In this work, the operating characteristics of quantum dot (QD) lasers with asymmetric barrier layers (ABLs) are studied. Several different cases are examined, in particular: 1) Effect of excited states on static and dynamic operating characteristics Within QDs, in addition to the lasing ground state, carriers can be captured into excited states, where they then decay into the ground state. This excited-state-mediated capture impacts the operating characteristics, limiting the maximum output power and modulation bandwidth. Three separate cases are considered: only indirect capture with electron-hole symmetry, both direct and indirect capture with electron-hole symmetry, and both direct and indirect capture of electrons but only indirect capture of holes. The impact of different parameters on the operating characteristics is studied, with values for maximizing the output power and modulation bandwidth being found. In addition, it is found that parasitic recombination in the active region in the space between QDs causes the output power to saturate at high injection currents for the cases of indirect capture for both electrons and holes and indirect capture for holes but direct and indirect capture for electrons, although the presence of the ABLs causes it to reach saturation at much lower currents. 2) QD laser with only a single ABL To be effective, the materials for ABLs must be carefully chosen to ensure that the band edges properly align to allow one carrier to enter the active region while preventing the other from overshooting it. Due to this requirement, it may arise that a suitable material only exists for one ABL but not the other. The performance of a QD laser with only a single ABL is considered and compared to a conventional QD laser. Specifically, the output power and characteristic temperature are calculated. While the single ABL laser only offers a negligible increase in output power compared to the conventional laser, it offers a considerable increase in characteristic temperature. 3) Analytical derivation of alpha factor in QD lasers with and without ABLs The alpha factor of a semiconductor laser describes the spectral linewidth broadening that occurs in semiconductor lasers due to changes in the refractive index due to the carrier density. While it has been studied experimentally, there has been little work done on deriving the alpha factor of QD lasers analytically. An expression for the alpha factor is found in this work using the real and imaginary parts of the complex susceptibility. For QD lasers with no inhomogeneous broadening, as well as ones with equilibrium filling of QDs with narrow line of QD size distribution, the alpha factor is independent of carrier density, and is therefore the same for any QD lasers, with or without ABLs. For QD lasers with equilibrium filling without a narrow line of QD size distribution, the alpha factor depends on carrier density, allowing for a potential difference between conventional and ABL QD lasers, however the difference between the two will be lessened. / Doctor of Philosophy / Semiconductor lasers are the most widely used laser, due in part to their ability to be controlled using electricity. Semiconductor lasers are used in a wide variety of consumer electronics, such as optical drives, as well as being used in fiber optic communications, where data is transmitted using the laser's light. Fiber optic communications transmit data by controlling the laser's output, where a high output (brighter light) represents a digital one, and a low output (dimmer light) represents a digital zero. Because semiconductor lasers can be directly controlled by changing the amount of current they receive, their output can easily be changed, allowing fast transfer of data. Despite their benefits, semiconductor lasers suffer from a drawback known as parasitic recombination. Parasitic recombination is a process that makes a significant portion of the current injected to generate useful light go to waste, which negatively impacts the laser's performance. One solution to parasitic recombination is the addition of asymmetric barrier layers (ABLs). By adding ABLs, parasitic recombination can be completely removed. In this work, several different cases of semiconductor quantum dot (QD) laser with ABLs are examined. Starting from a set of equations, the operating characteristics of the lasers in the different cases are found. First, the case of excited states is examined. The presence of excited states in semiconductor lasers impacts the rate that current can be converted to light, lowering their performance. By solving the starting rate equations, which describe the way different values change over time, the performance of the laser can be calculated. Specifically, the impact of several tunable parameters on the output power and modulation bandwidth are examined. The modulation bandwidth is how fast the laser output can be changed, which is equivalent to how fast data can be transmitted. Optimum values for the DC injection current, QD surface density (number of QDs per area), and laser cavity length are found.

No description available.

Oxido nítrico (NO) é uma molécula que participa de várias atividades fisiológicas no organismo, entre as quais incluem-se ação vasodilatadora e antitumoral. Entretanto sua resposta biológica é dependente da concentração, que quando alta apresenta citotoxicidade. Um fator limitante para sua aplicação em sistemas biológicos é seu curto tempo de meia vida no organismo, o que direcionou os estudos de complexos de rutênio-nitrosilo (RuNO) como doadores de NO. Complexos RuNO apresentam interesse especial devido suas propriedades termoestáveis e fotoquímicas. O uso da luz como um estímulo externo torna-se vantajoso pela capacidade de controlar-se a localização, o tempo de liberação da droga e a dosagem. A terapia fotodinâmica (TFD) tem sido aplicada na terapia clínica contra o câncer. TFD depende da concentração de oxigênio para a produção de espécies reativas, o que é limitado em alguns tipos de tumores devido a hipóxia. Os Pontos quânticos (PQs), semicondutor nanocristalino, destacam-se como materais funcionais com propriedade ópticas únicas dependentes do tamanho. Podem atuar como antenas na captação de luz e fotossensibilização de complexos rutênio-nitrosilo para a liberação de moléculas bioativas. Neste trabalho descrevemos a síntese e caracterização de diferentes PQs (CdS, CdSe e CdTe) utilizando diferentes agentes passivantes (ATG, TOPO e AMP)e a síntese e caracterização do complexo rutênio-nitrosilo cis-[Ru(NO)(4-amp)(bpy)2]3+ (4-amp= 4-aminopiridina; bpy = 2,2 \'bipiridina. Estudos das propriedades fotofísicas e avaliação fotoquímica da interação entre PQ e RuNO foram realizados como também a avaliação da atividade citotóxica x desta associação sobre cultura de células de melanoma murino B16-F10. As medidas das propriedades fotofísicas demonstraram interação pela supressão da fluorescência analisada pela equação de Stern-Volmer. Pela determinação do número de sítios de ligação (≈ 2) e a constante de ligação (kb) verificou-se que a interação entre as espécies apresentaram supressão da emissão em um gráfico não linear de Stern-Volmer resultante do processo de agregação entre os compostos. Os dados obtidos corroboram para o mecanismo proposto, demonstrando que cada PQ540 interage com duas moléculas de RuNO. Ainda observou-se que, sob irradiação na região do visível, em 532 nm, aumenta-se o número de mols de NO liberado de no mínimo 6 vezes quando irradiado na presença de PQs comparado à irradiação do complexo sozinho em solução. O processo de transferência eletrônica fotoinduzida foi proposto como o mecanismo fotoquímico para a liberação de NO, enquanto que o processo de transferência de energia mostrou-se desfavorável devido a não sobreposição entre os espectros de absorção do complexo nitrosilo e o espectro de emissão do PQ. As análises de imagem fluorescentes demonstraram o potencial dos PQs como marcadores celulares. As concentrações utilizadas nos experimentos não demonstraram toxicidade sobre as células de melanoma murino na ausência de luz. Porém quando irradiadas, apresentaram citotoxicidade parcial. Portanto, essa transferência pode ocorrer pela redução do NO+ para NO0, seguida pela liberação de NO ou por fotoaquação e consequente fotoredução do nitrito em solução. / Nitric oxide (NO) is a molecule involved in many physiological activities in human body among them include vasodilator and antitumoral. However, the biological response is concentration dependent and in high concentrations it causes cytotoxicity. A limiting factor for biological applications is the short half-life of NO in the body which has led to the research of nitrosyl ruthenium complexes (RuNO) as NO donors. RuNO complexes are of special interest because of their thermal stability and photochemical properties. The use of light as an external stimulus is advantageous as we can track the location, timing of drug release and dosage. Photodynamic therapy (PDT) has been used in clinical therapy for cancer treatment. PDT depends on oxygen concentrations for reactive oxygen species production what is limited in some types of tumors because of hypoxia. The Quantum dots (QDs), semiconductor nanocrystal, as functional materials, possess unique optical size-dependent properties. QDs can act as antennas in capturing light and photosensitizing ruthenium- nitrosyl complexes for release of bioactive molecules. In this work we describe the synthesis and characterization of different PQs (CdS, CdSe and CdTe) using different passivating agents (TGA, TOPO and MPA), the synthesis and characterization of ruthenium- nitrosyl complex cis-[ Ru(NO)(4- amp)( bpy )2]3+ (4 -amp = 4 - aminopyridine; bpy = 2,2 \'bipyridine ). The photophysical properties and photochemical evaluation from the interaction between QD and RuNO were done as well the citotoxicity activity from thi association on murine melanoma cell line B16-F10 . Measurements of photophysical xii properties show interactions by the quenching of fluorescence plotted with the Stern-Volmer equation. By determining the number of binding sites (≈ 2) and the binding constants ( kb ) it was found that the interaction between the species presented an emission suppression in a nonlinear curve Stern- Volmer plot resulted by the aggregation process between both compounds. The data corroborates the proposed mechanism that QD540 interacts with two molecules of RuNO. It was also observed that under irradiation in the visible region, 532 nm, that moles of NO released increases at least 6 times when irradiated in the presence of QDs compared to the irradiation of the RuNO complex alone in solution. The process of photo induced electron transfer was proposed as the mechanism for photochemical release of NO while the process of energy transfer was deemed unfavorable due to no overlap between nitrosyl complex absorption and the QD emission spectrum. The fluorescence image analysis demonstrated the potential of QDs as cell markers. The concentrations used in the experiments have not shown toxicity on murine melanoma cells in the absence of light. However when irradiated, QDs exhibited partial cytotoxicity. Therefore, this transfer may occur by the reduction of NO+ to NO0, followed by the release of NO or photoaquation and subsequent photoreduction of nitrite in solution.

Oxido nítrico (NO) é uma molécula que participa de várias atividades fisiológicas no organismo, entre as quais incluem-se ação vasodilatadora e antitumoral. Entretanto sua resposta biológica é dependente da concentração, que quando alta apresenta citotoxicidade. Um fator limitante para sua aplicação em sistemas biológicos é seu curto tempo de meia vida no organismo, o que direcionou os estudos de complexos de rutênio-nitrosilo (RuNO) como doadores de NO. Complexos RuNO apresentam interesse especial devido suas propriedades termoestáveis e fotoquímicas. O uso da luz como um estímulo externo torna-se vantajoso pela capacidade de controlar-se a localização, o tempo de liberação da droga e a dosagem. A terapia fotodinâmica (TFD) tem sido aplicada na terapia clínica contra o câncer. TFD depende da concentração de oxigênio para a produção de espécies reativas, o que é limitado em alguns tipos de tumores devido a hipóxia. Os Pontos quânticos (PQs), semicondutor nanocristalino, destacam-se como materais funcionais com propriedade ópticas únicas dependentes do tamanho. Podem atuar como antenas na captação de luz e fotossensibilização de complexos rutênio-nitrosilo para a liberação de moléculas bioativas. Neste trabalho descrevemos a síntese e caracterização de diferentes PQs (CdS, CdSe e CdTe) utilizando diferentes agentes passivantes (ATG, TOPO e AMP)e a síntese e caracterização do complexo rutênio-nitrosilo cis-[Ru(NO)(4-amp)(bpy)2]3+ (4-amp= 4-aminopiridina; bpy = 2,2 \'bipiridina. Estudos das propriedades fotofísicas e avaliação fotoquímica da interação entre PQ e RuNO foram realizados como também a avaliação da atividade citotóxica x desta associação sobre cultura de células de melanoma murino B16-F10. As medidas das propriedades fotofísicas demonstraram interação pela supressão da fluorescência analisada pela equação de Stern-Volmer. Pela determinação do número de sítios de ligação (≈ 2) e a constante de ligação (kb) verificou-se que a interação entre as espécies apresentaram supressão da emissão em um gráfico não linear de Stern-Volmer resultante do processo de agregação entre os compostos. Os dados obtidos corroboram para o mecanismo proposto, demonstrando que cada PQ540 interage com duas moléculas de RuNO. Ainda observou-se que, sob irradiação na região do visível, em 532 nm, aumenta-se o número de mols de NO liberado de no mínimo 6 vezes quando irradiado na presença de PQs comparado à irradiação do complexo sozinho em solução. O processo de transferência eletrônica fotoinduzida foi proposto como o mecanismo fotoquímico para a liberação de NO, enquanto que o processo de transferência de energia mostrou-se desfavorável devido a não sobreposição entre os espectros de absorção do complexo nitrosilo e o espectro de emissão do PQ. As análises de imagem fluorescentes demonstraram o potencial dos PQs como marcadores celulares. As concentrações utilizadas nos experimentos não demonstraram toxicidade sobre as células de melanoma murino na ausência de luz. Porém quando irradiadas, apresentaram citotoxicidade parcial. Portanto, essa transferência pode ocorrer pela redução do NO+ para NO0, seguida pela liberação de NO ou por fotoaquação e consequente fotoredução do nitrito em solução. / Nitric oxide (NO) is a molecule involved in many physiological activities in human body among them include vasodilator and antitumoral. However, the biological response is concentration dependent and in high concentrations it causes cytotoxicity. A limiting factor for biological applications is the short half-life of NO in the body which has led to the research of nitrosyl ruthenium complexes (RuNO) as NO donors. RuNO complexes are of special interest because of their thermal stability and photochemical properties. The use of light as an external stimulus is advantageous as we can track the location, timing of drug release and dosage. Photodynamic therapy (PDT) has been used in clinical therapy for cancer treatment. PDT depends on oxygen concentrations for reactive oxygen species production what is limited in some types of tumors because of hypoxia. The Quantum dots (QDs), semiconductor nanocrystal, as functional materials, possess unique optical size-dependent properties. QDs can act as antennas in capturing light and photosensitizing ruthenium- nitrosyl complexes for release of bioactive molecules. In this work we describe the synthesis and characterization of different PQs (CdS, CdSe and CdTe) using different passivating agents (TGA, TOPO and MPA), the synthesis and characterization of ruthenium- nitrosyl complex cis-[ Ru(NO)(4- amp)( bpy )2]3+ (4 -amp = 4 - aminopyridine; bpy = 2,2 \'bipyridine ). The photophysical properties and photochemical evaluation from the interaction between QD and RuNO were done as well the citotoxicity activity from thi association on murine melanoma cell line B16-F10 . Measurements of photophysical xii properties show interactions by the quenching of fluorescence plotted with the Stern-Volmer equation. By determining the number of binding sites (≈ 2) and the binding constants ( kb ) it was found that the interaction between the species presented an emission suppression in a nonlinear curve Stern- Volmer plot resulted by the aggregation process between both compounds. The data corroborates the proposed mechanism that QD540 interacts with two molecules of RuNO. It was also observed that under irradiation in the visible region, 532 nm, that moles of NO released increases at least 6 times when irradiated in the presence of QDs compared to the irradiation of the RuNO complex alone in solution. The process of photo induced electron transfer was proposed as the mechanism for photochemical release of NO while the process of energy transfer was deemed unfavorable due to no overlap between nitrosyl complex absorption and the QD emission spectrum. The fluorescence image analysis demonstrated the potential of QDs as cell markers. The concentrations used in the experiments have not shown toxicity on murine melanoma cells in the absence of light. However when irradiated, QDs exhibited partial cytotoxicity. Therefore, this transfer may occur by the reduction of NO+ to NO0, followed by the release of NO or photoaquation and subsequent photoreduction of nitrite in solution.

Cette thèse s’inscrit dans le domaine de l'opto-mécanique et propose l'utilisation de différentes techniques de mesure et de manipulation des propriétés mécaniques de nano-structures.La première partie de ce travail est dédiée aux fils photoniques. Ces objets sont des structures en GaAs en forme de cône inversé, avec une longueur d’une dizaine de µm et un diamètre inférieur au µm, contenant une couche de boîtes quantiques à l'intérieur. Nous avons démontré une méthode de réglage statique du spectre de photoluminescence de ces boîtes quantiques sensibles à la contrainte, en utilisant des nano-manipulateurs pour contraindre mécaniquement les fils. De plus, grâce à la dépendance spatiale du décalage spectral, il est possible d’établir une carte de la position des boîtes quantiques.La deuxième partie de ce travail concerne la mise en mouvement de ces fils photoniques à l’aide d’un faisceau laser modulé à la fréquence de résonance mécanique. Les mécanismes physiques à l’origine de ces effets sont présentés et discutés.Dans la troisième partie, nous présentons une méthode permettant l’observation d'oscillations mécaniques de nano-fils fins (moins de 50 nm de diamètre) en utilisant un microscope électronique à balayage. Cette méthode originale offre la possibilité de contrôler de nombreux types de structures micro et nano-électromécaniques, dont la détection du mouvement n’est pas possible optiquement en raison de la limite de diffraction de la lumière. De plus, cette méthode permet également d'agir sur les propriétés mécaniques des structures via une force de contre-réaction qui devient non négligeable pour ces structures très légères. Cela ouvre la possibilité d'études fondamentales complémentaires liées au refroidissement du mouvement mécanique. / This thesis is related to the field of opto-mechanics and the use of different techniques for the measurement and manipulation of mechanical properties of nano-structures.First part of the work is dedicated to the photonic wires. These objects are GaAs structures with an inverted conical shape of length of the order of 10 µm and diameter of less than 1 µm, containing a layer of InAs quantum dots inside. Wide-range static stress-tuning of quantum dots photoluminescence spectrum was demonstrated using nano-manipulators to bend the wires. Additionally, owing to the spatial dependence of the spectral shift, this technique offers the possibility of QD positions mapping.The second part of this work concerns the optical actuation of these photonic wires. A laser beam focused on the wire and modulated at the mechanical resonance frequency can set the wire in motion. The physical mechanisms responsible for these effects are presented and discussed.In the third part is presented a method enabling the detection of mechanical oscillations of small (less than 50 nm in diameter) nanowires with the use of a Scanning Electron Microscope. This original method offers a possibility to detect the motion of many types of micro- and nano-electromechanical devices which are too small to be detected optically owing to light diffraction limit.Moreover, this method also affects the mechanical properties of the structures via a back-action force that becomes non-negligible for such small devices. It opens up the possibility for further fundamental studies related to cooling of the mechanical motion.

The cost effective comb based laser sources are considered to be one of the prominent emitters used in optical communication (OC) and photonic integrated circuits (PIC). With the rising demand for delivering triple-play services (voice, data and video) in FTTH and FTTP-based WDM-PON networks, metropolitan area network (MAN), and short-reach rack-to-rack optical computer communications, a versatile and cost effective WDM transmitter design is required, where several DFB lasers can be replaced by a cost effective broadband comb laser to support on-chip optical signaling. Therefore, high performance quantum dot (Q.Dot) comb lasers need to satisfy several challenges before real system implementations. These challenges include a high uniform broadband gain spectrum from the active layer, small relative intensity noise with lower bit error rate (BER) and better temperature stability. Thus, such short wavelength comb lasers offering higher bandwidth can be a feasible solution to address these challenges. However, they still require thorough characterization before implementation. In this project, we briefly characterized the novel quantum dot comb laser using duty cycle based electrical injection and temperature variations where we have observed the presence of reduced thermal conductivity in the active layer. This phenomenon is responsible for the degradation of device performance. Hence, different performance trends, such as broadband emission and spectrum stability were studied with pulse and continuous electrical pumping. The tested comb laser is found to be an attractive solution for several applications but requires further experiments in order to be considered for photonic intergraded circuits and to support next generation computer-communications.

No description available.

I present photonics applications of PbS quantum-dot-doped (QD-doped) glasses. The dissertation consists of two major parts: bulk material applications (Cr:forsterite laser modelocking, bleaching dynamics, optical gain, and photoluminescence) and the fabrication of QD-doped ion-exchanged waveguides.When this work began, these PbS QD-doped glasses were the state-of-the-art in QD glasses due to their narrow size distribution. Modelocking of a Cr:forsterite laser using this glass as a saturable absorber had been demonstrated, with little understanding of the dynamics. This work began by studying the dynamics of the saturable absorber to explain the ps-pulse width.In the bulk measurements, I functioned as secondary researcher. In the laser modelocking and bleaching measurements, my contribution was laser cavity alignment, sample preparation, collecting autocorrelation traces, and aiding in the setup and data collection for the bleaching measurements. On this work, I coauthored one refereed journal article in Applied Physics Letters [1] and one refereed conference paper [2], for which I am third and second author, respectively.For the gain measurements, I aided in the setup and data collection, whereas I set-up and took most of the luminescence data. The gain measurements resulted in one second-author refereed journal article in Applied Physics Letters [3] and I presented the luminescence results at CLEO2000 [4].I took the lead role in the waveguide fabrication and characterization and authored refereed journal articles in Applied Physics Letters [5], Journal of Applied Physics [6], and Journal of the Optical Society of America B [7]. I also presented an invited talk at Photonics West [8] and presented at CLEO2004 [9]. Additionally, I have been a coauthor of presentations at the Nanotechnology Symposium (2006), American Ceramic Society [10], and Photonics Europe (2006) [11]. A book chapter in The Photonics Handbook, 2nd edition [12] also discusses this work.The next step is to focus on reducing the waveguide losses. This requires new, circular wafers with better surface quality and glass homogeneity. I suggest using silver-film ion exchange followed by a field-assisted burial to eliminate the surface interaction.

Doctor of Philosophy / Department of Chemistry / Viktor Chikan / Semiconducting nanoparticles have emerged in the past few decades as an interesting material with great potential in various interdisciplinary applications such as light-emitting devices, solar cells and field-effect transistors, mostly notably for their size-dependent electronic structure and properties. Manipulation of their electronic-optical characters through defects control is one of the most important approaches towards realization of these applications. This thesis focuses on understanding the role of defects, including their impact on carrier density and conductivity at both room and elevated temperature, their impact on growth kinetics of colloidal nanoparticles and new opportunities for dopant control. To achieve these goals, colloidal CdSe quantum dots are doped with gallium atoms and important changes in electronic and optical properties of the material are reported, which shows a significant impact on the growth kinetics of quantum dots, and reveals clues about the mechanism of the gallium dopant incorporation into the CdSe. It is shown that the gallium doping significantly impacts the conductivity of CdSe thin film made of the quantum dots as well as the photoluminescence and chemical reactivity of the quantum dots, in agreement with the expected n-type character. P3HT/CdSe hybrid cells are constructed with Ga-, In- and Sn-doped CdSe QDs, demonstrating high conductivity and stronger electronic coupling which leads to enhanced charge separation and transport efficiency, both essential for hybrid inorganic-organic solar cells. This work also demonstrates a novel heating method that can drastically improve size distribution control of colloidal nanoparticle synthesis. Sub-2-nm ultra-small CdSe QDs are prepared with the induction (magnetic) heating and show excellent agreement of its emission profile compared with natural sunlight. The impact of extreme high heating rate on the development of more accurate nucleation and growth theories are also discussed. Finally, this study also investigates the stabilization of charges from intrinsic defects by looking for altered blinking behaviors of CdSe nanorods (NRs) under different polar environments. TMOS-PTMOS gradient films are prepared with infusion withdrawal dip-coating technique. Although no significant differences are observed of the fluorescence statistics of these NRs, permanent bleaching induced by exciting laser light is discovered, which significantly lowers raw blinking spot count and increases the “off” time of these fluorophores.

Doctor of Philosophy / Department of Chemistry / Viktor Chikan / Doping quantum dots to increase conductivity is a crucial step towards being able to fabricate a new generation of electronic devices built on the “bottom-up” platform that are smaller and more efficient than currently available. Indium, tin, and gallium have been used to dope CdSe in both the bulk and thin film regimes and introduce n-type electron donation to the conduction band. CdSe quantum dots have been successfully doped with indium, tin, and gallium using the Li4[Cd10Se4(SPh16)] single source precursor combined with metal chloride compounds. Doping CdSe quantum dots is shown to effect particle growth dynamics in the “heterogeneous growth regime.” Doping with indium, tin, and gallium introduce donor levels 280, 100, and 50 meV below the conduction band minimum, respectively. Thin films of indium and tin doped quantum dots show improved conductivity over films of undoped quantum dots. Transient Absorption spectroscopy indicates that indium doping introduces a new electron energy level in the conduction band that results in a 70 meV blue shift in the 1Se absorption bleach position. Novel characterization methods such as in-situ fluorescence growth monitoring, single quantum dot EDS acquisition, static and time-resolved temperature dependant fluorescence spectroscopy were developed in the course of this work as well. These results show that doping CdSe quantum dots with indium, tin, and gallium has not only been successful but has introduced new electronic properties to the quantum dots that make them superior to traditional CdSe quantum dots.