Positive Encounters: An Investigative Study on the Effects of Interactions between Cations and Quantum Dots

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

Growth and application of planar III-V semiconductor nanowires grown with MOCVD

The semiconductor nanowire has been widely studied over the past decade and identified as a promising nanotechnology building block with application in photonics and electronics. The flexible bottom-up approach to nanowire growth allows for straightforward fabrication of complex 1D nanostructures with interesting optical, electrical, and mechanical properties. III-V nanowires in particular are useful because of their direct bandgap, high carrier mobility, and ability to form heterojunctions and have been used to make devices such as light-emitting diodes, lasers, and field-effect transistors. However, crystal defects are widely reported for III-V nanowires when grown in the common out-of-plane <111>B direction. Furthermore, commercialization of nanowires has been limited by the difficulty of assembling nanowires with predetermined position and alignment on a wafer-scale. In this thesis, planar III-V nanowires are introduced as a low-defect and integratable nanotechnology building block grown with metalorganic chemical vapor deposition. Planar GaAs nanowires grown with gold seed particles self-align along the <110> direction on the (001) GaAs substrate. Transmission electron microscopy reveals that planar GaAs nanowires are nearly free of crystal defects and grow laterally and epitaxially on the substrate surface. The nanowire morphology is shown to be primarily controlled through growth temperature and an ideal growth window of 470 +\- 10 °C is identified for planar GaAs nanowires. Extension of the planar growth mode to other materials is demonstrated through growth of planar InAs nanowires. Using a sacrificial layer, the transfer of planar GaAs nanowires onto silicon substrates with control over the alignment and position is presented. A metal-semiconductor field-effect transistor fabricated with a planar GaAs nanowire shows bulk-like low-field electron transport characteristics with high mobility. The aligned planar geometry and excellent material quality of planar III-V nanowires may lead to highly integrated III-V nanophotonics and nanoelectronics.

Localização em espaços interiores por luz visível para robôs móveis

Esta dissertação investiga a localização em espaços interiores através da comunicação por luz visível para robôs móveis, com base nos LEDs fixos nos edifícios, dando particular atenção à simulação e desenho do sensor, com vista ao desenvolvimento de um sensor de localização. Explica-se o crescimento da tecnologia LED e da constante necessidade de localização do homem em espaços interiores. Apresentado algumas características do LED e dos foto-detetores existentes. Com uma breve referencia a algumas das comunicações por luz visível de baixo débito possíveis de implementar. O desenvolvimento do protótipo do sensor inicia-se, principalmente, pela simulação de alguns dispositivos essenciais e das suas caraterísticas, como o emissor LED no controlo do ^angulo de meia potência (HPA) e a altura a que se encontra, e no recetor foto-díodo e a sua restrição de campo de visão (FOV). Simula-se o sensor pretendido com o número de foto-díodos necessários otimizando o espaço físico disponível e fazendo não só um refinamento no FOV mas também na distribuição espacial dos foto-díodos com funções predefinidas para a redução de incertezas de decisão de localização do robô. Estes resultados permitiram a construção física do sensor, desde o suporte para os foto-díodos, tendo em conta todas as medidas durante as simulações, e terminando com o desenvolvimento dos sensores e a sua integração completa. O tratamento de dados da leitura dos sinais recebidos do sensor são tratados por um microcontrolador, permitindo calcular parâmetros fundamentais no cálculo da posição. No final, os resultados teóricos bem como os práticos obtidos ao longo do desenvolvimento e possíveis propostas para trabalhos futuros que beneficiam desta investigação

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.

Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Optical Wireless Communication for Mobile Platforms

The past few decades have witnessed the widespread adaptation of wireless devices such as cellular phones and Wifi-connected laptops, and demand for wireless communication is expected to continue to increase. Though radio frequency (RF) communication has traditionally dominated in this application space, recent decades have seen an increasing interest in the use of optical wireless (OW) communication to supplement RF communications. In contrast to RF communication technology, OW systems offer the use of largely unregulated electromagnetic spectrum and large bandwidths for communication. They also offer the potential to be highly secure against jamming and eavesdropping. Interest in OW has become especially keen in light of the maturation of light-emitting diode (LED) technology. This maturation, and the consequent emerging ubiquity of LED technology in lighting systems, has motivated the exploration of LEDs for wireless communication purposes in a wide variety of applications. Recent interest in this field has largely focused on the potential for indoor local area networks (LANs) to be realized with increasingly common LED-based lighting systems. We envision the use of LED-based OW to serve as a supplement to RF technology in communication between mobile platforms, which may include automobiles, robots, or unmanned aerial vehicles (UAVs). OW technology may be especially useful in what are known as RF-denied environments, in which RF communication may be prohibited or undesirable. The use of OW in these settings presents major challenges. In contrast to many RF systems, OWsystems that operate at ranges beyond a few meters typically require relatively precise alignment. For example, some laser-based optical wireless communication systems require alignment precision to within small fractions of a degree. This level of alignment precision can be difficult to maintain between mobile platforms. Additionally, the use of OW systems in outdoor settings presents the challenge of interference from ambient light, which can be much brighter than any LED transmitter. This thesis addresses these challenges to the use of LED-based communication between mobile platforms. We propose and analyze a dual-link LED-based system that uses one link with a wide transmission beam and relaxed alignment constraints to support a more narrow, precisely aligned, higher-data-rate link. The use of an optical link with relaxed alignment constraints to support the alignment of a more precisely aligned link motivates our exploration of a panoramic imaging receiver for estimating the range and bearing of neighboring nodes. The precision of such a system is analyzed and an experimental system is realized. Finally, we present an experimental prototype of a self-aligning LED-based link.

Raman Spectroscopy and DFT calculations for the Electronic Structure Characterization of Conjugated Polymers

In the last three decades, there has been a broad academic and industrial interest in conjugated polymers as semiconducting materials for organic electronics. Their applications in polymer light-emitting diodes (PLEDs), polymer solar cells (PSCs), and organic field-effect transistors (OFETs) offer opportunities for the resolution of energy issues as well as the development of display and information technologies1. Conjugated polymers provide several advantages including low cost, light weight, good flexibility, as well as solubility which make them readily processed and easily printed, removing the conventional photolithography for patterning2. A large library of polymer semiconductors have been synthesized and investigated with different building blocks, such as acenes or thiophene and derivatives, which have been employed to design new materials according to individual demands for specific applications. To design ideal conjugated polymers for specific applications, some general principles should be taken into account, including (i) side chains (ii) molecular weights, (iii) band gap and HOMO and LUMO energy levels, and (iv) suited morphology.3-6 The aim of this study is to elucidate the impact that substitution exerts on the molecular and electronic structure of π-conjugated polymers with outstanding performances in organic electronic devices. Different configurations of the π-conjugated backbones are analyzed: (i) donor-acceptor configuration, (ii) 1D lineal or 2D branched conjugated backbones, and (iii) encapsulated polymers (see Figure 1). Our combined vibrational spectroscopy and DFT study shows that small changes in the substitution pattern and in the molecular configuration have a strong impact on the electronic characteristics of these polymers. We hope this study can advance useful structure-property relationships of conjugated polymers and guide the design of new materials for organic electronic applications.

Influence of alkylphosphonic acid grafting on the electronic and magnetic properties of La2/3Sr1/3MnO3 surfaces

Self-assembled monolayers (SAMs) are highly promising materials for molecular engineering of electronic and spintronics devices thanks to their surface functionalization properties. In this direction, alkylphosphonic acids have been used to functionalize the most common ferromagnetic electrode in organic spintronics: La2/3Sr1/3MnO3 (LSMO). However, a study on the influence of SAMs grafting on LSMO electronic and magnetic properties is still missing. In this letter, we probe the influence of alkylphosphonic acids-based SAMs on the electronic and magnetic properties of the LSMO surface using different spectroscopies. We observe by X-ray photoemission and X-ray absorption that the grafting of the molecules on the LSMO surface induces a reduction of the Mn oxidation state. Ultraviolet photoelectron spectroscopy measurements also show that the LSMO work function can be modified by surface dipoles opening the door to both tune the charge and spin injection efficiencies in organic devices such as organic light-emitting diodes.

Reforestation challenges in Scandinavia

In the keynote, major reforestation challenges in Scandinavia will be highlighted. The following countries make up Scandinavia: Iceland, Norway, Sweden, Finland and Denmark. For Iceland, with only a forest cover of 2%, a major reforestation challenge is the deforestation and overgrazing in combination with land degradation and extensive soil erosion. The challenges include the conflicts with livestock farmers. For centuries the commons were used for sheep and horse grazing. However, more and more of farmer grazing land have been fenced up, allowing the regeneration of birch and plantations of other species to increase. With a forest cover of 37% and 69% respectively, for decades a major reforestation challenge in Norway and Sweden has been the risk of seedling damages from the pine weevil. Unprotected seedlings can have a survival rate of less than 25% after being planted. Pine weevils feed on the bark of planted young seedlings at regeneration sites. If the seedling is girdled, it will not survive. In Sweden, and soon in Norway, pesticides have been forbidden. In the keynote, new methods and technology will be presented based on non-chemical protection. In Finland, with a forest cover of 75%, a major reforestation challenge is linked to the forest structure. The structure of Finnish forestry includes many private forests in combination with small regeneration sites. This implies a situation where logistics and methods for lifting and field storage provide a major challenge in order to preserve seedling quality until the planting date. Due to this situation, new logistic systems and technologies are being developed in Finland, including new seedling cultivation programs (including cultivation under Light Emitting Diodes (LEDs)) to match the access of fresh planting stock to different planting dates. In Denmark, with a forest cover of 13%, a major reforestation challenge is the possibility of future plantations based on a wide range of relevant species. For this to become a realistic option, new methods and technology have to be developed in reforestation activities that support this possibility. These methods and technology should make it possible to not be limited to certain species due to problems and restrictions during field establishment. This due to the prospect of establishing stable, healthy, and productive stands of various forest species that can be adapted to future climate change.

Degree of Conversion and Temperature Increase of a Composite Resin Light Cured with an Argon Laser and Blue LED

Different light sources and power densities used on the photoactivation process may provide changes in the degree of conversion (DC%) and temperature ( T) of the composite resins. Thus, the purpose of this study was to evaluate the DC (%) and T (degrees C) of the microhybrid composite resin (Filtek (TM) Z-250, 3M/ESPE) photoactivated with one argon laser and one LED (light-emitting diode) with different power densities. For the KBr pellet technique, the composite resin was placed into a metallic mould (2-mm thickness, 4-mm diameter) and photoactivated as follows: a continuous argon laser (CW) and LED LCUs with power density values of 100, 400, 700, and 1000 mW/cm(2) for 20 s. The measurements for DC (%) were made in a FTIR spectrometer Bomen ( model MB 102, Quebec, Canada). Spectroscopy ( FTIR) spectra for both uncured and cured samples were analyzed using an accessory of the reflectance diffusion. The measurements were recorded in absorbance operating under the following conditions: 32 scans, 4 cm(-1) resolution, 300 to 4000-cm(-1) wavelength. The percentage of unreacted carbon double bonds (% C=C) was determined from the ratio of absorbance intensities of aliphatic C=C (peak at 1638 cm(-1)) against an internal standard before and after the curing of the specimen: aromatic C-C (peak at 1608 cm(-1)). For T (degrees C), the samples were created in a metallic mould (2-mm thickness, 4-mm diameter) and photoactivated for 20 s. The thermocouple was attached to the multimeter allowing temperature readings. The DC (%) and T (degrees C) were submitted to ANOVA and Tukey`s test (p < 0.05). The degree of conversion values varied from 35.0 to 50.0% ( 100 to 1000 mW/cm(2)) for an argon laser and from 41.0 to 49% (100 to 1000 mW/cm(2)) for an LED. The temperature change values varied from 1.1 to 13.1 degrees C (100 to 1000 mW/cm(2)) for an argon laser and from 1.9 to 15.0 degrees C (100 to 1000 mW/cm(2)) for an LED. The power densities showed a significant effect on the degree of conversion and changes the temperature for both light-curing units.

Synthesis and luminescence properties of Sm3+ doped CaTiO3 nanophosphor for application in white LED under NUV excitation

CaTiO3:Sm3+ (1-11 mol%) nanophosphors were successfully synthesized by a low temperature solution combustion method LCS]. The structural and morphological properties of the phosphors were studied by using Powder X-ray diffractometer (PXRD), Fourier transform infrared (FTIR), X-ray photo electron spectroscopy (XPS), scanning electron microscope (SEM) and transmission electron microscopy (TEM). TEM studies indicate that the size of the phosphor is similar to 20-35 nm. Photoluminescence (PL) properties of Sm3+ (1-11 mol%) doped CaTiO3 for NUV excitation (407 nm) was studied in order to investigate the possibility of its use in White light emitting diode (WLED) applications. The emission spectra consists of intra 4f transitions of Sm3+, such as (4)G(5/2) -> H-6(5/2) (561 nm), (4)G(5/2) -> H-6(7/2) (601-611 nm), (4)G(5/2) -> H-6(9/2) (648 nm) and (4)G(5/2) -> H-6(11/2) (703 nm) respectively. Further, the emission at 601-611 nm show strong orange-red emission and can be applied to the orange-red emission of phosphor for the application for near ultra violet (NUV) excitation. Thermoluminescence (TL) of the samples irradiated with gamma source in the dose range 100-500 Gy was recorded at a heating rate of 5 degrees C s(-1). Two well resolved glow peaks at 164 degrees C and 214 degrees C along with shouldered peak at 186 degrees C were recorded. TL intensity increases up to 300 Gy and thereafter, it decreases with further increase of dose. The kinetic parameters namely activation energy (E), frequency factor (s) and order of kinetics were estimated and results were discussed in detail. (C) 2014 Elsevier B.V. All rights reserved.

Phosphor-conversion white light using InGaN ultraviolet laser diode

We fabricated a phosphor-conversion white light using an InGaN laser diode that emits 405 nm near-ultraviolet (n-UV) light and phosphors that emit in the blue and yellow regions when excited by the n-UV and blue light, respectively.The relationship of the luminous flux and the luminous efficacy of the white light with injection current was discussed. The luminous flux increased linearly with increasing current above the threshold of the laser diode, and at 80 mA injection current, the luminous flux and luminous efficacy were estimated to be 5.7 lm and 13 lm/w, respectively. The shift of the Commission International de I'Eclairage coordinates, color temperature, and color rendering index with current are very slight and negligible, which indicates that the blue and the yellow phosphors have an excellent stability and a highly stable white light can be obtained by this way. (c) 2008 American Institute of Physics.

White light emission from ultraviolet laser diode

A phosphor-conversion white light using an InGaN laser diode that emits 405 nm near-ultraviolet (n-UV) light and phosphors that emit in the red/green/blue region when excited by the n-UV light was fabricated. The relationship of the luminous flux and the luminous efficacy of the white light with injection current were discussed. Based on the evaluation method for luminous efficacy of light sources established by the Commission International de I'Eclairage (CIE) and the phosphor used in this experiment, a theoretical analysis of the experiment results and the maximum luminous efficacy of this white light fabrication method were also presented.

White light emission from fiber pigtailed laser module

We fabricated a phosphor-conversion white light using an InGaN laser diode that emits 445 nm and phosphor that emit in the yellow. The InGaN laser diode was coupled to an optical fiber firstly and the phosphor was excited by the laser light output from the fiber. At 350 mA injection current the luminous flux and the luminous efficacy was 73 lm and 42.7 lm/W, respectively. The luminance was estimated to be 50 cd/mm(2). The relationship of the luminous flux and the luminous efficacy of the white light with injection current were measured and discussed.