Dispersions of Semiconductor Nanoparticles in Thermotropic Liquid Crystal: From Optical Modification to Assisted Self-Assembly

Author(s): Rodarte, Andrea L. | Advisor(s): Ghosh, Sayantani; Hirst, Linda S. | Abstract: The interaction of semiconducting quantum dot nanoparticles (QDs) within thermotropic liquid crystalline (LC) materials are studied in this thesis. LC materials are ideal for bottom-up organization of nanoparticles as an active matrix that can be externally manipulated via electric or magnetic fields. In addition, the optical properties of QDs can be modified by the surrounding LC resulting in novel devices such as a quantum dot/liquid crystal laser. The first system studies the dispersion of spherical nanoparticles in the phase. The dispersion is investigated with the use of polarized optical microscopy, fluorescence microscopy and confocal scanning microscopy. Quantum dots well dispersed in the isotropic phase are expelled from ordered domains of LC at the phase transition. Under controlled conditions, the majority of QDs in the system can form ordered three dimensional assemblies that are situated at defect points in the liquid crystal. The internal order of the assemblies is probed utilizing Forster resonance energy transfer (FRET), combined with small angle X-ray scattering (SAXS). Furthermore, the location of these assemblies can be predetermined with the use of beads as defect nucleation points in the cell. The interaction of QDs in a cholesteric liquid crystal (CLC) is also investigated. The reflection band created by the periodic change of index of refraction in a planar aligned CLC acts as a 1-D photonic cavity when the CLC is doped with a low concentration of QDs. A Cano-wedge cell varies the pitch of the CLC leading to the formation of Grandjean steps. This spatially tunes the photonic stop band, changing the resonance condition and continuously altering both the emission wavelength and polarization state of the QD ensemble. Using high resolution spatially and spectrally resolved photoluminescence measurements, the emission is shown to be elliptically polarized and that the tilt of the ellipse, while dependent on the emission wavelength, additionally varies with distance across the Grandjean steps. Using ultrafast spectroscopic techniques the time-resolved emission from QD ensembles in CLC matrices with either planar or homeotropic alignment is observed. In the case of planar alignment and a well-defined spectral stop band the emergence of a second, faster decay time of less than 2 ns is observed. This short recombination pathway is observed only in samples where the QD emission spectrum partially overlaps the CLC stop band by 50% or more. Samples prepared with homeotropic alignment do not have a stop band and, consequently, do not lead to spectral or dynamical modulation of the QD emission. These observations indicate that coupling between the excitonic and the photonic cavity modes results in an enhancement and modulation of spontaneous emission in the liquid crystal medium. This work opens up the possibility of designing new QD based optical devices, such as tunable single photon sources, where spatial control of wavelength and polarization of the embedded QDs would allow great flexibility and added functionalities.For hybrid materials such as soft tunable photonic devices like liquid crystal lasers, stable dispersions of nanoparticles in LC are desired. For the system we investigate functionalizing the nanoparticles with LC like ligands. Isotropic and mesogenic ligands attached to the surface of CdSe (core only) and CdSe/ZnS (core/shell) QDs. The mesogenic ligand's flexible arm structure enhances ligand alignment with the local liquid crystal director, enhancing QD dispersion in the isotropic and nematic phases. To characterize QD dispersion on different length scales, fluorescence microscopy, x-ray scattering and scanning confocal photoluminescent imaging are used. These combined techniques demonstrate that the LC-modified QDs do not aggregate into the dense clusters observed for dots with simple isotropic ligands when dispersed in liquid crystal, but loosely associate in a fluid-like aggregate with an average inter-particle spacing of g10nm. The major goal in this research is to identify the strengths and weaknesses of utilizing liquid crystal materials for hybrid and metamaterials. The techniques developed within this thesis will be useful for the next step of bottom-up metamaterial fabrication.