Surface morphology dependent photoluminescence from colloidal silicon nanocrystals

Monodisperse 1-2 nm silicon nanocrystals are synthesized in reverse micelles and have their surfaces capped with either allylamine or 1-heptene to produce either hydrophilic or hydrophobic silicon nanocrystals. Optical characterization (absorption, PL, and time-resolved PL) is performed on colloidal solutions with the two types of surface-capped silicon nanocrystals with identical size distributions. Direct evidence is obtained for the modification of the optical properties of silicon nanocrystals by the surface-capping molecule. The two different surface-capped silicon nanocrystals show remarkably different optical properties.

Energy transfer dynamics of nanocrystal-polymer composites

Steady-state and time-resolved photoluminescence spectroscopy are used to examine the photoluminescent properties of nanocrystal-polymer composites consisting of colloidal PbS nanocrystals blended with poly(2-methoxy-5(2-ethylhexyloxy)-p-phenylene vinylene). Quenching of the emission from the conjugated polymer due to the PbS nanocrystals is observed along with band edge emission from the ligand capped PbS nanocrystals. A decrease in the photoluminescence lifetime of MEH-PPV is also observed in the thin film nanocrystal-polymer composite materials. Photoluminescence excitation spectroscopy of the PbS nanocrystal emission from the composite shows features attributed to MEH-PPV providing evidence of a Forster transfer process.

Carrier transport in PbS nanocrystal conducting polymer composites

In this letter we report the carrier mobilities in an inorganic nanocrystal: conducting polymer composite. The composite material in question (lead sulphide nanocrystals in the conducting polymer poly [2-methoxy-5-(2(')-ethyl-hexyloxy)-p-phenylene vinylene] (MEH-PPV) was made using a single-pot, surfactant-free synthesis. Mobilties were measured using time of flight techniques. We have found that the inclusion of PbS nanocrystals in MEH-PPV both balances and markedly increases the hole and electron mobilities-the hole mobility is increased by a factor of similar to 10(5) and the electron mobility increased by similar to 10(7) under an applied bias of 5 kV cm(-1). These results explain why dramatic improvements in electrical conductivity and photovoltaic performance are seen in devices fabricated from these composites.

Time-resolved photoluminescence spectroscopy of ligand-capped PbS nanocrystals

PbS nanocrystals are synthesized using colloidal techniques and have their surfaces capped with oleic acid. The absorption band edge of the PbS nanocrystals is tuned between 900 and 580 nm. The PbS nanocrystals exhibit tuneable photoluminescence with large non-resonant Stokes shifts of up to 500 mcV. The magnitude of the Stokes shift is found to be dependent upon the size of PbS nanocrystals. Time-resolved photoluminescence spectroscopy of the PbS nanocrystals reveals that the photouminescence has an extraordinarily long lifetime of 1 mus. This long fluorescence lifetime is attributed to the effect of dielectric screening similar to that observed in other IV-VI semiconductor nanocrystals.

Non-linear photoluminescence from purified aqueous PbS nanocrystals

A simple and effective method for purifying photoluminescent water-soluble surface passivated PbS nanocrystals has been developed. Centrifuging at high speeds removes PbS nanocrystals that exhibit strong red band edge photoluminescence from an original solution containing multiple nanocrystalline species with broad photoluminescence spectra. The ability to purify the PbS nanocrystals allowed two-photon photoluminescence spectroscopy to be performed on water-soluble PbS nanocrystals and be attributed to band edge recombination. (c) 2006 Elsevier B.V. All rights reserved.

Ultrashort pulse generation from diode laser devices

This thesis presents a detailed, experiment-based study of generation of ultrashort optical pulses from diode lasers. Simple and cost-effective techniques were used to generate high power, high quality optical short pulses at various wavelength windows. The major achievements presented in the thesis is summarised as follows. High power pulses generation is one of the major topics discussed in the thesis. Although gain switching is the simplest way for ultrashort pulse generation, it proves to be quite effective to deliver high energy pulses on condition that the pumping pulses with extremely fast rising time and high enough amplitude are applied on specially designed pulse generators. In the experiment on a grating-coupled surface emitting laser (GCSEL), peak power as high as 1W was achieved even when its spectral bandwidth was controlled within 0.2nm. Another experiment shows violet picosecond pulses with peak power as high as 7W was achieved when the intensive electrical pulses were applied on optimised DC bias to pump on InGaN violet diode laser. The physical mechanism of this phenomenon, as we considered, may attributed to the self-organised quantum dots structure in the laser. Control of pulse quality, including spectral quality and temporal profile, is an important issue for high power pulse generation. The ways to control pulse quality described in the thesis are also based on simple and effective techniques. For instance, GCSEL used in our experiment has a specially designed air-grating structure for out-coupling of optical signals; hence, a tiny flat aluminium mirror was placed closed to the grating section and resulted in a wavelength tuning range over 100nm and the best side band suppression ratio of 40dB. Self-seeding, as an effective technique for spectral control of pulsed lasers, was demonstrated for the first time in a violet diode laser. In addition, control of temporal profile of the pulse is demonstrated in an overdriven DFB laser. Wavelength tuneable fibre Bragg gratings were used to tailor the huge energy tail of the high power pulse. The whole system was compact and robust. The ultimate purpose of our study is to design a new family of compact ultrafast diode lasers. Some practical ideas of laser design based on gain-switched and Q-switched devices are also provided in the end.

Synthesis and evaluation of nanoparticle-polymer composites

This thesis describes the synthesis of functionalised polymeric material by variety of free-radical mediated polymerisation techniques including dispersion emulsion, seeded emulsion, suspension and bulk polymerisation reactions. Organic fluorophores and nanoparticles such as quantum dots were incorporated within polymeric materials, in particular, thiol-functionalised polymer microspheres, which were fluorescently labelled either during synthesis or by covalent attachment post synthesis. The resultant fluorescent polymeric conjugates were then assessed for their utility in biological systems as an analytical tool for cells or biological structures. Quantum dot labelled, thiol-functionalised microspheres were assessed for their utility in the visualisation and tracking of red blood cells. Determination of the possible internalisation of fluorescent microspheres into red blood cells was required before successful tracking of red blood cells could take place. Initial work appeared to indicate the presence of fluorescent microspheres inside red blood cells by the process of beadfection. A range of parameters were also investigated in order to optimise beadfection. Thiol-functionalised microspheres labelled successfully with organic fluorophores were used to image the tear film of the eye. A description of problems encountered with the covalent attachment of hydrophilic, thiol-reactive fluorescent dyes to a variety of modified polymer microspheres is also included in this section. Results indicated large microspheres were particularly useful when tracking the movement of fluid along the tear meniscus. Functional bulk polymers were synthesised for assessment of their interaction with titanium dioxide nanoparticles. Thiol-functionalised polymethyl methacrylate and spincoated thiouronium-functionalised polystyrene appeared to facilitate the attachment of titanium dioxide nanoparticles. Interaction assays included the use of XPS analysis and processes such as centrifugation. Attempts to synthesise 4-vinyl catechol, a compound containing hydroxyl moieties with potential for coordination with titanium dioxide nanoparticles, were also carried out using 3,4-dihydroxybenzaldehyde as the starting material.

A micro-opto-electro-mechanical system (MOEMS) for microstructure manipulation

Microstructure manipulation is a fundamental process to the study of biology and medicine, as well as to advance micro- and nano-system applications. Manipulation of microstructures has been achieved through various microgripper devices developed recently, which lead to advances in micromachine assembly, and single cell manipulation, among others. Only two kinds of integrated feedback have been demonstrated so far, force sensing and optical binary feedback. As a result, the physical, mechanical, optical, and chemical information about the microstructure under study must be extracted from macroscopic instrumentation, such as confocal fluorescence microscopy and Raman spectroscopy. In this research work, novel Micro-Opto-Electro-Mechanical-System (MOEMS) microgrippers are presented. These devices utilize flexible optical waveguides as gripping arms, which provide the physical means for grasping a microobject, while simultaneously enabling light to be delivered and collected. This unique capability allows extensive optical characterization of the structure being held such as transmission, reflection, or fluorescence. The microgrippers require external actuation which was accomplished by two methods: initially with a micrometer screw, and later with a piezoelectric actuator. Thanks to a novel actuation mechanism, the "fishbone", the gripping facets remain parallel within 1 degree. The design, simulation, fabrication, and characterization are systematically presented. The devices mechanical operation was verified by means of 3D finite element analysis simulations. Also, the optical performance and losses were simulated by the 3D-to-2D effective index (finite difference time domain FDTD) method as well as 3D Beam Propagation Method (3D-BPM). The microgrippers were designed to manipulate structures from submicron dimensions up to approximately 100 μm. The devices were implemented in SU-8 due to its suitable optical and mechanical properties. This work demonstrates two practical applications: the manipulation of single SKOV-3 human ovarian carcinoma cells, and the detection and identification of microparts tagged with a fluorescent "barcode" implemented with quantum dots. The novel devices presented open up new possibilities in the field of micromanipulation at the microscale, scalable to the nano-domain.

Periodic polymer photonic bandgap structures for on-chip optical cavities

Integrated on-chip optical platforms enable high performance in applications of high-speed all-optical or electro-optical switching, wide-range multi-wavelength on-chip lasing for communication, and lab-on-chip optical sensing. Integrated optical resonators with high quality factor are a fundamental component in these applications. Periodic photonic structures (photonic crystals) exhibit a photonic band gap, which can be used to manipulate photons in a way similar to the control of electrons in semiconductor circuits. This makes it possible to create structures with radically improved optical properties. Compared to silicon, polymers offer a potentially inexpensive material platform with ease of fabrication at low temperatures and a wide range of material properties when doped with nanocrystals and other molecules. In this research work, several polymer periodic photonic structures are proposed and investigated to improve optical confinement and optical sensing. We developed a fast numerical method for calculating the quality factor of a photonic crystal slab (PhCS) cavity. The calculation is implemented via a 2D-FDTD method followed by a post-process for cavity surface energy radiation loss. Computational time is saved and good accuracy is demonstrated compared to other published methods. Also, we proposed a novel concept of slot-PhCS which enhanced the energy density 20 times compared to traditional PhCS. It combines both advantages of the slot waveguide and photonic crystal to localize the high energy density in the low index material. This property could increase the interaction between light and material embedded with nanoparticles like quantum dots for active device development. We also demonstrated a wide range bandgap based on a one dimensional waveguide distributed Bragg reflector with high coupling to optical waveguides enabling it to be easily integrated with other optical components on the chip. A flexible polymer (SU8) grating waveguide is proposed as a force sensor. The proposed sensor can monitor nN range forces through its spectral shift. Finally, quantum dot - doped SU8 polymer structures are demonstrated by optimizing spin coating and UV exposure. Clear patterns with high emission spectra proved the compatibility of the fabrication process for applications in optical amplification and lasing.

The Application of Fluorescent Nanocrystals to Study the Distribution of Neuropeptides in the Aedes Aegypti Mosquito

Semiconductor nanocrystals, also known as quantum dots (QDs), have been used in studies involving mice and human tissues, but never before in research on insects. We used QDs to study the distribution of two neuropeptides in the Aedes aegypti mosquito, the vector of both dengue and yellow fever. These neuropeptides play a significant role in the production of juvenile hormone, a hormone that controls biting behavior, metamorphosis, and reproduction throughout the life of the mosquito. The two neuropeptides allatostatin-C (AS-C) and allatotropin (AT) function as inhibitory (AS-C) and stimulatory (AT) regulators of juvenile hormone synthesis in the corpus allatum gland. In other insects, they also affect heart rate, gut movement, and nutrient uptake. Conjugating these neuropeptides to quantum dots via a streptavidinlbiotin link, we were able to expose the mosquito corpus allatum and abdomen to allatostatin-C and allatotropin and then to visualize their distribution under UV light using confocal and compound light microscopy. Histological sections of the whole mosquito, incubations of tissues with conjugates (in vitro), and microinjections of conjugates into the mosquito (in vivo) were performed. The results showed that quantum dots can be used to detect neuropeptide distribution in the mosquito. The more we understand about these neuropeptides and juvenile hormone, the more we can contribute to stopping the spread of infectious diseases, such as dengue and yellow fever.

Experimental analysis of novel telecom source materials and devices

Incumbent telecommunication lasers emitting at 1.5 µm are fabricated on InP substrates and consist of multiple strained quantum well layers of the ternary alloy InGaAs, with barriers of InGaAsP or InGaAlAs. These lasers have been seen to exhibit very strong temperature dependence of the threshold current. This strong temperature dependence leads to a situation where external cooling equipment is required to stabilise the optical output power of these lasers. This results in a significant increase in the energy bill associated with telecommunications, as well as a large increase in equipment budgets. If the exponential growth trend of end user bandwidth demand associated with the internet continues, these inefficient lasers could see the telecommunications industry become the dominant consumer of world energy. For this reason there is strong interest in developing new, much more efficient telecommunication lasers. One avenue being investigated is the development of quantum dot lasers on InP. The confinement experienced in these low dimensional structures leads to a strong perturbation of the density of states at the band edge, and has been predicted to result in reduced temperature dependence of the threshold current in these devices. The growth of these structures is difficult due to the large lattice mismatch between InP and InAs; however, recently quantum dots elongated in one dimension, known as quantum dashes, have been demonstrated. Chapter 4 of this thesis provides an experimental analysis of one of these quantum dash lasers emitting at 1.5 µm along with a numerical investigation of threshold dynamics present in this device. Another avenue being explored to increase the efficiency of telecommunications lasers is bandstructure engineering of GaAs-based materials to emit at 1.5 µm. The cause of the strong temperature sensitivity in InP-based quantum well structures has been shown to be CHSH Auger recombination. Calculations have shown and experiments have verified that the addition of bismuth to GaAs strongly reduces the bandgap and increases the spin orbit splitting energy of the alloy GaAs1−xBix. This leads to a bandstructure condition at x = 10 % where not only is 1.5 µm emission achieved on GaAs-based material, but also the bandstructure of the material can naturally suppress the costly CHSH Auger recombination which plagues InP-based quantum-well-based material. It has been predicted that telecommunications lasers based on this material system should operate in the absence of external cooling equipment and offer electrical and optical benefits over the incumbent lasers. Chapters 5, 6, and 7 provide a first analysis of several aspects of this material system relevant to the development of high bismuth content telecommunication lasers.

A Micro-Opto-Electro-Mechanical System (MOEMS) for Microstructure Manipulation

Microstructure manipulation is a fundamental process to the study of biology and medicine, as well as to advance micro- and nano-system applications. Manipulation of microstructures has been achieved through various microgripper devices developed recently, which lead to advances in micromachine assembly, and single cell manipulation, among others. Only two kinds of integrated feedback have been demonstrated so far, force sensing and optical binary feedback. As a result, the physical, mechanical, optical, and chemical information about the microstructure under study must be extracted from macroscopic instrumentation, such as confocal fluorescence microscopy and Raman spectroscopy. In this research work, novel Micro-Opto-Electro-Mechanical-System (MOEMS) microgrippers are presented. These devices utilize flexible optical waveguides as gripping arms, which provide the physical means for grasping a microobject, while simultaneously enabling light to be delivered and collected. This unique capability allows extensive optical characterization of the structure being held such as transmission, reflection, or fluorescence. The microgrippers require external actuation which was accomplished by two methods: initially with a micrometer screw, and later with a piezoelectric actuator. Thanks to a novel actuation mechanism, the “fishbone”, the gripping facets remain parallel within 1 degree. The design, simulation, fabrication, and characterization are systematically presented. The devices mechanical operation was verified by means of 3D finite element analysis simulations. Also, the optical performance and losses were simulated by the 3D-to-2D effective index (finite difference time domain FDTD) method as well as 3D Beam Propagation Method (3D-BPM). The microgrippers were designed to manipulate structures from submicron dimensions up to approximately 100 µm. The devices were implemented in SU-8 due to its suitable optical and mechanical properties. This work demonstrates two practical applications: the manipulation of single SKOV-3 human ovarian carcinoma cells, and the detection and identification of microparts tagged with a fluorescent “barcode” implemented with quantum dots. The novel devices presented open up new possibilities in the field of micromanipulation at the microscale, scalable to the nano-domain.

Nanotechnology in food industry II: risk assessment and legislation

Currently, there is increasing use of nanomaterials in the food industry thanks to the many advantages offered and make the products that contain them more competitive in the market. Their physicochemical properties often differ from those of bulk materials, which require specialized risk assessment. This should cover the risks to the health of workers and consumers as well as possible environmental risks. The risk assessment methods must go updating due to more widespread use of nanomaterials, especially now that are making their way down to consumer products. Today there is no specific legislation for nanomaterials, but there are several european dispositions and regulations that include them. This review gives an overview of the risk assessment and the existing current legislation regarding the use of nanotechnology in the food industry.

Growth and characterization of III-V compound semiconductor nanostructures by metalorganic chemical vapor deposition

Planar <110> GaAs nanowires and quantum dots grown by atmospheric MOCVD have been introduced to non-standard growth conditions such as incorporating Zn and growing them on free-standing suspended films and on 10° off-cut substrates. Zn doped nanowires exhibited periodic notching along the axis of the wire that is dependent on Zn/Ga gas phase molar ratios. Planar nanowires grown on suspended thin films give insight into the mobility of the seed particle and change in growth direction. Nanowires that were grown on the off-cut sample exhibit anti-parallel growth direction changes. Quantum dots are grown on suspended thin films and show preferential growth at certain temperatures. Envisioned nanowire applications include twin-plane superlattices, axial pn-junctions, nanowire lasers, and the modulation of nanowire growth direction against an impeding barrier and varying substrate conditions.

Image-Guided Precision Manipulation of Cells and Nanoparticles in Microfluidics

Manipulation of single cells and particles is important to biology and nanotechnology. Our electrokinetic (EK) tweezers manipulate objects in simple microfluidic devices using gentle fluid and electric forces under vision-based feedback control. In this dissertation, I detail a user-friendly implementation of EK tweezers that allows users to select, position, and assemble cells and nanoparticles. This EK system was used to measure attachment forces between living breast cancer cells, trap single quantum dots with 45 nm accuracy, build nanophotonic circuits, and scan optical properties of nanowires. With a novel multi-layer microfluidic device, EK was also used to guide single microspheres along complex 3D trajectories. The schemes, software, and methods developed here can be used in many settings to precisely manipulate most visible objects, assemble objects into useful structures, and improve the function of lab-on-a-chip microfluidic systems.