Strongly Chiral Liquid Crystals in Nanoemulsions.

Liquid crystal (LC) emulsions represent a class of confined soft matter that exhibit exotic internal organizations and size-dependent properties, including responses to chemical and physical stimuli. Past studies have explored micrometer-scale LC emulsion droplets but little is known about LC ordering within submicrometer-sized droplets. This paper reports experiments and simulations that unmask the consequences of confinement in nanoemulsions on strongly chiral LCs that form bulk cholesteric and blue phases (BPs). A method based on light scattering is developed to characterize phase transitions of LCs within the nanodroplets. For droplets with a radius to the pitch ratio (Rv /p0 ) as small as 2/3, the BP-to-cholesteric transition is substantially suppressed, leading to a threefold increase of the BP temperature interval relative to bulk behavior. Complementary simulations align with experimental findings and reveal the dominant role of chiral elastic energy. For Rv /p0  ≈ 1/3, a single LC phase forms below the clearing point, with simulations revealing the new configuration to contain a τ-1/2 disclination that extends across the nanodroplet. These findings are discussed in the context of mechanisms by which polymer networks stabilize BPs and, more broadly, for the design of nanoconfined soft matter.

Blue-phase liquid crystal droplets.

Blue phases of liquid crystals represent unique ordered states of matter in which arrays of defects are organized into striking patterns. Most studies of blue phases to date have focused on bulk properties. In this work, we present a systematic study of blue phases confined into spherical droplets. It is found that, in addition to the so-called blue phases I and II, several new morphologies arise under confinement, with a complexity that increases with the chirality of the medium and with a nature that can be altered by surface anchoring. Through a combination of simulations and experiments, it is also found that one can control the wavelength at which blue-phase droplets absorb light by manipulating either their size or the strength of the anchoring, thereby providing a liquid-state analog of nanoparticles, where dimensions are used to control absorbance or emission. The results presented in this work also suggest that there are conditions where confinement increases the range of stability of blue phases, thereby providing intriguing prospects for applications.

Low-temperature properties of polymer-stabilised liquid-crystal blue phases.

The temperature dependences of the Kerr coefficient and the response time in the electrooptical effect of polymer-stabilised blue phases (PSBPs) of liquid crystals (LCs) with various polymer concentrations are investigated in a wide temperature range including temperatures lower than room temperature. The Kerr coefficients are found to abruptly decrease at low temperature, and the response time-temperature relation obeys the Arrhenius equation. For comparison of the Kerr effect and molecular rotation at low temperature, various physical properties such as permittivity, rotational relaxation time and dielectric relaxation strength of the PSBPs are investigated. The electrooptical response times and the dielectric relaxation times show different temperature dependences, and rotation of LC molecules in PSBPs was sufficiently active at low temperature and not strongly affected by the polymer.

Achiral Nanoparticle-Enhanced Chiral Twist and Thermal Stability of Blue Phase Liquid Crystals.

Blue phase liquid crystals (BPLCs) are chiral mesophases with 3D order, which makes them a promising template for doping nanoparticles (NPs), yielding tunable nanomaterials attractive for microlasers and numerous microsensor applications. However, doping NPs to BPLCs causes BP lattice extension, which translates to elongation of operating wavelengths of light reflection. Here, it is demonstrated that small (2.4 nm diameter) achiral gold (Au) NPs decorated with designed LC-like ligands can enhance the chiral twist of BPLCs (i.e., reduce cell size of the single BP unit up to ∼14% and ∼7% for BPI and BPII, respectively), translating to a blue-shift of Bragg reflection. Doping NPs also significantly increases the thermal stability of BPs from 5.5 °C (for undoped BPLC) up to 22.8 °C (for doped BPLC). In line with our expectations, both effects are saturated, and their magnitude depends on the concentration of investigated nanodopants as well the BP phase type. Our research highlights the critical role of functionalization of Au NPs on the phase sequence of BPLCs. We show that inappropriate selection of surface ligands can destabilize BPs. Our BPLC and Au NPs are photochemically stable and exhibit great miscibility, preventing NP aggregation in the BPLC matrix over the long term. We believe that our findings will improve the fabrication of advanced nanomaterials into 3D periodic soft photonic structures.

Control of Monodomain Polymer-Stabilized Cuboidal Nanocrystals of Chiral Nematics by Confinement.

Liquid crystals are important components of optical technologies. Cuboidal crystals consisting of chiral liquid crystals-the so-called blue phases (BPs), are of particular interest due to their crystalline structures and fast response times, but it is critical that control be gained over their phase behavior as well as the underlying dislocations and grain boundaries that arise in such systems. Blue phases exhibit cubic crystalline symmetries with lattice parameters in the 100 nm range and a network of disclination lines that can be polymerized to widen the range of temperatures over which they occur. Here, we introduce the concept of strain-controlled polymerization of BPs under confinement, which enables formation of strain-correlated stabilized morphologies that, under some circumstances, can adopt perfect single-crystal monodomain structures and undergo reversible crystal-to-crystal transformations, even if their disclination lines are polymerized. We have used super-resolution laser confocal microscopy to reveal the periodic structure and the lattice planes of the strain and polymerization stabilized BPs in 3D real space. Our experimental observations are supported and interpreted by relying on theory and computational simulations in terms of a free energy functional for a tensorial order parameter. Simulations are used to determine the orientation of the lattice planes unambiguously. The findings presented here offer opportunities for engineering optical devices based on single-crystal, polymer-stabilized BPs whose inherent liquid nature, fast dynamics, and long-range crystalline order can be fully exploited.

Experimental Advances in Nanoparticle-Driven Stabilization of Liquid-Crystalline Blue Phases and Twist-Grain Boundary Phases.

Recent advances in experimental studies of nanoparticle-driven stabilization of chiral liquid-crystalline phases are highlighted. The stabilization is achieved via the nanoparticles' assembly in the defect lattices of the soft liquid-crystalline hosts. This is of significant importance for understanding the interactions of nanoparticles with topological defects and for envisioned technological applications. We demonstrate that blue phases are stabilized and twist-grain boundary phases are induced by dispersing surface-functionalized CdSSe quantum dots, spherical Au nanoparticles, as well as MoS2 nanoplatelets and reduced-graphene oxide nanosheets in chiral liquid crystals. Phase diagrams are shown based on calorimetric and optical measurements. Our findings related to the role of the nanoparticle core composition, size, shape, and surface coating on the stabilization effect are presented, followed by an overview of and comparison with other related studies in the literature. Moreover, the key points of the underlying mechanisms are summarized and prospects in the field are briefly discussed.

Stimuli-Responsive Cubosomes Formed from Blue Phase Liquid Crystals.

Cubosomes formed from blue phase liquid crystals (BPs) dispersed in aqueous media exhibit optical responses to biological amphiphiles. In this study, the formation of aqueous dispersions of BPs is reported, and the effects of confinement and lipids on the phase behavior, optical appearance, and morphology of BP droplets are characterized.