xv, 153 p. : ill. (some col.) / Lead sulfide nanocrystals (PbS-NCs) are an important class of semiconductor nanomaterials that are active in the near-infrared and exhibit unique properties distinct from their bulk analogues, notably, size tunability of the band gap and solution processability. One factor influencing PbS-NC properties is the presence of an organic ligand shell, which forms the interface between the nanocrystal core and its environment. The specific focus of this dissertation is how ionic functionalization of the ligand shell alters the physical and chemical properties of the resulting PbS-NC/ligand complex. Short-chain ligands can improve photoconductivity in PbS-NC thin films, but there are few solution-based preparations available. Chapter II demonstrates how ionic groups can enable functionalization of PbS-NCs with two short- chain thiol ligands - sodium 3-mercaptopropanesulfonate (MT) and sodium 2,3-dimercaptopropanesulfonate (DT) - via a solution-phase exchange procedure. Despite a structural similarity, DT-functionalized PbS-NCs (PbS-DT) are more stable to oxidation than MT-functionalized PbS-NCs (PbS-MT). The relative stabilities are explained in terms of different binding modes to the nanocrystal surface (bidentate vs. monodentate) and oxidation pathways (intermolecular vs. intramolecular). Toxicology studies on nanomaterials have been limited by the availability of water-soluble samples with systematically controlled structures. As examples of such materials, PbS-DT and PbS-MT nanocrystals are studied in Chapter III for their toxicological impacts on embryonic zebrafish. PbS-DT solutions induce less toxicity than PbS-MT solutions, which is explained in terms of the relative stabilities of the nanocrystal solutions. Finally, Chapter IV investigates the hitherto unexplored effects of ionic functionalization on the optical/electrical properties of PbS-NC thin films, with an emphasis on understanding how counter ions affect the photoconductivity of PbS-DT thin films. Films containing small counter ions exhibit increased dark conductivity and responsivity with time under an applied bias, whereas films containing larger or multivalent counter ions show a suppression of this behavior. These results are discussed in terms of ion motion and ion-assisted carrier injection at the PbS-NC/electrode interface. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: David R. Tyler, Chair; Mark C. Lonergan, Advisor; Catherine J. Page, Inside Member; Andrew Marcus, Inside Member; Hailin Wang, Outside Member

abstract: The energy band gap of a semiconductor material critically influences the operating wavelength of an optoelectronic device. Realization of any desired band gap, or even spatially graded band gaps, is important for applications such as lasers, light-emitting diodes (LEDs), solar cells, and detectors. Compared to thin films, nanowires offer greater flexibility for achieving a variety of alloy compositions. Furthermore, the nanowire geometry permits simultaneous incorporation of a wide range of compositions on a single substrate. Such controllable alloy composition variation can be realized either within an individual nanowire or between distinct nanowires across a substrate. This dissertation explores the control of spatial composition variation in ternary alloy nanowires. Nanowires were grown by the vapor-liquid-solid (VLS) mechanism using chemical vapor deposition (CVD). The gas-phase supersaturation was considered in order to optimize the deposition morphology. Composition and structure were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD). Optical properties were investigated through photoluminescence (PL) measurements. The chalcogenides selected as alloy endpoints were lead sulfide (PbS), cadmium sulfide (CdS), and cadmium selenide (CdSe). Three growth modes of PbS were identified, which included contributions from spontaneously generated catalyst. The resulting wires were found capable of lasing with wavelengths over 4000 nm, representing the longest known wavelength from a sub-wavelength wire. For CdxPb1-xS nanowires, it was established that the cooling process significantly affects the alloy composition and structure. Quenching was critical to retain metastable alloys with x up to 0.14, representing a new composition in nanowire form. Alternatively, gradual cooling caused phase segregation, which created heterostructures with light emission in both the visible and mid-infrared regimes. The CdSSe alloy system was fully explored for spatial composition variation. CdSxSe1-x nanowires were grown with composition variation across the substrate. Subsequent contact printing preserved the designed composition gradient and led to the demonstration of a variable wavelength photodetector device. CdSSe axial heterostructure nanowires were also achieved. The growth process involved many variables, including a deliberate and controllable change in substrate temperature. As a result, both red and green light emission was detected from single nanowires. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2012

Colloidal quantum dots (CQDs) are potentially low-cost, solution-processable semiconductors which are endowed, through their nanoscale dimensions, with strong absorption, band gap tunability, high dielectric constants and enhanced stability. CQDs are contenders as a standalone PV technology as well as a potential back layer for augmenting established photovoltaic (PV) technologies, such as Si. However, owing to their small size (ca. few nanometers), CQDs are prone to surface trap states that inhibit charge transport and threaten their otherwise wonderful optoelectronic properties. Surface traps have also, indirectly, impeded scalable and industry-compatible fabrication of these solar cells, as all of the reports, to date, have relied on spin-coating with sophisticated and tedious ligand exchange schemes, some of which need to be performed in low humidity environments. In this thesis, we posit that an in-depth understanding of the process-structure-property-performance relationship in CQDs can usher in fresh insights into the nature and origin of surface traps, lead to novel ways to mitigate them, and finally help achieve scalable fabrication. To this end, we probe the CQD surfaces and their interactions with process solvents, linkers, and ambient environment employing a suite of spectroscopic techniques. These fundamental insights help us develop facile chemical and physical protocols to mitigate surface traps such as solvent engineering, remote molecular doping, and oxygen doping, directly leading to better-performing solar cells. Our efforts finally culminate in the realization of >10% efficient, air-stable CQD solar cells scalably fabricated in an ambient environment of high, uncontrolled R.H. (50-65%). As-prepared solar cells fabricated in high humidity ambient conditions are found to underperform, however, an oxygen-doping recipe is devised to mitigate the moisture-induced surface traps and recover device performances. Importantly, these solar cells are fabricated at coating speeds of >15 m min-1 with roll-to-roll compatible techniques such as blade and bar coating requiring 1/25th the CQD material consumed by the standard spin-coated devices, overcoming the two major challenges of manufacturability and scalability faced by CQD PV.

No description available.

No description available.

Thesis (Ph.D.)--McMaster University (Canada), 1991. / Source: Dissertation Abstracts International, Volume: 53-01, Section: B, page: 0503. Supervisor: I. D. Brown.

No description available.

The coherent properties of semiconductor nanostructures are inherently difficult to measure and one-dimensional spectroscopies are often unable to separate inhomogeneous and homogeneous linewidths. We have refined and improved a method of performing multidimensional Fourier transform spectroscopy based on four-wave mixing (FWM) experiments in the box geometry. We have modified our system with broadband beamsplitters in all interferometer arms, high-resolution translation stages and the ability to work in reflection geometry. By improving the phase-stability of our setup and scanning pulse delays with sub-optical cycle precision, we are able to reproduce 2DFT spectra of GaAs multiple quantum wells. With the FWM signal reflected from the sample surface instead of transmitted through, we show that very low pulse powers can be used to generate coherent 2D signals from colloidal PbS quantum dots. Dephasing times are particularly difficult to measure in small colloidal quantum dots due to environmental broadening effects from the colloidal growth. We show that low-temperature pure excitonic dephasing can be measured via time-integrated measurements as well as from the cross-diagonal linewidths of 2DFT spectra. Ultrafast sub-picosecond dephasing times are measured at 5 K in 3 nm PbS quantum dots, while excitation-density-dependence is investigated in these dots. By retrieving the global phase with an all-optical method, we are able to retrieve the real-part 2D spectra of PbS quantum dots.

The assembly of nanostructures into “multi”-dimensional materials is one of the main topics occurring in nanoscience today. It is now possible to produce high quality nanostructures reproducibly but for their further application larger structures that are easier to handle are required. Nevertheless during their assembly their nanometer size and accompanying properties must be maintained. This challenge was addressed in this work. Lead chalcogenides have been chosen as an example system because they are expected to offer great opportunities as thermoelectric materials. Three different ways to achieve assemblies of lead chalcogenide nanostructures were used and the resulting structures characterized with respect to their potential application as thermoelectric material. The first means by which a “multi”-dimensional assembly of lead chalcogenide quantum dots can be produced is the formation of porous structures such as aerogels and xerogels. A procedure, where the addition of an initiator such as oxidizers or incident radiation is unnecessary, is introduced and the formation process studied by absorption spectroscopy. The time-consuming aggregation step could be significantly reduced by employing a slightly elevated temperature during gelation that does not lead to any observable differences within the resulting gel structures. After either supercritical or subcritical drying, highly porous monolithic gel structures can be achieved. During the gel formation the size and the shape of the particles changed and they were directly linked together. Nevertheless the resulting porous structures remain crystalline and size dependent effects of the optical properties could be shown. Gels produced from a mixture of PbS and PbSe QDs show a homogenous distribution of both materials but it is not clear to what extent they form an alloy. Although the particles are directly linked together the resulting porous structures possess a very high resistivity and so it was not possible to characterize the semiconductor aerogels with regard to their thermoelectric properties. To achieve an enhanced conductivity porous structures containing PbS and Au nanoparticles have been produced. As has been seen for the pure semiconductor gels the size of the PbS quantum dots has increased and elongated particles were formed. In contrast to the PbS QDs the Au nanoparticles did not change their size and shape and are unevenly distributed within the PbS network. Through the use of the gold nanoparticles the conductivity could be increased and although the conductivity is still quite small, it was possible to determine Seebeck coefficients near room temperature for a mixed semiconductor-metal gel. The second means by which QD solids could be formed was by the compaction of the QD building blocks into a material that is still nanostructured. Therefore the synthesis of PbS was optimized to achieve sufficient amounts of PbS quantum dots. The ligands used in the synthesis of the QDs unfortunately act as an insulating layer resulting in QD solids with resistivities as high as 2 Gigaohm. For this reason different surface modification strategies were introduced to minimize the interparticle distance and to increase the coupling between the QDs so as to increase the conductivity of the resulting quantum dot solids. One very promising method was the exchange of the initial ligands by shorter ones that can be destroyed at lower temperatures. By such heat treatments the resistivity could be decreased by up to six orders of magnitude. For the pressing of the quantum dots two different compaction methods (SPS and hydraulic pressing) were compared. While the grain growth within the SPS pressed samples is significantly higher the same densification can be achieved by a cold hydraulic pressing as well as by SPS. The densification could be further increased through the use of preheated PbS QDs due to the destruction of the ligands. Samples which had been surface modified with MPA and subsequently thermally treated show the best results with respect to their thermopower and resistivities. Nevertheless the conductivity of the QD solids is still too high for them to be used as efficient thermoelectric materials. The final assembly method does not involve QDs but instead with one dimensional nanowires. Therefore a synthesis was developed that enables the formation of PbS nanowires of different diameters and one that is easy up-scalable. By the use of a less reactive sulfur precursor and an additional surfactant the formation of nuclei is significantly retarded and within an annealing time of two hours nanowires can be formed presumably by an oriented attachment mechanism. Single crystalline nanowires with a diameter of 65-105 nm could be achieved with the longest axes of the nanowires being parallel to [100]. The resulting nanowires were used as building blocks for film formation on glass substrates by an easily implemented method that requires no special equipment. To characterize the films with a view to their possible application as a thermoelectric material, surface modifications of the films were performed to improve the charge transfer in the films and the Seebeck coefficients of the resulting films measured. Therefore the previous approach of using MPA was applied and a subsequent thermal treatment demonstrated very promising results. In addition an crosslinking ligand was used for surface treatment that leads to similar results as was observed for the thermally treated MPA approach. Both approaches lead to an order of magnitude decrease in the resistivity and due to the fewer grain boundaries present in the films composed of nanowires as compared to the QD assemblies the conductivity is significantly higher. The Seebeck coefficient measurements show that the thermal treatment only slightly affects the Seebeck coefficients. Therefore a significantly higher power factor could be achieved for the nanowire films than for the QD solids.

Made available in DSpace on 2016-04-18T21:39:46Z (GMT). No. of bitstreams: 3 Jackson Sen Kiat Ong1.pdf: 336586 bytes, checksum: 52b71abae661534b419bd2bda584dc4a (MD5) Jackson Sen Kiat Ong2.pdf: 1278219 bytes, checksum: ec194da3074f4dd751b05ea76d3b09f6 (MD5) Jackson Sen Kiat Ong4.pdf: 1869905 bytes, checksum: e24bb294662a8c0696b7e5fda65c5f7c (MD5) Previous issue date: 2008-01-29 / Fundação de Amparo a Pesquisa do Estado de São Paulo / Photonic Crystal Fibers (PCFs) have led to renewed attention to the fiber optics field due to the several unique properties resulting from their microstructured profile. In particular, this profile enables one to insert liquids and polymers into the fiber so that they efficiently interact with light, which can be used for chemical and biological sensing, nonlinear optics, and the development of active photonic devices. Several applications require selectively inserting the sample into the core of a hollow-core PCF, leaving cladding holes unfilled. This dissertation presents two contributions toward the development of core-filled PCFs. Loss mechanisms in liquid-core PCFs are studied and fluorescence from a quantum-dot-doped polymer-core PCF is demonstrated. Loss studies were motivated by the evaluation of the transmission of light at 633 nm in 5-7 cm long water-core PCF samples the tips of which are cleaved at left in air. It was generally found that transmission was less than 5%, while water attenuation alone would lead to ~98% transmission. Liquid evaporation was found to be an important additional loss mechanism and its rate was determined both through microscopy and optical coherence tomography (OCT) in capillary fibers and PCFs filled with deionized water, ethanol and toluene. Although the evaporation rate in ethanol was found to be higher, for all samples a few hundreds of micrometers at the fiber tips are emptied over minutes. A method to prevent evaporation consisting of sealing the fiber tips with a clear UV curable polymer (NOA 73) was successfully tested. Filling a PCF with active elements can lead to optical amplification and laser action. Researchers at NTT recently observed fluorescence at 609nm from CdSe quantum dots in the core of a 1m long PCF. In this dissertation, the fluorescence emission is described from ~2.2 nm PbS quantum dots was observed with a specified emission peak of 890 nm. The quantum dots were suspended in NOA73 and inserted in the core of 7-9 cm long PCFs of with a hollow core diameter of 10.9 5m. The fiber was pumped by a 2.5 mW He-Ne laser or a 679 nm, 390 mW diode laser and its emission was characterized. A maximum fluorescence power of 2.2 5W and a maximum efficiency of 0.03% were achieved. Varying the quantum dot concentration revealed that lower concentrations lead to higher efficiencies. / Fibras de cristal fotônico (PCFs) têm levado a uma atenção renovada ao campo das fibras ópticas devido às diversas propriedades exclusivas resultantes do seu perfil microestruturado. Em particular, este perfil permite a introdução de líquidos e polímeros na fibra de modo que estes interajam eficientemente com a luz, levando a aplicações em sensoriamento químico e biológico, óptica não-linear, e o desenvolvimento de dispositivos fotônicos ativos. Diversas aplicações requerem a inserção seletiva da amostra no núcleo de uma PCF de núcleo oco, deixando buracos da casca sem preenchimento. Esta dissertação apresenta duas contribuições para o desenvolvimento de PCFs de núcleo preenchido. Os mecanismos de perda em PCFs de núcleo líquido são estudados e a fluorescência de uma PCF de núcleo polimérico dopado com pontos quânticos é demonstrada. Os estudos da perda foram motivados pela análise da transmissão da luz em 633 nm em amostras de 5-7 cm de PCF de núcleo de água cujas pontas eram clivadas e deixadas no ar. Geralmente a transmissão encontrada era menor do que 5%, enquanto que a atenuação da água poderia levar a ~98% de transmissão. Verificou-se que a evaporação do líquido era um mecanismo de perda importante e sua taxa foi determinada através de microscopia e de tomografia por coerência óptica (OCT) em fibras capilares e PCFs preenchidas com água deionizada, etanol e o tolueno. Embora a taxa da evaporação no etanol seja maior, para todas as amostras algumas centenas de micrômetros nas pontas da fibra são esvaziadas em minutos. Um método para impedir a evaporação que consiste em selar as pontas da fibra com um polímero curável por UV (NOA 73) foi testado com sucesso. O preenchimento de uma PCF com elementos ativos pode conduzir a amplificação óptica e ação laser. Pesquisadores da NTT observaram recentemente fluorescência em 609 nm em pontos quânticos de CdSe no núcleo de uma PCF de 1 m de comprimento. Nesta dissertação, a emissão de fluorescência é observada com pontos quânticos de PbS de ~2,2 nm e pico de emissão nominal em 890 nm. Os pontos quânticos foram suspensos em NOA73 e introduzidos no núcleo de PCFs de 7-9 cm de comprimento e núcleo oco de 10,9 5m de diâmetro. A fibra foi bombeada por um laser de He-Ne de 2,5 mW ou um laser de diodo de 679 nm e 390 mW e sua emissão foi caracterizada. Uma fluorescência com potência máxima de 2,2 5W e eficiência máxima de 0,03% foi obtida. Variando a concentração de pontos quânticos observou-se que baixas concentrações levam a eficiências mais elevadas.