Thermally reconfigurable monoclinic nematic colloidal fluids.

Fundamental relationships are believed to exist between the symmetries of building blocks and the condensed matter phases that they form1. For example, constituent molecular and colloidal rods and disks impart their uniaxial symmetry onto nematic liquid crystals, such as those used in displays1,2. Low-symmetry organizations could form in mixtures of rods and disks3-5, but entropy tends to phase-separate them at the molecular and colloidal scales, whereas strong elasticity-mediated interactions drive the formation of chains and crystals in nematic colloids6-11. To have a structure with few or no symmetry operations apart from trivial ones has so far been demonstrated to be a property of solids alone1, but not of their fully fluid condensed matter counterparts, even though such symmetries have been considered theoretically12-15 and observed in magnetic colloids16. Here we show that dispersing highly anisotropic charged colloidal disks in a nematic host composed of molecular rods provides a platform for observing many low-symmetry phases. Depending on the temperature, concentration and surface charge of the disks, we find nematic, smectic and columnar organizations with symmetries ranging from uniaxial1,2 to orthorhombic17-21 and monoclinic12-15. With increasing temperature, we observe unusual transitions from less- to more-ordered states and re-entrant22 phases. Most importantly, we demonstrate the presence of reconfigurable monoclinic colloidal nematic order, as well as the possibility of thermal and magnetic control of low-symmetry self-assembly2,23,24. Our experimental findings are supported by theoretical modelling of the colloidal interactions between disks in the nematic host and may provide a route towards realizing many low-symmetry condensed matter phases in systems with building blocks of dissimilar shapes and sizes, as well as their technological applications.

Plasmonic gold-cellulose nanofiber aerogels.

Assembly of plasmonic nanomaterials into a low refractive index medium, such as an aerogel, holds a great promise for optical metamaterials, optical sensors, and photothermal energy converters. However, conventional plasmonic aerogels are opaque and optically isotropic composites, impeding them from being used as low-loss or polarization-dependent optical materials. Here we demonstrate a plasmonic-cellulose nanofiber composite aerogel that comprises of well-dispersed gold nanorods within a cellulose nanofiber network. The cellulose aerogel host is highly transparent owing to the small scattering cross-section of the nanofibers and forms a nematic liquid crystalline medium with strong optical birefringence. We find that the longitudinal surface plasmon resonance peak of gold nanorods shows a dramatic shift when probed for the cellulose aerogel compared with the wet gels. Simulations reveal the shift of surface plasmon resonance peak with gel drying can be attributed to the change of the effective refractive index of the gels. This composite material may provide a platform for three- dimensional plasmonic devices ranging from optical sensors to metamaterials.

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.

Mesostructured Composite Materials with Electrically Tunable Upconverting Properties.

A promising approach of designing mesostructured materials with novel physical behavior is to combine unique optical and electronic properties of solid nanoparticles with long-range ordering and facile response of soft matter to weak external stimuli. Here, orientationally ordered nematic liquid crystalline dispersions of rod-like upconversion nanoparticles are designed, practically realized, and characterized. Boundary conditions on particle surfaces, defined through surface functionalization, promote spontaneous unidirectional self-alignment of the dispersed rod-like nanoparticles, mechanically coupled to the molecular ordering direction of the thermotropic nematic liquid crystal host. As host is electrically switched at low voltages ≈ 1 V, nanorods rotate, yielding tunable upconversion and polarized luminescence properties of the composite. Spectral and polarization dependencies are characterized and explained through invoking models of electrical switching of liquid crystals and upconversion dependence on crystalline matrices of nanorods, and their potential practical uses are discussed.

Plasmon-enhanced energy transfer for improved upconversion of infrared radiation in doped-lanthanide nanocrystals.

Upconversion of infrared radiation into visible light has been investigated for applications in photovoltaics and biological imaging. However, low conversion efficiency due to small absorption cross-section for infrared light (Yb(3+)), and slow rate of energy transfer (to Er(3+) states) has prevented application of upconversion photoluminescence (UPL) for diffuse sunlight or imaging tissue samples. Here, we utilize resonant surface plasmon polaritons (SPP) waves to enhance UPL in doped-lanthanide nanocrystals. Our analysis indicates that SPP waves not only enhance the electromagnetic field, and hence weak Purcell effect, but also increase the rate of resonant energy transfer from Yb(3+) to Er(3+) ions by 6 fold. While we do observe strong metal mediated quenching (14-fold) of green fluorescence on flat metal surfaces, the nanostructured metal is resonant in the infrared and hence enhances the nanocrystal UPL. This strong Coulombic effect on energy transfer can have important implications for other fluorescent and excitonic systems too.

Imaging of director fields in liquid crystals using stimulated Raman scattering microscopy.

We demonstrate an approach for background-free three-dimensional imaging of director fields in liquid crystals using stimulated Raman scattering microscopy. This imaging technique is implemented using a single femtosecond pulsed laser and a photonic crystal fiber, providing Stokes and pump frequencies needed to access Raman shifts of different chemical bonds of molecules and allowing for chemically selective and broadband imaging of both pristine liquid crystals and composite materials. Using examples of model three-dimensional structures of director fields, we show that the described technique is a powerful tool for mapping of long-range molecular orientation patterns in soft matter via polarized chemical-selective imaging.

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.

Anisotropic electrostatic screening of charged colloids in nematic solvents.

The physical behavior of anisotropic charged colloids is determined by their material dielectric anisotropy, affecting colloidal self-assembly, biological function, and even out-of-equilibrium behavior. However, little is known about anisotropic electrostatic screening, which underlies all electrostatic effective interactions in such soft or biological materials. In this work, we demonstrate anisotropic electrostatic screening for charged colloidal particles in a nematic electrolyte. We show that material anisotropy behaves markedly different from particle anisotropy. The electrostatic potential and pair interactions decay with an anisotropic Debye screening length, contrasting the constant screening length for isotropic electrolytes. Charged dumpling-shaped near-spherical colloidal particles in a nematic medium are used as an experimental model system to explore the effects of anisotropic screening, demonstrating competing anisotropic elastic and electrostatic effective pair interactions for colloidal surface charges tunable from neutral to high, yielding particle-separated metastable states. Generally, our work contributes to the understanding of electrostatic screening in nematic anisotropic media.

Self-organization of nanoparticles and molecules in periodic Liesegang-type structures.

Chemical organization in reaction-diffusion systems offers a strategy for the generation of materials with ordered morphologies and structural hierarchy. Periodic structures are formed by either molecules or nanoparticles. On the premise of new directing factors and materials, an emerging frontier is the design of systems in which the precipitation partners are nanoparticles and molecules. We show that solvent evaporation from a suspension of cellulose nanocrystals (CNCs) and l-(+)-tartaric acid [l-(+)-TA] causes phase separation and precipitation, which, being coupled with a reaction/diffusion, results in rhythmic alternation of CNC-rich and l-(+)-TA-rich rings. The CNC-rich regions have a cholesteric structure, while the l-(+)-TA-rich bands are formed by radially aligned elongated bundles. The moving edge of the pattern propagates with a finite constant velocity, which enables control of periodicity by varying film preparation conditions. This work expands knowledge about self-organizing reaction-diffusion systems and offers a strategy for the design of self-organizing materials.

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.

Liquid crystal self-assembly of upconversion nanorods enriched by depletion forces for mesostructured material preparation.

Monodisperse rod-like colloidal particles are known for spontaneously forming both nematic and smectic liquid crystal phases, but their self-assembly was typically exploited from the fundamental soft condensed matter physics perspective. Here we demonstrate that depletion interactions, driven by non-adsorbing polymers like dextran and surfactants, can be used to enrich the self-organization of photon-upconversion nanorods into orientationally ordered nematic and smectic-like membrane colloidal superstructures. We study thermodynamic phase diagrams and demonstrate polarization-dependent photon upconversion exhibited by the ensuing composites, which arises from the superposition of unique properties of the solid nanostructures and the long-range ordering enabled by liquid crystalline self-organization. Finally, we discuss how our method of utilizing self-assembly due to the steric and electrostatic interactions, along with attractive depletion forces, can enable technological uses of lyotropic colloidal liquid crystals and mesostructured composite materials enabled by them, even when they are formed by anisotropic nanoparticles with relatively small aspect ratios.

Electric Switching of Fluorescence Decay in Gold-Silica-Dye Nematic Nanocolloids Mediated by Surface Plasmons.

Tunable composite materials with interesting physical behavior can be designed through integrating unique optical properties of solid nanostructures with facile responses of soft matter to weak external stimuli, but this approach remains challenged by their poorly controlled coassembly at the mesoscale. Using scalable wet chemical synthesis procedures, we fabricated anisotropic gold-silica-dye colloidal nanostructures and then organized them into the device-scale (demonstrated for square-inch cells) electrically tunable composites by simultaneously invoking molecular and colloidal self-assembly. We show that the ensuing ordered colloidal dispersions of shape-anisotropic nanostructures exhibit tunable fluorescence decay rates and intensity. We characterize how these properties depend on low-voltage fields and polarization of both the excitation and emission light, demonstrating a great potential for the practical realization of an interesting breed of nanostructured composite materials.

Triclinic nematic colloidal crystals from competing elastic and electrostatic interactions.

The self-assembly of nanoparticles can enable the generation of composites with predesigned properties, but reproducing the structural diversity of atomic and molecular crystals remains a challenge. We combined anisotropic elastic and weakly screened electrostatic interactions to guide both orientational and triclinic positional self-ordering of inorganic nanocrystals in a nematic fluid host. The lattice periodicity of these low-symmetry colloidal crystals is more than an order of magnitude larger than the nanoparticle size. The orientations of the nanocrystals, as well as the crystallographic axes of the ensuing triclinic colloidal crystals, are coupled to the uniform alignment direction of the nematic host, which can be readily controlled on large scales. We examine colloidal pair and many-body interactions and show how triclinic crystals with orientational ordering of the semiconductor nanorods emerge from competing long-range elastic and electrostatic forces.

Metal nanoparticle dispersion, alignment, and assembly in nematic liquid crystals for applications in switchable plasmonic color filters and E-polarizers.

Viewing angle characteristics of displays and performance of electro-optic devices are often compromised by the quality of dichroic thin-film polarizers, while dichroic optical filters usually lack tunability and cannot work beyond the visible part of optical spectrum. We demonstrate that molecular-colloidal organic-inorganic composites formed by liquid crystals and relatively dilute dispersions of orientationally ordered anisotropic gold nanoparticles, such as rods and platelets, can be used in engineering of switchable plasmonic polarizers and color filters. The use of metal nanoparticles instead of dichroic dyes allows for obtaining desired polarizing or scattering and absorption properties not only within the visible but also in the infrared parts of an optical spectrum. We explore spontaneous surface-anchoring-mediated alignment of surface-functionalized anisotropic gold nanoparticles and its control by low-voltage electric fields, elastic colloidal interactions and self-assembly, as well as the uses of these effects in defining tunable properties of the ensuing organic-inorganic nanostructured composites. Electrically tunable interaction of the composites may allow for engineering of practical electro-optic devices, such as a new breed of color filters and plasmonic polarizers.

Plasmon-Exciton Interactions Probed Using Spatial Coentrapment of Nanoparticles by Topological Singularities.

We study plasmon-exciton interaction by using topological singularities to spatially confine, selectively deliver, cotrap and optically probe colloidal semiconductor and plasmonic nanoparticles. The interaction is monitored in a single quantum system in the bulk of a liquid crystal medium where nanoparticles are manipulated and nanoconfined far from dielectric interfaces using laser tweezers and topological configurations containing singularities. When quantum dot-in-a-rod particles are spatially colocated with a plasmonic gold nanoburst particle in a topological singularity core, its fluorescence increases because blinking is significantly suppressed and the radiative decay rate increases by nearly an order of magnitude owing to the Purcell effect. We argue that the blinking suppression is the result of the radiative rate change that mitigates Auger recombination and quantum dot ionization, consequently reducing nonradiative recombination. Our work demonstrates that topological singularities are an effective platform for studying and controlling plasmon-exciton interactions.