Nanoparticle localization within chiral liquid crystal defect lines and nanoparticle interactions.

Self-assembly of colloidal particles into predefined structures is a promising way to design inexpensive manmade materials with advanced macroscopic properties. Doping of nematic liquid crystals (LCs) with nanoparticles has a series of advantages in addressing these grand scientific and engineering challenges. It also provides a very rich soft matter platform for the discovery of unique condensed matter phases. The LC host naturally allows the realization of diverse anisotropic interparticle interactions, enriched by the spontaneous alignment of anisotropic particles due to the boundary conditions of the LC director. Here we demonstrate theoretically and experimentally that the ability of LC media to host topological defect lines can be used as a tool to probe the behavior of individual nanoparticles as well as effective interactions between them. LC defect lines irreversibly trap nanoparticles enabling controlled particle movement along the defect line with the use of a laser tweezer. Minimization of Landau-de Gennes free energy reveals a sensitivity of the ensuing effective nanoparticle interaction to the shape of the particle, surface anchoring strength, and temperature, which determine not only the strength of the interaction but also its repulsive or attractive character. Theoretical results are supported qualitatively by experimental observations. This work may pave the way toward designing controlled linear assemblies as well as one-dimensional crystals of nanoparticles such as gold nanorods or quantum dots with tunable interparticle spacing.

Aerogel from Sustainably Grown Bacterial Cellulose Pellicles as a Thermally Insulative Film for Building Envelopes.

Improving building energy performance requires the development of new highly insulative materials. An affordable retrofitting solution comprising a thin film could improve the resistance to heat flow in both residential and commercial buildings and reduce overall energy consumption. Here, we propose cellulose aerogel films formed from pellicles produced by the bacteria Gluconacetobacter hansenii as insulation materials. We studied the impact of the density and nanostructure on the aerogels' thermal properties. A thermal conductivity as low as 13 mW/(K·m) was measured for native pellicle-based aerogels that were dried as-is with minimal post-treatment. The use of waste from the beer brewing industry as a solution to grow the pellicle maintained the cellulose yield obtained with standard Hestrin-Schramm media, making our product more affordable and sustainable. In the future, our work can be extended through further diversification of food wastes as the substrate sources, facilitating higher potential production and larger applications.

Control of quantum dot emission by colloidal plasmonic pyramids in a liquid crystal.

We study the plasmon-enhanced fluorescence of a single semiconducting quantum dot near the apex of a colloidal gold pyramid spatially localized by the elastic forces of the liquid crystal host. The gold pyramid particles were manipulated within the liquid crystal medium by laser tweezers, enabling the self-assembly of a semiconducting quantum dot dispersed in the medium near the apex of the gold pyramid, allowing us to probe the plasmon-exciton interactions. We demonstrate the effect of plasmon coupling on the fluorescence lifetime and the blinking properties of the quantum dot. Our results demonstrate that topological defects around colloidal particles in liquid crystal combined with laser tweezers provide a platform for plasmon exciton interaction studies and potentially could be extended to the scale of composite materials for nanophotonic applications.

Electrostatically controlled surface boundary conditions in nematic liquid crystals and colloids.

Differing from isotropic fluids, liquid crystals exhibit highly anisotropic interactions with surfaces, which define boundary conditions for the alignment of constituent rod-like molecules at interfaces with colloidal inclusions and confining substrates. We show that surface alignment of the nematic molecules can be controlled by harnessing the competing aligning effects of surface functionalization and electric field arising from surface charging and bulk counterions. The control of ionic content in the bulk and at surfaces allows for tuning orientations of shape-anisotropic particles like platelets within an aligned nematic host and for changing the orientation of director relative to confining substrates. The ensuing anisotropic elastic and electrostatic interactions enable colloidal crystals with reconfigurable symmetries and orientations of inclusions.

Hybrid molecular-colloidal liquid crystals.

Order and fluidity often coexist, with examples ranging from biological membranes to liquid crystals, but the symmetry of these soft-matter systems is typically higher than that of the constituent building blocks. We dispersed micrometer-long inorganic colloidal rods in a nematic liquid crystalline fluid of molecular rods. Both types of uniaxial building blocks, while freely diffusing, interact to form an orthorhombic nematic fluid, in which like-sized rods are roughly parallel to each other and the molecular ordering direction is orthogonal to that of colloidal rods. A coarse-grained model explains the experimental temperature-concentration phase diagram with one biaxial and two uniaxial nematic phases, as well as the orientational distributions of rods. Displaying properties of biaxial optical crystals, these hybrid molecular-colloidal fluids can be switched by electric and magnetic fields.

Tuning and Switching a Plasmonic Quantum Dot "Sandwich" in a Nematic Line Defect.

We study the quantum-mechanical effects arising in a single semiconductor core/shell quantum dot (QD) controllably sandwiched between two plasmonic nanorods. Control over the position and the "sandwich" confinement structure is achieved by the use of a linear-trap liquid crystal (LC) line defect and laser tweezers that "push" the sandwich together. This arrangement allows for the study of exciton-plasmon interactions in a single structure, unaltered by ensemble effects or the complexity of dielectric interfaces. We demonstrate the effect of plasmonic confinement on the photon antibunching behavior of the QD and its luminescence lifetime. The QD behaves as a single emitter when nanorods are far away from the QD but shows possible multiexciton emission and a significantly decreased lifetime when tightly confined in a plasmonic "sandwich". These findings demonstrate that LC defects, combined with laser tweezers, enable a versatile platform to study plasmonic coupling phenomena in a nanoscale laboratory, where all elements can be arranged almost at will.

Colloidal Surfaces with Boundaries, Apex Boojums, and Nested Elastic Self-Assembly of Nematic Colloids.

Self-assembly of colloidal particles is poised to become a powerful composite material fabrication technique, but remains challenged by a limited control over the ensuing structures. We develop a new breed of nematic colloids that are physical analogs of a mathematical surface with boundary, interacting with the molecular alignment field without inducing defects when flat. However, made from a thin nanofoil, they can be shaped to prompt formation of self-compensating defects that drive preprogramed elastic interactions mediated by the nematic host. To show this, we wrap the nanofoil on all triangular side faces of a pyramid, except its square base. The ensuing pyramidal cones induce point defects with fractional hedgehog charges of opposite signs, spontaneously align with respect to the far-field director to form elastic dipoles and nested assemblies with tunable spacing. Nanofoils shaped into octahedrons interact as elastic quadrupoles. Our findings may drive realization of low-symmetry colloidal phases.

Molecular germanium selenophosphate salts: phase-change properties and strong second harmonic generation.

A new series of germanium chalcophosphates with the formula A(4)GeP(4)Q(12) (A = K, Rb, Cs; Q = S, Se) have been synthesized. The selenium compounds are isostructural and crystallize in the polar orthorhombic space group Pca2(1). The sulfur analogues are isostructural to one another but crystallize in the centrosymmetric monoclinic space group C2/c. All structures contain the new molecular anion [GeP(4)Q(12)](4-); however, the difference between the sulfides and selenides arises from the change in crystal packing. Each discrete molecule is comprised of two ethane-like P(2)Q(6) units that chelate to a central tetrahedral Ge(4+) ion in a bidentate fashion. The selenides were synthesized pure by stoichiometric reaction of the starting materials, whereas the sulfides contained second phases. The band gaps of the molecular salts are independent of the alkali metal counterions and have a value of 2.0 eV for the selenides and 3.0-3.1 eV for the sulfides. All A(4)GeP(4)Se(12) compounds melt congruently, and the potassium analogue can be quenched to give a glassy phase that retains its short-range order as shown by Raman spectroscopy and powder X-ray diffraction. Interestingly, K(4)GeP(4)Se(12) is a phase-change material that reversibly converts between glassy and crystalline states and passes through a metastable crystalline state upon heating just before crystallizing into its slow-cooled form. Initial second harmonic generation (SHG) experiments showed crystalline K(4)GeP(4)Se(12) outperforms the other alkali metal analogues and exhibits the strongest second harmonic generation response among reported quaternary chalcophosphates, ~30 times that of AgGaSe(2) at 730 nm. A more thorough investigation of the nonlinear optical (NLO) properties was performed across a range of wavelengths that is almost triple that of previous reports (λ = 1200-2700 nm) and highlights the importance of broadband measurements. Glassy K(4)GeP(4)Se(12) also exhibits a measurable SHG response with no poling.