This summer Kyle Kabasaras presented his original research project at the UC Merced undergrad research symposium.
Investigating quantum dot assembly in a cholesteric liquid crystal
An ongoing goal in condensed matter physics is directly controlling the self-assembly of quantum dots (QDs) into specific structures while maintaining their original electronic and optical properties. One method of controlling the self-assembly of QDs is to disperse them within a liquid crystal (LC) medium and apply a variety of thermal stimulations. Recently, our lab developed a method of creating spherical, vesicle-shaped QDs within a nematic LC. Vesicle formation depends on the QD concentration in the LC as well as the LC’s intermolecular dispersion forces and thermal properties. In this project, we investigate the dispersion of CdSe/ZnS (core/shell) QDs in a cholesteric LC (CLC) mediumand predict the QD aggregations to cluster near the LC defects. By varying parameters such as QD concentration and temperature, we exploit the CLC’s sensitive optical and thermal properties. To observe these effects, we apply spectrophotometry, polarized optical microscopy, and fluorescence microscopy. These techniques highlight the aggregation of QDs within the host CLC and identify how LC phase transitions determine where QDaggregates form. This work illustrates the possibility of new LC-based QD devices, and we will continue by exploring the lasing potential of our sample.
“All optical switching of nematic liquid crystal films driven by localized surface plasmons” M.T. Quint, S. Delgado, Z.S. Nuno, L.S. Hirst and S. Ghosh, OPTICS EXPRESS, 23,5, 6888 (2015) Link
We have demonstrated an all-optical technique for reversible in-plane and out-of-plane switching of nematic liquid crystal molecules in few micron thick films. Our method leverages the highly localized electric fields (“hot spots”) and plasmonic heating that are generated in the near-field region of densely packed gold nanoparticle layers optically excited on-resonance with the localized surface plasmon absorption. Using polarized microscopy and transmission measurements, we observe this switching from homeotropic to planar over a temperature range starting at room temperature to just below the isotropic transition, and at on-resonance excitation intensity less than 0.03 W/cm2. In addition, we controllably vary the in-plane directionality of the liquid crystal molecules in the planar state by altering the linear polarization of the incident excitation. Using discrete dipole simulations and control measurements, we establish spectral selectivity in this new and interesting perspective for photonic application using low light power.
“Self-assembled nanoparticle micro-shells templated by liquid crystal sorting”A. R. Rodarte, B.H. Cao, H. Panesar, R.J. Pandolfi, M. Quint, L. Edwards, S. Ghosh, J.E. Hein and L.S. Hirst, Soft Matter, 10.1039/C4SM02326A (2015) Link
A current goal in nanotechnology focuses on the assembly of different nanoparticle types into 3D organized structures. In this paper we report the use of a liquid crystal host phase in a new process for the generation of micron-scale vesicle-like nanoparticle shells stabilized by ligand–ligand interactions. The constructs formed consist of a robust, thin spherical layer, composed of closely packed quantum dots (QDs) and stabilized by local crystallization of the mesogenic ligands. Ligand structure can be tuned to vary QD packing within the shell and made UV cross-linkable to allow for intact shell extraction into toluene. The assembly method we describe could be extended to other nanoparticle types (metallic, magnetic etc.), where hollow shell formation is controlled by thermally sorting mesogen-functionalized nanoparticles in a liquid crystalline host material at the isotropic to nematic transition. This process represents a versatile method for making non-planar 3D nano-assemblies.
The design and development of multifunctional composite materials from artificial nano-constituents is one of the most compelling current research areas. This drive to improve over nature and produce ‘meta-materials’ has met with some success, but results have proven limited with regards to both the demonstration of synergistic functionalities and in the ability to manipulate the material properties post-fabrication and in situ. Here, magnetic nanoparticles (MNPs) and semiconducting quantum dots (QDs) are co-assembled in a nematic liquid crystalline (LC) matrix, forming composite structures in which the emission intensity of the quantum dots is systematically and reversibly controlled with a small applied magnetic field (<100 mT). This magnetic field-driven brightening, ranging between a two- to three-fold peak intensity increase, is a truly cooperative effect: the LC phase transition creates the co-assemblies, the clustering of the MNPs produces LC re-orientation at atypical low external field, and this re-arrangement produces compaction of the clusters, resulting in the detection of increased QD emission. These results demonstrate a synergistic, reversible, and an all-optical process to detect magnetic fields and additionally, as the clusters are self-assembled in a fluid medium, they offer the possibility for these sensors to be used in broad ranging fluid-based applications.
“Tuning quantum dot organization in liquid crystal for robust photonics applications”
A.L. Rodarte, Z.S. Nuno, B.H. Cao, R. J. Pandolfi, M. Quint, S. Ghosh, J. Hein and L.S. Hirst, CHEM PHYS CHEM, Volume 15, Issue 7, pages 1413–1421, (2014)Link
Mesogenic ligands have the potential to provide control over the dispersion and stabilization of nanoparticles in liquid crystal (LC) phases. The creation of such hybrid materials is an important goal for the creation of soft tunable photonic devices, such as the LC laser. Herein, we present a comparison of isotropic and mesogenic ligands attached to the surface of CdSe (core-only) and CdSe/ZnS (core/shell) quantum dots (QDs). The mesogenic ligand′s flexible arm structure enhances ligand alignment, with the local LC director promoting QD dispersion in the isotropic and nematic phases. To characterize QD dispersion on different length scales, we apply fluorescence microscopy, X-ray scattering, and scanning confocal photoluminescent imaging. 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 droplet with an average interparticle spacing >10 nm. Embedding the QDs in a cholesteric cavity, we observe comparable coupling effects to those reported for more closely packed isotropic ligands.
“Dye sensitized cholesteric liquid crystalline photonic luminescent solar concentrator”
A.L. Rodarte, F. Cisneros, L.S. Hirst and S. Ghosh, LIQUID CRYSTALS, DOI:10.1080/02678292.2014.924163, (2014) Link
We have developed organic dye-integrated thin-film liquid crystalline photonic luminescent solar concentrators (LSCs), where the chirality of the liquid crystal (LC) results in the formation of a one-dimensional photonic cavity. By varying the different LSC parameters, including dye concentration, spectral position of the photonic band-gap and the LC phase, and by using spectroscopic and electrical characterisation, we have systematically studied the effects of self-absorption, incident absorption and confinement of down-converted emission on optical efficiency. Our results demonstrate that the efficiency of our LSCs is significantly enhanced in the LC phase when the photonic band-gap is at long wavelengths (>600 nm), overcoming associated low incident absorption and higher self-absorption. We reach the significant conclusion that focusing on improving the confinement of dye-emitted photons, rather than on increasing incident absorption, is a more promising route to enhancing thin-film LC-based LSC performance.