Indiana University-Purdue University Indianapolis (IUPUI) / The expansion of the applications of direct band gap semiconductor nanocrystals (NCs) has been a result of the control colloidal synthetic methods offer on the optoelectronic properties. These properties are readily controlled by the surface chemistry and even a small change in the surface passivating ligand can show profound effects. Furthermore, the choice of surface passivating ligand also impacts the NC shape evolution, which in turn influence the surface area, quantum yield, and charge transport properties that are critical to optimize device fabrication. In this dissertation, the unique aspects of surface chemistry that control both NC shape evolution and optoelectronic properties are investigated. We began by investigating how surface chemistry controls the shape evolution of methyl ammonium lead bromide (CH3NH3PbBr3) perovskite NCs. In addition to the surface passivating ligand, the reaction temperature and solvent system were also examined. Through a series of control experiments, the critical parameter for the formation of quantum wires (QWs) was found to be the presence of a long chain acid, while the quantum platelets (QPLs) required a long chain amine and chlorinated solvent, and quantum cube (QC) formation was kinetically driven. The higher ordered stacking of the QPLs and bundling of the QWs was also found to be controlled by surface ligand chemistry. Next we further examined how surface chemistry impacts shape evolution, but in the system of metal chalcogenide NCs. We developed a versatile, low temperature, and gram scale synthesis of QWs, QPLs, and quantum rods (QRs) using both cadmium and zinc as metal precursors and sulfur and selenium as chalcogenide precursors. Through systematic investigation of both the surface chemistry and reaction progression, the growth and formation mechanism was also determined. The 1D QW growth required a long chain amine while the QPLs required the presence of both a long and short chain amine to drive 2D growth. Finally, the QRs would found to be a kinetically-controlled process. Ultrasmall semiconductor NCs are known to possess high surface to volume ratios and therefore even a minute change in surface chemistry will have a significant impact on the optoelectronic properties. Our investigation focused on (CdSe)34 NCs, and how exchanging native amine ligands with various chalcogenol based ligands influences these properties. These NCs lie in the strong confinement regime and therefore have a higher probability of undergoing exciton delocalization, resulting in red shifts of the first excitonic peak and reduction of the optical band gap. Additionally, we examined different characteristics of the ligand (level of conjugation, electron withdrawing or donating nature of para-substitution, binding mode and head group) to examine how these parameters impact exciton delocalization. We observed the highest shift in the optical band gap (of 650 meV) after exchanging the native amine ligands with pyrene dithiocarbamate. Through this investigation it was determined that ligand characteristics (specifically conjugation and binding mode) have significant influence in the proposed hole delocalization. Finally, we continued the investigation of how surface chemistry controls optoelectronic properties of ultrasmall NCs, but expand our work to those of methyl ammonium lead halide. We developed a low temperature and colloidal synthesis of white-light emitting NCs with a diameter of 1.5 nm. Through precise manipulation of the surface halide ions, it was possible to tailor the emission to match that of nearly pure white light.

Novel organic conjugated materials have led to new technologies in the field of flexible electronics, with applications in the area of sensors, field effect transistors, or photovoltaic devices. Several material parameters and properties come into play in these devices, including energy of the frontier molecular orbitals, thin film morphology, and charge transport. These properties can be controlled by the chemistry of organic materials, and through processing conditions. In particular, this dissertation focuses on the isoindigo unit as an electron deficient unit to tune polymer light absorption, charge separation, charge transport in the first part of this dissertation, and morphology control in organic photovoltaic (OPV) devices in a subsequent section. The first part of this dissertation introduces the synthesis and properties of isoindigo-containing polymers as n-type, p-type, or ambipolar semiconductors, and their application in all-polymer or polymer:fullerene blends OPV active layers. It is found that polymers with phenyl linkages along the backbone tend to have broader light absorption than polymers with alternating phenyl-thiophene rings; however, steric hindrance in the former leads to low charge mobilities, and poor device performance. In addition, this section highlights the importance of controlling phase separation in OPV devices by focusing on all-polymer blends, which show large phase separation, and polymer:fullerene blends, where the morphology can be controlled through processing additives generating a two-fold increase in device efficiency. Looking at poly(oligothiophene-isoindigo) polymers as model systems, emphasis is placed on photovoltage losses in these devices due to a decrease in effective energy gap between the polymers and fullerene as the oligothiophene donating strength is increased, as well as explanation of the device parameters through description of morphology as solubility is varied. The second portion of this dissertation focuses on solution properties of polymers and their correlation to thin film morphology. A first study investigates the influence of alkyl side chains on solubility, molecular packing, and phase separation in blends of poly(terthiophene-alt-isoindigo) with fullerenes. Specifically, as side chains are lengthened, solubility is increased, but with limited impact on the blends morphology. On the other hand increased backbone torsion leads to variations in energy levels, polymer packing and large phase separation in blends with fullerenes. These thermodynamic parameters are to put in perspective with the kinetic control of film formation during the coating process. This is discussed in a second study, which looks at the mechanism of thin film formation when processing additives are used. In particular, this study highlights the interactions that provide a driving force for polymer crystallite formation, depending on the mechanism followed when aliphatic and aromatic additives are used. These observations are then used to predict the morphology in spin-coated thin films.

Thesis advisor: Shih-Yuan Liu / This dissertation describes progress in the field of polycyclic boron- nitrogen-containing systems, especially for potential application in organic-based optoelectronic devices and hydrogen storage materials. The replacement of a BN unit for a CC unit organic compounds (BN/CC isosterism) can have a profound effect on the electronic structure and even function of a given molecular topology without changing its physical structure very much. Direct comparison between a BN-containing molecule and its direct all-carbon analogue is crucial to establishing the origin of these differences. The synthesis and optoelectronic characterization of boron- nitrogen-containing analogues of naphthalene, anthracene, and tetracene are disclosed. Also examined herein is the aromatic Claisen rearrangement applied to an azaboryl allyl ether. Finally, the chemistry of saturated BN heterocycles, including an iridium-catalyzed transfer dehydrogenation method for synthesizing BN-fused azaborines. Also disclosed is the actual application of these cyclic amine-boranes in supplying hydrogen for a proton exchange membrane (PEM) fuel cell. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

In this study, we study polymer-dispersed blue-phase liquid-crystal (PDBPLC)films. The PDBPLC film is fabricated by using BPLC instead of nematic LC in a PDLC film. The experimental results show that the PDBPLC films and can be switchable as the conventional PDLC. The polymer morphology of the PDBPLC is affected by the concentration of monomer in the BPLC/monomer mixture. The PDBPLC exhibits a good contrast ratio with monomer concentration of 39.17 wt%. The rise time of PDBPLC films decreases as the polymer concentration increases. Moreover, the results also show that a complete phase separation occurs with the exposure time of 20 minutes. For the future work, we will improve the high driving voltage and low ratio of the PDBPLC film.

Colloidal semiconductor nanocrystal quantum dots (QDs) have been extensively studied for applications in optoelectronic devices, biosensing, and imaging. Recent interest has turned to heavy metal-free compositions such as indium phosphide as an alternative to cadmium- and lead-based materials. Photoluminescence emission from InP QDs is size-tunable over a wide spectral range, providing superior color tuning compared to traditional CdSe QD but their optical properties and chemical synthesis is less well established. This study examines how InP-based heterostructures can be engineered to enhance their utility as heavy metal-free fluorophores emitting throughout the visible and near infrared (NIR) wavelength ranges by addressing three fundamental materials design and synthesis issues. First, the bandgap engineering of InP-based QDs is achieved by varying the core size, shell composition, and shell thickness of a core/shell heterostructures, generating emitters spanning 500 – 1100 nm. Second, the brightness mismatch between small blue/green emitters and large red-emitting QDs is addressed by tuning the absorption cross-section and extinction coefficient by synthesizing a series of QDs with a combination of core sizes, shell thicknesses, and shell compositions, resulting in a rainbow of brightness-matched InP emitters. Finally, the synthesis of inverted InP heterostructures, producing the reddest-emitting InP QDs ever reported by generating photoluminescence from a quantum confined InP shell, was significantly improved. The non-toxic nature of InP in conjunction with its unique optical properties render it an excellent candidate for use in in vitro and in vivo clinical or commercial settings.

The global increase in internet usage requires an upgrade of the existing infrastruc- ture. Lasers are a key proponent to improving existing systems, and engineering better gain materials aids in this effort. (InGa)As is the leading material in this field for 1.55 μm communication wavelengths, but can be improved on by changing the substrate from InP to GaAs. Another improvement would be reducing the losses due to Auger recombination. (InGa)(BiAs) is suggested to alleviate many of these issues, as it can be grown on a GaAs substrate and is capable of decreased Auger recombination. By analyzing prospective alloys (and existing ones) using spatial electron localization, a superior candidate for industrial use can be suggested. The localization captures the disorder introduced by alloying and can be associated with material properties such as the gain characteristics and photoluminescence linewidths. These properties are important factors in determining a successor. The subject of two-dimensional materials is another topic which has shown promise in various applica- tions. Examples include flexible, transparent, and miniaturized electronics. Recent research done by Al Balushi et al. suggests that GaN may be stabilized in a two-dimensional sys- tem. By extending the material modelling approach from the telecommunication application to this system, we were able to show which III-V isoelectronic elements can be substituted into GaN. This two-dimensional system may be the only candidate capable of spanning the visible spectrum. We found Phosphorus to be the strongest candidate for decreasing the band gap. / Thesis / Master of Applied Science (MASc)

One antiaromatic polycyclic hydrocarbon (PH) with and without solubilizing tert-butyl substituents, namely s-indaceno[2,1-a:6,5-a′]dipyrene (IDPs), has been synthesized by a four-step protocol. The IDPs represent the longitudinal, peri-extension of the indeno[1,2-b]fluorene skeleton towards a planar 40 π-electron system. Their structures were unambiguously confirmed by X-ray crystallographic analysis. The optoelectronic properties were studied by UV/vis absorption spectroscopy and cyclic voltammetry. These studies revealed that peri-fusion renders the IDP derivatives with a narrow optical energy gap of 1.8 eV. The maximum absorption of IDPs is shifted by 160 nm compared to the parent indenofluorene. Two quasi-reversible oxidation as well as reduction steps indicate an excellent redox behavior attributed to the antiaromatic core. Formation of the radical cation and the dication was monitored by UV/vis absorption spectroscopy during titration experiments. Notably, the fusion of s-indacene with two pyrene moieties lead to IDPs with absorption maxima approaching the near infrared (NIR) regime.

Made available in DSpace on 2015-03-03T15:16:25Z (GMT). No. of bitstreams: 1 EdvanM_TESE.pdf: 3369226 bytes, checksum: 764b7a9d291d433b871e24f1776af89d (MD5) Previous issue date: 2011-07-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this work we present a study for the structural, electronic and optical properties, at ambient conditions of SrSnO3, SrxBa1?xSnO3 (x = 0:2; 0:4; 0:6; 0:8) and BaSnO3 crystals, all of them member of perovskite-type earth stannates class, ASnO3. The theoretical model employed was based on the density functional theory (DFT), considering both the local density and the generalized gradient approximations, LDA-CAPZ and GGA-PBE (OPIUM), respectively. For orthorhombic SrSnO3, the electronic band structure, density of states, complex dielectric function, optical absorption, and the infrared and Raman spectra were computed. Calculated lattice parameters are closed to the experimental measurements, and an indirect band gap E(S -> t ?)=1.97 eV (2.27 eV) was obtained within the GGA (LDA) level of calculation. E ective masses for holes and electrons were estimated, being very anisotropic in comparison with similar results for orthorhombic CaSnO3. The complex dielectric function and the optical absorption of SrSnO3 are sensitive to the plane of polarization of the incident light. The infrared spectrum between 100-600 cm-?1 was obtained, with its main peaks being assigned, and a good agreement between experimental and theoretical peaks of the Raman spectrum of orthorhombic SrSnO3 was achieved. For SrxBa1?xSnO3 series, their electronic properties were investigated. The cubic Sr0:2Ba0:8SnO3 has an indirect band gap, while tetragonal Sr0:4Ba0:6SnO3, orthorhombic Sr0:6Ba0:4 SnO3 and Sr0:8Ba0:2SnO3 exhibit a direct band gap. The Kohn-Sham minimum electronic band gap oscillates of 2.62 eV (tetragonal Sr0:4Ba0:6SnO3, LDA) to 1.52 eV (orthorhombic Sr0:6Ba0:4Sn O3, LDA). The effective masses for holes and electrons were estimated, being anisotropic in the series. For cubic BaSnO3, the electronic band structure, density of states, dielectric function and optical absorption were calculated, as well as the infrared absorption spectra after computing the vibrational modes of the crystal at q = 0. Dielectric optical permittivities and polarizabilities at w = 0 and w = ?? were also obtained. An indirect band gap E(R -> T?) of 1.01 eV and 0.74 eV was achieved within the LDA-CAPZ and the GGA-PBE, respectively, which is smaller than the experimental data ( ?? 3.1 eV). Effective masses of holes and electrons were estimated by parabolic tting along di erent directions at the valence band maximum and conduction band minimum, being highly isotropic for electrons and anisotropic for holes, allowing us to suggest that indirect gap cubic BaSnO3 is a semiconductor with potential for optoelectronic applications. The optical properties reveal a degree of isotropy for the crystal with respect to di erent polarization planes of incident light. The infrared spectrum between 100-600 cm?-? was obtained, with its main peaks being assigned / Apresentamos neste trabalho um estudo das propriedades estruturais, eletr?nicas e ?pticas, em temperatura ambiente dos cristais de SrSnO3, SrxBa1xSnO3 (x = 0:2; 0:4; 0:6; 0:8) e BaSnO3, todos eles membros da classe das perovskitas do tipo estanatos terrosos, ASnO3. O nosso modelo te?rico foi baseado na teoria do funcional da densidade (DFT) considerando as aproxima??es da densidade local e do gradiente generalizado, LDA-CAPZ e GGA-PBE (OPIUM), respectivamente. Para o SrSnO3 ortor?mbico, foram calculadas a estrutura de bandas eletr?nica, densidade de estados, fun??o diel?trica complexa, absor??o ?ptica e os espectros infravermelho e Raman. Os par?metros de rede calculados est?o pr?ximos dos resultados experimentais, e um band gap indireto E(S !)=1.97 eV (2.27 eV) foi obtido dentro do n?vel GGA (LDA) de c?lculo. As massas efetivas dos buraco e dos el?trons foram estimadas, sendo elas muito anisotr?picas em compara??o com os resultados similares para o CaSnO3 ortor?mbico. Al?m disso, nossos resultados mostram que a fun??o diel?trica complexa e a absor??o ?ptica do SrSnO3 s?o sens?veis ao plano de polariza??o da luz incidente. O espectro infravermelho entre 100{600 cm1 foi obtido, com seus principais picos sendo assinalados, e uma boa concord?ncia dos resultados experimentais e te?ricos do espectro Raman do SrSnO3 ortor?mbico foram alcan?ados. Para a s?rie SrxBa1xSnO3, as propriedades eletr?nicas foram investigadas. O Sr0:2Ba0:8 SnO3 c?bico possui um band gap indireto, enquanto o Sr0:4Ba0:6SnO3 tetragonal, os ortor?mbicos Sr0:6Ba0:4SnO3 e Sr0:8Ba0:2SnO3 exibem um band gap direto. O band gap eletr?nico m?nimo de Kohn-Sham oscila de 2.62 eV (Sr0:4Ba0:6SnO3 tetragonal, LDA) at? 1.52 eV (Sr0:6Ba0:4SnO3 ortor?mbico, LDA). As massas efetivas de buracos e de el?trons foram estimadas, sendo anisotr?picas nas s?ries. vi Para o BaSnO3 c?bico, foram calculadas a estrutura de bandas eletr?nica, densidade de estados, fun??o diel?trica e absor??o ?ptica, bem como o espectro infravermelho de absor??o ap?s computar os modos de vibra??o do cristal em q = 0. A permissividade ?ptica diel?trica e as polarizabilidades em ! = 0 e ! = 1 foram obtidas. Um band gap indireto E(R !) de 1.01 eV e 0.74 eV foi obtido com o LDA-CAPZ e o GGA-PBE, respectivamente, que ? menor que o dado experimental (3.1 e V). As massas efetivas de buraco e de el?tron foram estimadas atrav?s de um ajuste parab?lico ao longo de diferentes dire??es no m?ximo da banda de val?ncia e no m?nimo da banda de condu??o, sendo muito isotr?pico para el?trons e anisotr?pico para buracos, permitindo-nos sugerir que o BaSnO3 c?bico de gap indireto ? um semicondutor com potencial para aplica??es optoeletr?nicas. As propriedades ?pticas revelaram um grau de isotropia para o cristal com respeito aos diferentes planos de polariza??o de luz incidente. O espectro infravermelho entre 100{600 cm 1 foi obtido, com seus principais picos sendo assinalados

Zweidimensionale (2D) Übergangsmetalldichalcogenide (TMDCs) gehören zu den attraktivsten neuen Materialien für optoelektronische Bauelemente der nächsten Generation. Um die überlegene Funktionalität der mit TMDCs verbundenen Bauelemente zu realisieren, ist ein umfassendes Verständnis ihrer elektronischen Struktur, einschließlich, aber nicht beschränkt auf die Auswirkungen von Defekten auf die elektronischen Eigenschaften und die Ausrichtung der Energieniveaus (ELA) an den TMDCs-Grenzflächen, unerlässlich, aber derzeit nicht ausreichend. Um einen tieferen Einblick in die elektronischen Eigenschaften von TMDCs und den damit verbundenen Grenzflächen in Kombination mit molekularen Halbleitern (MSCs) zu erhalten, untersuchen wir i) die fundamentale Bandstruktur von Monolagen (ML) TMDCs und die durch Schwefelfehlstellen (SVs) induzierte Renormierung der Bandstruktur, um eine solide Grundlage für ein besseres Verständnis der elektronischen Eigenschaften von polykristallinen dünnen Filmen zu schaffen, und ii) die optoelektronischen Eigenschaften ausgewählter MSC/ML-TMDCs-Grenzflächen. Darüber hinaus wird iii) der Einfluss des Substrats auf die elektronischen Eigenschaften einer MSC/ML-TMDC-Grenzfläche untersucht, um das Bauelementedesign zu steuern. Die Charakterisierung erfolgt hauptsächlich durch winkelaufgelöste Photoelektronenspektroskopie (ARPES), ergänzt durch Photolumineszenz (PL), Raman-Spektroskopie, UV-Vis-Absorption, Rastertransmissionselektronenmikroskopie (TEM) und Rasterkraftmikroskopie (AFM). Unsere Ergebnisse tragen zu einem besseren Verständnis der Auswirkungen von Defekten auf ML-TMDC und verwandte Grenzflächen mit MSCs bei, wobei auch die Auswirkungen der Substrate berücksichtigt werden, und sollten dazu beitragen, unser Verständnis des elektronischen Verhaltens in TMDC-verwandten Geräten zu verbessern. / Two-dimensional (2D) transition metal dichalcogenides (TMDCs) are amongst the most attractive emerging materials for next-generation optoelectronic devices. To realize the superior functionality of the TMDCs related devices, a comprehensive understanding of their electronic structure, including but not limited to the impact of defects on the electronic properties and energy level alignment (ELA) at TMDCs interfaces, is essential but presently not sufficient. In an attempt to get a deep insight into the electronic properties of TMDCs and the related interfaces combined with molecular semiconductors (MSCs), we investigate i) the fundamental band structure of monolayer (ML) TMDCs and band structure renormalization induced by sulfur vacancies (SVs), in order to provide a solid foundation for a better understanding the electronic properties of polycrystalline thin films and ii) the optoelectronic properties of selected MSC/ML-TMDC interface. In addition, iii) the impact of the substrate on the electronic properties of the MSC/ML-TMDC interface is investigated for guiding device design. The characterization is mainly performed by using angle-resolved photoelectron spectroscopy (ARPES), with complementary techniques including photoluminescence (PL), Raman spectroscopies, UV-vis absorption, scanning transmission electron microscopy (TEM), and atomic force microscopy (AFM) measurements. Our findings contribute to achieving a better understanding of the impact of defects on ML-TMDC and related interfaces with MSCs considering the substrates’ effect and should help refine our understanding of the electronic behavior in TMDC-related devices.