieved by variation of the ammonium salts used to form the micelles. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases from 3.5 to 4.5 nm. A polydisperse sample with a mixed emission profile is prepared and separated by centrifugation into individual sized NCs which each showed blue and green emission only, with total suppression of other emission colours. A new, efficient one step synthesis of Ge NCs with in situ passivation and straightforward purification steps is also reported. Ge NCs are formed by co-reduction of a mixture of GeCl4 and n-butyltrichlorogermane; the latter is used both as a capping ligand and a germanium source. The surface-bound layer of butyl chains both chemically passivates and stabilises the Ge NCs. Optical spectroscopy confirmed that these NCs are in the strong quantum confinement regime, with significant involvement of surface species in exciton recombination processes. The PL QY is determined to be 37 %, one of the highest values reported for organically terminated Ge NCs. A synthetic method is developed to produce size monodisperse Ge NCs with modified surface chemistries bearing carboxylic acid, acetate, amine and epoxy functional groups. The effect of these different surface terminations on the optical properties of the NCs is also studied. Comparison of the emission properties of these Ge NCs showed that the wavelength position of the PL maxima could be moved from the UV to the blue/green by choice of the appropriate surface group. We also report the application of water-soluble Ge NCs as a fluorescent sensing platform for the fast, highly selective and sensitive detection of Fe3+ ions. The luminescence quenching mechanism is confirmed by lifetime and absorbance spectroscopies, while the applicability of this assay for detection of Fe3+ in real water samples is investigated and found to satisfy the US Environmental Protection Agency requirements for Fe3+ levels in drinkable water supplies.

Droplet etching of deep nanoholes for filling with self-aligned complex quantum structures

Strain-free epitaxial quantum dots (QDs) are fabricated by a combination of Al local droplet etching (LDE) of nanoholes in AlGaAs surfaces and subsequent hole filling with GaAs. The whole process is performed in a conventional molecular beam epitaxy (MBE) chamber. Autocorrelation measurements establish single-photon emission from LDE QDs with a very small correlation function g (2)(0)≃ 0.01 of the exciton emission. Here, we focus on the influence of the initial hole depth on the QD optical properties with the goal to create deep holes suited for filling with more complex nanostructures like quantum dot molecules (QDM). The depth of droplet etched nanoholes is controlled by the droplet material coverage and the process temperature, where a higher coverage or temperature yields deeper holes. The requirements of high quantum dot uniformity and narrow luminescence linewidth, which are often found in applications, set limits to the process temperature. At high temperatures, the hole depths become inhomogeneous and the linewidth rapidly increases beyond 640 °C. With the present process technique, we identify an upper limit of 40-nm hole depth if the linewidth has to remain below 100 μeV. Furthermore, we study the exciton fine-structure splitting which is increased from 4.6 μeV in 15-nm-deep to 7.9 μeV in 35-nm-deep holes. As an example for the functionalization of deep nanoholes, self-aligned vertically stacked GaAs QD pairs are fabricated by filling of holes with 35 nm depth. Exciton peaks from stacked dots show linewidths below 100 μeV which is close to that from single QDs.