Master of Science / Department of Chemistry / Emily McLaurin / Quantum dots (QDs) are novel semiconductors of interest for applications because of their special tunable properties. Among the many types of QDs, InP QDs attract attention because they do not have toxic-heavy-metal elements such as Cd or Pb. Charge-transfer (CT) is important in applications of InP QDs. CT consists of two or more molecules and some of them donate electrons and others accept those electrons. An understanding of CT between QDs with tetracyanoquinodimethane (TCNQ) is important for applications of QDs in photovoltaic and photocatalytic materials. TCNQ is an organic electron acceptor and CT complexes of TCNQ exhibit metallic electric conductivity. Previous research about CT between QDs and TCNQ examined PbS and CdSe QDs, but toxic-heavy-metals limit future application of these materials. So, it is important to research CT between InP QDs and TCNQ. This thesis examines how the amount of InP QDs (QD:TCNQ ratio) and diameters of InP QDs affect the CT between InP QDs and TCNQ. In this thesis, InP QDs are synthesized by a microwave-assisted ionic liquid (MAIL) method and InP QDs of different sizes are isolated using size-selective precipitation. Then, TCNQ-InP QD solutions are prepared with different ratios, with and without light, and with InP QDs of different sizes. These InP QDs and InP QDs-TCNQ samples are characterized using UV-Vis-NIR absorption, photoluminescence (PL), time-correlated single photon counting (TCSPC), and FT-IR spectroscopies. In Chapter 2, the details of synthesizing InP QDs, size selection, and preparation of different TNCQ-InP QD solutions are presented. Then, factors that affect the interaction between InP QDs and TCNQ and possible reasons for these factors are discussed. Based on calculations and experimental results, the carbon atom with the biggest amount of positive charge in TCNQ and phosphorous in InP QDs are likely the acceptor and donor, respectively. CT is affected by the amount of InP QDs in solution, and more InP QDs will reduce more TCNQ. The CT is also affected by the size of the InP QDs and enhanced by light.

Here we present direct investigation of the lasing behaviour by performing gain spectroscopy of solution-based CQDs enabled via in-situ tuning of the feedback wavelength of an open-access hemispherical microcavity. The investigation is performed on two different types of CQDs, namely spherical CdSe/CdS core-shell CQDs and nanopletelets (NPs). The lasing threshold and the differential gain/slope efficiency of the fundamental cavity mode are measured as a function of their spectral position over a spectral range of ∼ 32 nm and of ∼ 42 nm for the spherical CQDs and NPs, respectively. The results of the gain spectroscopy are described using theoretical models, providing insights into the mechanism governing the observed lasing behaviour. Furthermore, the open-access cavity architecture provides a very convenient way of producing in-situ tunable lasing, and single-mode lasing of the fundamental cavity mode over a spectral range of ∼ 25 nm and ∼ 37 nm is demonstrated using spherical CQDs and NPs, respectively. In addition, the stability of laser emission is investigated, with the lasing intensity of the fundamental cavity mode remaining constant over a time period of almost 6 mins. It is hoped that the results will provide a detailed understanding of the lasing behaviour of CQDs. This information can be fed back into the design of CQDs in which the lasing threshold can be reduced to the point where useful devices can be constructed, and in the design of resonant optical feedback structures for which the appropriate wavelength must be carefully selected.

In this thesis type II colloidal quantum dots (CQDs) with zinc blende crystal structure were investigated. The optical properties were characterized by steady state absorption and photoluminescence (PL) spectroscopy for all the samples, and the PL quantum yield was measured for selected samples by using both absolute and relative methods. Exciton dynamics and interactions were investigated by time-resolved PL (TRPL).The exciton-exciton interaction energy for CdSe, CdSe/CdTe and CdSe/CdTe/CdS CQDs was investigated using TRPL spectroscopy, an established method. The TRPL results were compared with previous results from ultrafast transient absorption (TA) measurements and theoretical predictions. The discrepancies between the TRPL and TA results and the theoretical calculations suggest that TRPL data has been misinterpreted in the literature. The single exciton recombination dynamics for CdSe, CdSe/CdTe and CdSe/CdTe/CdS CQDs were investigated. The effects of non-radiative recombination were identified from the PL transients by using a theoretically-calculated radiative lifetime as a fitting parameter. The combined rate of the non-radiative processes thus found was consistent with the localisation of holes into shallow traps by an Auger-mediated process. A rate equation analysis also showed how shallow trapping can give rise to the tri-exponential PL dynamics observed experimentally. Chloride passivation of CdTe CQDs resulted in a near-complete suppression of surface traps, producing a significant enhancement of the optical properties. PL quantum yield (PLQY) and PL lifetime in particular benefit from the chloride treatment. The radiative recombination rate that now could be extracted from PL transients for chloride treated samples was used to calculate the non-radiative recombination rate for the untreated samples. In addition, a study of the effects of air exposure on the PL, observed for both treated and untreated samples was undertaken and revealed the importance of the influence of the dielectric environment surrounding the traps states on recombination dynamics.

CdTe QDs capped with mercaptopropionic acid (MPA) and thioglycolic acid (TGA) were covalently linked to zinc and indium tetraaminophthalocyanines (TAPcs) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of formation of an amide bond between the MTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and the mixture of QDs and ZnTAPc (without chemical linking) showed Förster resonance energy transfer (FRET), though the linked showed less FRET, whereas the QD interactions with InTAPc yielded no evidence of FRET. Both MTAPcs quenched the QDs emission, with quenching constants of the order of 103–104M−1, binding constants of the order of 108-1010M-1 and the number of binding sites for the MTAPc upon the QD being 2. High energy transfer efficiencies were obtained (in some cases as high as 93%), due to the low donor to acceptor distances. Lastly, both MTAPc were shown to be poor optical limiters because their imaginary third-order susceptibility (Im[χ(3)]) was of the order of 10-17-10-16 (optimal range is 10-9-10-11), the hyperpolarizability (γ) of the order of 10-37-10-36 (optimal range is 10-29-10-34) and the k values were above one but below ten.

In this report we detail our work fabricating and measuring graphene quantum dots. We investigate a technique, relatively widely used in several other materials but not yet well investigated in graphene, known as Atomic Force Microscope Lithography (AFML). We then use AFML to fabricate graphene quantum dot systems. Transport measurements are carried out on our graphene quantum dots at low temperatures and high parallel magnetic fields and we try to understand the behaviour of spins in graphene. In our initial investigations into AFML we use graphene samples electrically contacted using standard electron-beam lithography. We were able to cut the graphene lattice by applying a negative voltage to the AFM tip and moving the tip across a grounded graphene surface. We have shown, by measuring the current through the AFM tip during lithography, that cutting of graphene is not current driven. Using a combination of transport measurements and scanning electron microscopy we show that , while indentations accompanied by tip current appear in the graphene lattice for a range of tip voltages, real cuts are characterized by a strong reduction of the tip current above a threshold voltage. The flexibility of the technique was then demonstrated by the fabrication, measurement, modification and re-measurement of graphene nanodevices with resolution down to 15 nm. We subsequently developed a shadow-masking technique to electrically contact graphene samples thus eliminating the use of chemical resists and the associated contamination of the graphene surface. With these pristine samples we were able to oxidise and hydrogenate the graphene using AFML. A graphene quantum dot was then fabricated using AFML oxidation. We also fabricated a graphene quantum dot using e-beam lithography in combination with oxygen plasma etching. We studied electron spin physics in these structures by J:1pplying large parallel magnetic fields at low temperatures and performing electrical transport measurements. We do not find an ordered filling sequence of spin states, which we assign to edge disorder and surface charge impurities.

Cette thèse porte sur l'étude de deux modèles mathématiques pour une tâchevisuelle élémentaire: le regroupement perceptuel de points 2D. Le premier modèletraite la détection d'alignements de point perceptuellement relevant. Ledeuxième modèle étend ce cadre au cas plus général de la bonne continuation depoints. Dans les deux cas, les modèles proposés sont invariants au changementd'échelle, et non supervisés. Ils sont conçus pour être robustes au bruit,jusqu'au point où les structures à détecter deviennent mathématiquementimpossibles de distinguer du bruit. Les expériences presentées montrent unecohérence entre notre théorie de détéction et les processus de démasquage ayantlieu dans la perception humaine.Les modèles proposés sont basés dans la méthodologie a contrario, uneformalisation du principe de non accidentalité dans la théorie de laperception. Cette thèse fait deux contributions au méthodes a contrario. Une estl'introduction de seuils de détection adaptatifs qui sont conditionnels auxenvirons des structures évaluées. La deuxième contribution est une nouvellestratégie raffinée pour résoudre la redondance de plusieurs détectionssignificatives.Finalement, l'utilité du détecteur d'alignements de points comme outil générald'analyse de données est démontrée avec son application a une problème classiqueen vision par ordinateur: la détection de points de fuite. Le détecteurd'alignements de points proposé, utilisé avec des outils standards, produit desrésultats améliorant l'état de l'art.Visant à la recherche reproductible, toutes les méthodes sont soumis au journalIPOL, en incluant descriptions détaillées des algorithmes, du code sourcecommenté et démonstrations en ligne pour chaque méthode. / This thesis studies two mathematical models for an elementary visual task: theperceptual grouping of dot patterns. The first model handles the detection ofperceptually relevant arrangements of collinear dots. The second model extendsthis framework to the more general case of good continuation of dots. In bothcases, the proposed models are scale invariant and unsupervised. They aredesigned to be robust to noise, up to the point where the structures to detectbecome mathematically indistinguishable from noise. The experiments presentedshow a good match of our detection theory with the unmasking processes takingplace in human perception, supporting their perceptual plausibility.The proposed models are based on the a contrario framework, a formalization ofthe non-accidentalness principle in perception theory. This thesis makes twocontributions to the a contrario methodology. One is the introduction ofadaptive detection thresholds that are conditional to the structure's localsurroundings. The second is a new refined strategy for resolving the redundancyof multiple meaningful detections. Finally, the usefulness of the collinear point detector as a general patternanalysis tool is demonstrated by its application to a classic problem incomputer vision: the detection of vanishing points. The proposed dot alignmentdetector, used in conjunction with standard tools, produces improved resultsover the state-of-the-art methods in the literature.Aiming at reproducible research, all methods are submitted to the IPOL journal,including detailed descriptions of the algorithms, commented reference sourcecodes, and online demonstrations for each one.

Quantum dots (QDs) have the potential to produce more than one exciton per incident photon, if the photon energy is greater than twice the band gap energy. This process of multiple exciton generation (MEG) has the potential to lead to a step change in the efficiency of solar panels, by utilising energy commonly wasted as heat in conventional solar cells. A wide range of CdSe/CdTe and CdTe/CdSe quantum dots with and without a CdS shell were synthesised with varying core sizes and shell thicknesses. The excited state dynamics of these samples were studied with transient absorption and photoluminescence studies, with their MEG efficiencies obtained. Record MEG efficiencies were obtained with values reaching 142 ± 9 % achieved. The charge separation afforded by the type-II electronic configuration, allowed the first attractive biexciton interaction for a type-II QD system, with the potential for reducing the creation energy for a second exciton this affords. Efficient surface passivation of QDs was achieved through the reaction of CdCl2 with CdTe QDs, with near unity photoluminescence quantum yields (PLQYs) achieved. The suppression of surface trap states resulted in mono-exponential photoluminescence decay traces, with a resultant increase in exciton lifetime. Further CdCl2 treatment was carried out on CdSe/CdTe quasi-type-II QDs with alternating ‘Cd rich’ and ‘Te rich’ surfaces to elucidate the processes involved in surface treatment. It is shown that Te surface atoms are preferentially etched upon treatment, with the reaction being more aggressive when ‘Te rich’ surfaces are treated. The importance of surface composition is studied with trap states associated with chalcogen dangling bonds more prevalent and hence the increased requirement for their passivation is outlined. Control of the core/shell interface is also shown to be important in reducing trap states and ultimately increasing PLQYs, which is desirable for many optoelectronic applications.

M.Sc. / This report illustrates the synthesis and characterization of CdS and CdSe nanoparticles in TOPO, HDA and hexamethylenediamine. The prepared nanoparticles were characterized using UV-visible and photoluminescence spectrophotometers for optical properties, transmission electron microscopy for shapes and sizes as well as powder X-ray diffractometer for structural analysis. The effect of monomer concentration and temperature were investigated on the growth of nanocrystals. The monomer concentration was varied by changing the amount of stabilizer. The particle sizes increased with an increase in monomer concentration. Higher monomer concentration resulted in polydispersed nanoparticles due to faster uncontrolled growth. Increasing the temperature resulted in a faster growth thus increasing the size of the particles. The growth also affected the shapes of the particles as the particles tend to grow anisotropical ly at higher monomer concentration and high temperatures. The formation of tretrapods at high temperatures was due to a kinetically driven reaction as a result of increased temperature. Hexamethylenediamine was found to be a poor capping agent for the prepared CdS nanoparticles. The particles prepared in the compound agglomerated at all temperatures used in preparation. Such results were associated with lower steric hindrance due to a shorter molecular chain. The polymer nanofibres were fabricated via electrospinning technique while varying the concentrations of the polymer solutions. Solutions of low viscosity gave beaded fibres as mixtures of droplets and fibres due to the collection of wet fibres. An increase in the concentration (viscosity) of the solutions resulted in the deposition of solid fibres with bigger diameters. The TGA results show that PMMA electrospun fibres demonstrate a significant increase in thermal stability compared to the powder polymer. However the changes were very minimal on the PEO fibres. CdS and CdSe nanoparticles were incorporated into PMMA and PEO and electrospun to fabricate composite fibres. The incorporation of the quantum dots caused an increase in the viscosity of the solutions and resulted in the collection of fibres with spiral morphology. However this increase of concentration caused an increase in the diameters of the composite fibres as evaluated from the SEM analysis. The EDS analysis showed the presence of Cd, S, and Se elements in the composite fibres due to the presence of CdS and CdSe. The XRD analysis of the composite showed no effect of the quantum dots on the amorphous peak of the PMMA. However on the PEO it showed a decrease in the intensity as the peaks as they become broader due to the decrease of crystallinty. The FTIR spectra showed that the presence of the quantum dots in the polymers on both PMMA and PEO. The optical analysis showed absorption and emissions peaks on the composites fibres due to the showed incorporated light emitter. These peaks were not affected by any change in the concentrations as a result of increased wt % of the quantum dots. Thermal analysis of the composite fibres demonstrates an increase in the thermal stability of the polymers after the incorporation of the quantum dots. Very small changes were observed for the quantum dots doped-PEO material compared to the doped PMMA. DSC analysis showed an increase in the glass transition temperature of the PMMA with increasing wt % of the CdS and CdSe. The addition of CdS and CdSe nanoparticles into PEO caused a decrease in the melting temperature of the polymer due to a decrease in the polymer crystallinity.

This dissertation explores the effect of nanometer-scale changes in structure on the energetics of photocatalytic and photovoltaic materials. Of particular interest are semiconductor nanocrystals (NCs), which have interesting chemical properties that lead to novel structures and applications. Chief among these properties are quantum confinement and the high surface area-to-volume ratio, which allow for chemical tuning of the energetics and structure of NCs. This tunable energetic landscape has led to increasing application of NCs in various areas of research, including solar energy conversion, light-emitting diode technologies, and photocatalysis. However, spectroscopic methods to determine the energetics of NCs have not been well developed, due to chemical complexities of relevant NCs such as polydispersity, capping ligand effects, core-shell structures, and other chemical modifications. In this work, we demonstrate and expand the utility of photoelectron spectroscopy (PES) to probe the energetics of NCs by considering the physical processes that lead to background and secondary photoemission to enhance photoemission from the sample of interest. A new methodology for the interpretation of UP spectra was devised in order to emphasize the minute changes to the UP spectra line shape that arise from nanoscopic changes to the NCs. We applied various established subtractions that correct for photon source satellites, secondary photoelectrons, and substrate photoemission. We then investigated the effect of ligand surface coverage on the surface chemistry and density of states at the top of valence band (VB). We systematically removed ligands by increasing numbers of purification steps for two diameters of NCs and found that doing so increased photoemission density at the top of the VB, which is due to undercoordinated surface atoms. Deeper VB structure was also altered, possibly due to reorganization of the atoms in the NC. Using the new UPS interpretation methodology, we examined the evolution of the valence band energy (EVB) of CdSe NCs as it was modified from spherical NC to rod to Au-NP tipped nanorod (NR). We also employed potential-modulated attenuated total reflectance spectroscopy (PM-ATR) to probe the conduction band energy (ECB) of the series. The EVB decreased with each modification, which is predicted with a band-bending model. This trend was also observed in the ECB, as revealed by spectroelectrochemistry, along with the appearance of new metal-semiconductor states in the band gap. UPS was finally used to investigate the even more complex Pt-NP tipped CdSe@CdS core@shell NR heterostructure. The addition of the CdS shell decreases the EVB relative to CdSe, as expected from common cation II-VI compounds. The Pt-NC increases the EVB, which, like the Au-CdSe NR, is predicted by employing a band-bending model. XPS revealed that PtSx-like chemical states were formed near the CdS-Pt interface. These experiments, along with the improved UP spectra interpretation methodology, demonstrate the wealth of information regarding surface chemistry and energetics that can be obtained with PES which can be applied to not only NCs, but also to metal oxide or molecular thin films.

The emergence of optical applications, such as lasers, fiber optics, and semiconductor based sources and detectors, has created a drive for smaller and more specialized devices. Nanophotonics is an emerging field of study that encompasses the disciplines of physics, engineering, chemistry, biology, applied sciences and biomedical technology. In particular, nanophotonics explores optical processes on a nanoscale. This dissertation presents nanophotonic applications that incorporate various forms of the organic polymer N-isopropylacrylamide (NIPA) with inorganic semiconductors. This includes the material characterization of NIPA, with such techniques as ellipsometry and dynamic light scattering. Two devices were constructed incorporating the NIPA hydrogel with semiconductors. The first device comprises a PNIPAM-CdTe hybrid material. The PNIPAM is a means for the control of distances between CdTe quantum dots encapsulated within the hydrogel. Controlling the distance between the quantum dots allows for the control of resonant energy transfer between neighboring quantum dots. Whereby, providing a means for controlling the temperature dependent red-shifts in photoluminescent peaks and FWHM. Further, enhancement of photoluminescent due to increased scattering in the medium is shown as a function of temperature. The second device incorporates NIPA into a 2D photonic crystal patterned on GaAs. The refractive index change of the NIPA hydrogel as it undergoes its phase change creates a controllable mechanism for adjusting the transmittance of light frequencies through a linear defect in a photonic crystal. The NIPA infiltrated photonic crystal shows greater shifts in the bandwidth per ºC than any liquid crystal methods. This dissertation demonstrates the versatile uses of hydrogel, as a means of control in nanophotonic devices, and will likely lead to development of other hybrid applications. The development of smaller light based applications will facilitate the need to augment the devices with control mechanism and will play an increasing important role in the future.