Terahertz Response of Excitons in Nanorod Heterostructures

Quantum-confined systems are one of the most promising ways to enable us to control a material's interactions with light. Nanorods in particular offer the right dimensions for exploring and manipulating the terahertz region of the spectrum. In this thesis, we model excitons confined inside a nanorod using the envelope function approximation. A region-matching transfer matrix method allows us to simulate excitonic states inside arbitrary heterostructures grown along the length of the rod. We apply the method to colloidal CdSe rods 70 nm in length and under 10 nm in diameter, capped with ligands of DDPA and pyridine. We extend past studies on these types of rods by taking into account their dielectric permittivity mismatch. Compared to previous calculations and experimentally measured terahertz absorption, we predict a higher energy main 1S$z$ to 2P$z$ transition peak. This indicates that the rods are likely larger in diameter than previously thought. We also investigate a nanorod with GaAs/Al$_{0.3}$Ga$_{0.7}$As coupled double dots. The excitonic transitions were found to be manipulable by varying the strength of an applied electric field. We employ quasi-static state population distributions to simulate the effects of exciton relaxation from optically active states to dim ground states. A critical value of the applied field, corresponding to the exciton binding energy of ~18 meV, was found to dramatically alter the terahertz absorption due to state mixing. Above this critical field, more nuanced shifts in transition energies were observed, and gain from radiative relaxation to the ground state is predicted.

Towards Accurate and Efficient Description of Excited States

Thesis (Ph.D.)--University of Washington, 2016-06

Optics and Optoelectronics of Two-dimensional Semiconducting Monolayers and Heterostructures

Thesis (Ph.D.)--University of Washington, 2016-06

Entangled two-photon source using biexciton emission of an asymmetric quantum dot in a cavity

A semiconductor based scheme has been proposed for generating entangled photon pairs from the radiative decay of an electrically pumped biexciton in a quantum dot. Symmetric dots produce polarization entanglement, but experimentally realized asymmetric dots produce photons entangled in both polarization and frequency. In this work, we investigate the possibility of erasing the “which-path” information contained in the frequencies of the photons produced by asymmetric quantum dots to recover polarization-entangled photons. We consider a biexciton with nondegenerate intermediate excitonic states in a leaky optical cavity with pairs of degenerate cavity modes close to the nondegenerate exciton transition frequencies. An open quantum system approach is used to compute the polarization entanglement of the two-photon state after it escapes from the cavity, measured by the visibility of two-photon interference fringes. We explicitly relate the two-photon visibility to the degree of the Bell-inequality violation, deriving a threshold at which Bell-inequality violations will be observed. Our results show that an ideal cavity will produce maximally polarization-entangled photon pairs, and even a nonideal cavity will produce partially entangled photon pairs capable of violating a Bell-inequality.

Criteria for quantum coherent transfer of excitations between chromophores in a polar solvent

We show that the quantum decoherence of Forster resonant energy transfer between two optically active molecules can be described by a spin-boson model. This allows us to give quantitative criteria that are necessary for coherent quantum oscillations of excitations between the chromophores. Experimental tests of our results should be possible with flourescent resonant energy transfer (FRET) spectroscopy. Although we focus on the case of protein-pigment complexes our results are also relevant to quantum dots and organic molecules in a dielectric medium. (c) 2006 Elsevier B.V. All rights reserved.

Optimization of microcavity OLED by varying the thickness of multi-layered mirror

We optimized the emission efficiency from a microcavity OLEDs consisting of widely used organic materials, N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine (NPB) as a hole transport layer and tris (8-hydroxyquinoline) (Alq(3)) as emitting and electron transporting layer. LiF/Al was considered as a cathode, while metallic Ag anode was used. TiO2 and Al2O3 layers were stacked on top of the cathode to alter the properties of the top mirror. The electroluminescence emission spectra, electric field distribution inside the device, carrier density, recombination rate and exciton density were calculated as a function of the position of the emission layer. The results show that for certain TiO2 and Al2O3 layer thicknesses, light output is enhanced as a result of the increase in both the reflectance and transmittance of the top mirror. Once the optimum structure has been determined, the microcavity OLED devices can be fabricated and characterized, and comparisons between experiments and theory can be made.

Effect of anode material and cavity design on the performance of microcavity OLEDs

We report on the effect of the replacement of the conventional ITO anode with the semitransparent metallic material on the performance of microcavity OLEDs. We performed comprehensive simulations of the emission from microcavity OLEDs consisting of widely used organic materials, N,N′-di(naphthalene-1- yl)-N,N′-diphenylbenzidine (NPB) as a hole transport layer and tris (8-hydroxyquinoline) (Alq3) as emitting and electron transporting layer. Silver and LiF/Al were considered as a cathode, while metallic (Au and Ag) anode was used and simulations were performed on devices with both the metallic and conventional ITO anode. The electroluminescence emission spectra, electric field distribution inside the device, carrier density, recombination rate and exciton density were calculated as a function of the position of the emission layer. The results show that the metallic anode enhances light output and that optimum emission from a microcavity OLED is achieved when the position of the recombination region is aligned with the antinode of the standing wave inside the cavity. The microcavity OLED devices with Ag/Ag and Ag/Au mirrors were fabricated and characterized. The experimental results have been compared to the simulations and the influence of the different anode, emission region width and position on the performance of microcavity OLEDs was discussed.

Functional carbon nanotubes for photonic applications

Carbon nanomaterials are an active frontier of research in current nanotechnology. Single wall Carbon Nanotube (SWNT) is a unique material which has already found several applications in photonics, electronics, sensors and drug delivery. This thesis presents a summary of the author’s research on functionalisation of SWNTs, a study of their optical properties, and potential for an application in laser physics. The first significant result is a breakthrough in controlling the size of SWNT bundles by varying the salt concentrations in N-methyl 2-pyrrolidone (NMP) through a salting out effect. The addition of Sodium iodide leads to self-assembly of CNTs into recognizable bundles. Furthermore, a stable dispersion can be made via addition polyvinylpyrrolidone (PVP) polymer to SWNTs-NMP dispersion, which indicates a promising direction for SWNT bundle engineering in organic solvents. The second set of experiments are concerned with enhancement of photoluminescence (PL), through the formation of novel macromolecular complexes of SWNTs with polymethine dyes with emission from enhanced nanotubes in the range of dye excitation. The effect appears to originate from exciton energy transfer within the solution. Thirdly, SWNT base-saturable absorbers (SA) were developed and applied to mode locking of fibre lasers. SWNT-based SAs were applied in both composite and liquid dispersion forms and achieved stable ultrashort generation at 1000nm, 1550nm, and 1800 nm for Ytterbium, Erbium and Thulium-doped fibre laser respectively. The work presented here demonstrates several innovative approaches for development of rapid functionalised SWNT-based dispersions and composites with potential for application in various photonic devices at low cost.

Resonance fluorescence spectrum of a \Lambda-type quantum emitter close to a metallic nanoparticle

We theoretically study the resonance fluorescence spectrum of a three-level quantum emitter coupled to a spherical metallic nanoparticle. We consider the case that the quantum emitter is driven by a single laser field along one of the optical transitions. We show that the development of the spectrum depends on the relative orientation of the dipole moments of the optical transitions in relation to the metal nanoparticle. In addition, we demonstrate that the location and width of the peaks in the spectrum are strongly modified by the exciton-plasmon coupling and the laser detuning, allowing to achieve controlled strongly subnatural spectral line. A strong antibunching of the fluorescent photons along the undriven transition is also obtained. Our results may be used for creating a tunable source of photons which could be used for a probabilistic entanglement scheme in the field of quantum information processing.

Étude spectroscopique des états localisés dans la bande interdite de composés GaAs₁₋ₓ Nₓ (x<0.1%)

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Resonance Energy Transfer-Based Molecular Switch Designed Using a Systematic Design Process Based on Monte Carlo Methods and Markov Chains

A RET network consists of a network of photo-active molecules called chromophores that can participate in inter-molecular energy transfer called resonance energy transfer (RET). RET networks are used in a variety of applications including cryptographic devices, storage systems, light harvesting complexes, biological sensors, and molecular rulers. In this dissertation, we focus on creating a RET device called closed-diffusive exciton valve (C-DEV) in which the input to output transfer function is controlled by an external energy source, similar to a semiconductor transistor like the MOSFET. Due to their biocompatibility, molecular devices like the C-DEVs can be used to introduce computing power in biological, organic, and aqueous environments such as living cells. Furthermore, the underlying physics in RET devices are stochastic in nature, making them suitable for stochastic computing in which true random distribution generation is critical.

In order to determine a valid configuration of chromophores for the C-DEV, we developed a systematic process based on user-guided design space pruning techniques and built-in simulation tools. We show that our C-DEV is 15x better than C-DEVs designed using ad hoc methods that rely on limited data from prior experiments. We also show ways in which the C-DEV can be improved further and how different varieties of C-DEVs can be combined to form more complex logic circuits. Moreover, the systematic design process can be used to search for valid chromophore network configurations for a variety of RET applications.

We also describe a feasibility study for a technique used to control the orientation of chromophores attached to DNA. Being able to control the orientation can expand the design space for RET networks because it provides another parameter to tune their collective behavior. While results showed limited control over orientation, the analysis required the development of a mathematical model that can be used to determine the distribution of dipoles in a given sample of chromophore constructs. The model can be used to evaluate the feasibility of other potential orientation control techniques.

A Molecular-scale Programmable Stochastic Process Based On Resonance Energy Transfer Networks: Modeling And Applications

While molecular and cellular processes are often modeled as stochastic processes, such as Brownian motion, chemical reaction networks and gene regulatory networks, there are few attempts to program a molecular-scale process to physically implement stochastic processes. DNA has been used as a substrate for programming molecular interactions, but its applications are restricted to deterministic functions and unfavorable properties such as slow processing, thermal annealing, aqueous solvents and difficult readout limit them to proof-of-concept purposes. To date, whether there exists a molecular process that can be programmed to implement stochastic processes for practical applications remains unknown.

In this dissertation, a fully specified Resonance Energy Transfer (RET) network between chromophores is accurately fabricated via DNA self-assembly, and the exciton dynamics in the RET network physically implement a stochastic process, specifically a continuous-time Markov chain (CTMC), which has a direct mapping to the physical geometry of the chromophore network. Excited by a light source, a RET network generates random samples in the temporal domain in the form of fluorescence photons which can be detected by a photon detector. The intrinsic sampling distribution of a RET network is derived as a phase-type distribution configured by its CTMC model. The conclusion is that the exciton dynamics in a RET network implement a general and important class of stochastic processes that can be directly and accurately programmed and used for practical applications of photonics and optoelectronics. Different approaches to using RET networks exist with vast potential applications. As an entropy source that can directly generate samples from virtually arbitrary distributions, RET networks can benefit applications that rely on generating random samples such as 1) fluorescent taggants and 2) stochastic computing.

By using RET networks between chromophores to implement fluorescent taggants with temporally coded signatures, the taggant design is not constrained by resolvable dyes and has a significantly larger coding capacity than spectrally or lifetime coded fluorescent taggants. Meanwhile, the taggant detection process becomes highly efficient, and the Maximum Likelihood Estimation (MLE) based taggant identification guarantees high accuracy even with only a few hundred detected photons.

Meanwhile, RET-based sampling units (RSU) can be constructed to accelerate probabilistic algorithms for wide applications in machine learning and data analytics. Because probabilistic algorithms often rely on iteratively sampling from parameterized distributions, they can be inefficient in practice on the deterministic hardware traditional computers use, especially for high-dimensional and complex problems. As an efficient universal sampling unit, the proposed RSU can be integrated into a processor / GPU as specialized functional units or organized as a discrete accelerator to bring substantial speedups and power savings.

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

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

Excitonic behaviour in polymeric semiconductors : the effect of morphology and composition in heterostructures

La compréhension des interrelations entre la microstructure et les processus électroniques dans les polymères semi-conducteurs est d’une importance primordiale pour leur utilisation dans des hétérostructures volumiques. Dans cette thèse de doctorat, deux systémes diffèrents sont étudiés ; chacun de ces systèmes représente une approche diffèrente pour optimiser les matériaux en termes de leur microstructure et de leur capacité à se mettre en ordre au niveau moléculaire. Dans le premier système, j’ai effectué une analyse complète des principes de fonctionnement d’une cellule photovoltaïque hybride à base des nanocristaux d’oxyde de zinc (ZnO) et du poly (3-hexylthiophène) (P3HT) par absorption photoinduite en régime quasi-stationnaire (PIA) et la spectroscopie PIA en pompage modulé dépendant de la fréquence. L’interface entre le donneur (le polymère P3HT) et l’accepteur (les nanoparticules de ZnO), où la génération de charges se produit, joue un rôle important dans la performance des cellules photovoltaïques hybrides. Pour améliorer le mécanisme de génération de charges du P3H: ZnO, il est indispensable de modifier l’interface entre ses constituants. Nous avons démontré que la modification d’interface moléculaire avec cis-bis (4, 40 - dicarboxy-2, 20bipyridine) ruthénium (II) (N3-dye) et a-Sexithiophen-2 yl-phosphonique (6TP) a améliorée le photocourant et la performance dans les cellules P3HT: ZnO. Le 6TP et le N3 s’attachent à l’interface du ZnO, en augmentant ainsi l’aire effective de la surface donneur :accepteur, ce qui contribue à une séparation de charge accrue. De plus, le 6TP et le N3 réduisent la densité de pièges dans le ZnO, ce qui réduit le taux de recombinaison des paires de charges. Dans la deuxième partie, jai introduit une matrice hôte polymérique de polystyréne à masse molaire ulra-élevée, qui se comporte comme un solide pour piéger et protéger une solution de poly [2-méthoxy, 5- (2´-éthyl-hexoxy) -1,4-phénylènevinylène- PPV] (MEHPPV) pour utilisation dans des dispositifs optoèlectroniques quantiques. Des travaux antérieurs ont montré que MEH-PPV en solution subit une transition de conformation, d’une conformation enroulé à haute température (phase bleue) à une conformation de chaîne étendue à basse température (phase rouge). La conformation de la chaîne étendue de la solution MEH-PPV favorise les caractéristiques nécessaires à l’amélioration des dispositifs optoélectroniques quantiques, mais la solution ne peut pas être incorporées dans le dispositif. J’ai démontré que la caractéristique de la phase rouge du MEH-PPV en solution se maintient dans une matrice hôte polymérique de polystyrène transformé de masse molaire très élevée, qui se comporte comme un solide (gel de MEH-PPV/UHMW PS), par le biais de la spectroscopie de photoluminescence (PL) dépendant de la température (de 290K à 80 K). La phase rouge du gel MEH-PPV/UHMW PS se manifeste par des largeurs de raie étroites et une intensité augmentée de la transition 0-0 de la progression vibronique dans le spectre de PL ainsi qu’un petit décalage de Stokes entre la PL et le spectre d’absorption à basse température. Ces approches démontrent que la manipulation de la microstructure et des propriétés électroniques des polymères semi-conducteurs ont un impact direct sur la performance de dispositifs pour leurs développements technologiques continus.

Étude spectroscopique des états localisés dans la bande interdite de composés GaAs₁₋� N� (x<0.1%)

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.