Cuiyu Zhang

Direct observation of liquid crystals using cryo‐TEM: Specimen preparation and low‐dose imaging

Liquid crystals (LCs) represent a challenging group of materials for direct transmission electron microscopy (TEM) studies due to the complications in specimen preparation and the severe radiation damage. In this paper, we summarize a series of specimen preparation methods, including thin film and cryo‐sectioning approaches, as a comprehensive toolset enabling high‐resolution direct cryo‐TEM observation of a broad range of LCs. We also present comparative analysis using cryo‐TEM and replica freeze‐fracture TEM on both thermotropic and lyotropic LCs. In addition to the revisits of previous practices, some new concepts are introduced, e.g., suspended thermotropic LC thin films, combined high‐pressure freezing and cryo‐sectioning of lyotropic LCs, and the complementary applications of direct TEM and indirect replica TEM techniques. The significance of subnanometer resolution cryo‐TEM observation is demonstrated in a few important issues in LC studies, including providing direct evidences for the existence of nanoscale smectic domains in nematic bent‐core thermotropic LCs, comprehensive understanding of the twist‐bend nematic phase, and probing the packing of columnar aggregates in lyotropic chromonic LCs. Direct TEM observation opens ways to a variety of TEM techniques, suggesting that TEM (replica, cryo, and in situ techniques), in general, may be a promising part of the solution to the lack of effective structural probe at the molecular scale in LC studies. Microsc. Res. Tech. 77:754–772, 2014.

Unexpected liquid crystalline behaviour of three-ring bent-core mesogens: bis(4-subst.-phenyl) 2-methyl-iso-phthalates

Three-ring bent-core bis(4-subst.-phenyl) 2-methyl-iso-phthalates exhibiting nematic, SmA and SmC phases are reported. The occurring mesophases have been identified by their optical textures and X-ray diffraction measurements which give also geometrical structural parameters like layer spacing and molecular tilt. Quantum chemical calculations on single molecules and X-ray structure analysis in the crystalline state indicate wide opening angles (about 155°) of the molecular legs due to the lateral methyl group in position 2 of the central phenyl ring. However solid state NMR spectroscopy in the liquid crystalline phases finds stronger molecular bending (bending angle to be about 138° in the SmA and about 146° in the nematic phase). Dielectric and SHG measurements give evidence that in the SmA phase a polar structure can be induced by application of an electric field which disappears in the isotropic liquid phase. The electric field not only leads to a slight textural change even in the SmA phase but also polar-type electric current response (PS about 200 nC cm−2) is observed. This unusual electro-optical behaviour is discussed on the basis of the orientation of polar clusters formed by the bent molecules. In the paper we not only attempt to characterize the mesophases and to describe their physical properties, but we also show that these types of molecules represent the borderline between bent-shaped and calamitic liquid crystals.

Helical nanofilaments of bent-core liquid crystals with a second twist

The B4 phase of bent-core liquid crystals has been shown to be an assembly of twisted layers stacked to form helical nanofilaments. Interestingly, some of them have structural colours that cannot be explained by the nanofilaments alone. Here cryogenic-transmission electron microscopy observations on 40-120 nm films of four bent-core liquid crystal materials show that the filaments are present even in contact with a carbon substrate with only minor deformation, thus representing bulk properties. We find that the subsequent arrays of nanofilaments are not parallel to each other, but rotate by an angle of 35-40° with respect to each other. This doubly twisted structure can explain the structural colour. Being principally different from the packing of molecules in the twist grain boundary and blue phases, the double-twist structure of helical nanofilaments expands the rich word of nanostructured organic materials.

A fibre forming smectic twist–bent liquid crystalline phase

We demonstrate the nanostructure and filament formation of a novel liquid crystal phase of a dimeric mesogen below the twist–bend nematic phase. The new fibre-forming phase is distinguished by a short-correlated smectic order combined with an additional nanoscale periodicity that is not associated with density modulation.

Nanostructure and dielectric properties of a twist-bend nematic liquid crystal mixture

We present freeze-fracture transmission electron microscopy (FF-TEM), dielectric spectroscopy and electro-optic measurements on a dimeric liquid crystal mixture, which previously was proposed to form the twist-bend nematic (Ntb) phase. Our FF-TEM studies provide a direct image of a 10.5 nm periodic structure, consistent with the expected nanoscale, heliconical twist-bend modulation of the molecular orientation. Dielectric measurements in the 100 Hz to 10 MHz range reveal three nearly Debye-type dispersion processes in the nematic and the twist-bend phase. Low frequency 8 V/µm electric fields applied on planar cells cause the optical-scale stripe texture (another characteristic feature of the Ntb phase) to disappear. Higher (>16 V/µm) fields gradually realign the heliconical axis along the electric field; it relaxes back after the field removal.

Two distinct modulated layer structures of an asymmetric bent-shape smectic liquid crystal

We present chemical synthesis, polarising optical microscopy, electric current, and small-angle X-ray scattering measurements on a strongly anisotropic bent-shape liquid crystal material. We find that it has two layer-undulated ferroelectric phases, M1 and M2. In the higher temperature M2 phase the undulation amplitude and period increases on cooling, similar to other published materials. It can be identified with a tilted modulated phase. In the M1 phase the molecular plane is not tilted, and – in sharp contrast with all prior observations – the modulation amplitude and period decrease on cooling. These observations can be explained with a ‘leaning’ director structure, where the leaning angle is decreasing on cooling.

Cryo-TEM studies of two smectic phases of an asymmetric bent-core material

Cryo-TEM studies on two smectic phases of an asymmetric bent-core liquid crystal material are presented and compared to prior X-ray results obtained in bulk samples. While the bulk samples have layer-modulated structures, those modulations are not observable in the 100-nm-thick TEM samples, indicating surface-induced suppression of the layer modulations. The observed layer spacing is in agreement with the X-ray results in the lower temperature smectic phase, but distinctly larger in the higher temperature phase. This indicates surface-induced suppression of the director tilt. Cryo-TEM textures resolve the profiles of individual smectic layers at the scales down to few nanometres and reveal the presence of edge and screw dislocations, twist grain boundaries, small-angle and large-angle tilt grain boundaries.

2-Alkoxy-1,3-thiazoles: A new core unit for incorporation into self-organising materials. Synthetic approach, mesomorphism, and electrooptic evaluation

The synthesis and transition temperatures of the first series of 2-alkoxy-1,3-thiazole-based liquid crystals are reported. The 2-alkoxy-1,3-thiazole moiety was generated in high yield via a selective SNAr reaction between 2,5-dibromo-1,3-thiazole and the corresponding long-chain alkoxide. The synthesis and mesomorphic properties of the aforementioned chevron-free 2-alkoxy-1,3-thiazole-based liquid crystals are discussed and compared with their 5-alkoxy-1,3-thiazole and phenyl based analogues. Electrooptical properties for both series of alkoxy-1,3-thiazole-based liquid crystals are also presented and discussed.

Nanostructures of Nematic Materials of Laterally Branched Molecules

The synthesis and small-angle X-ray scattering (SAXS) characterization is reported for 20 laterally branched mesogenic molecules, which are derived from the common rod-shaped 2,5-bis([4-(octyloxy)phenyl]carbonyloxy) benzoic acid unit. These compounds have a varying degree of flexibility, in that their lateral branch is formed upon conversion of the acid to either an ester or an amide, and most laterally branched molecules exhibit relatively wide nematic liquid-crystal phases with a direct nematic-to-crystal transition at lower temperatures. SAXS studies reveal the presence of smectic-like nanostructures (clusters) with short-range order in the nematic phase, with characteristic correlation lengths from 3 to over 10 nm. The smectic layers that are contained in these clusters are tilted with respect to the nematic director by angles ranging from 0° (i.e. untilted) to 55°. In some compounds, the intensity of the SAXS peak corresponding to the smectic layer spacing depends strongly on temperature. The main features of the nanostructures can be understood based on the molecular structure; therefore, guiding future synthetic work towards more precisely controlled and technologically useful nanostructures in nematics.

Nanostructure of edge dislocations in a smectic C* liquid crystal

We report on the first direct nanoscale imaging of elementary edge dislocations in a thermotropic smectic-C* liquid crystal with the Burgers vector equal to one smectic layer spacing d. We find two different types of dislocation profiles. In the dislocation of type A, the layers deformations lack mirror symmetry with respect to the plane perpendicular to the Burgers vector; the dislocation core size is on the order of d. In the dislocation of type S, the core is strongly anisotropic, extending along the Burgers vector over distances much larger (by a factor of 4) than d. The difference is attributed to a different orientation of the molecular tilt plane with respect to the dislocations axis; the asymmetric layers distortions are observed when the molecular tilt plane is perpendicular to the axis and the split S core is observed when the molecules are tilted along the line.