Ferroelectric liquid crystals smectic layer structures

Calamitic metallomesogens forming a chiral smectic C phase (SmC ) are ferroelectric materials. Due to the low symmetry of this phase when the helix is unwound (C2) the molecular dipoles are aUgned within the layers of the SmC phase, giving rise to ferroelectric order in the layers. Because the SmC phase has a helical structure, there is no net macroscopic dipole moment for the bulk phase. However, it is possible to unwind the helix by application of an external electric field or by surface anchoring in thin cells. Under such conditions, a well-aligned film of the ferroelectric liquid crystal can exhibit a net polarisation, called the spontaneous polarisation (Ps). Ferroelectric liquid crystals are of interest for display applications because the macroscopic polarisation can be switched very fast by an... 

Yoshino et al. [358] have investigated a derivative with mesogenic ester groups, poly(bis(4-methoxy-4 -hcxyloxy biphenyl) dipropargyl malonate), and find electrochemical doping with BF4to occur to both the main chain and the mesogenic unit in the side chain. The x-ray diffraction indicates a smectic phase between 80 and 115°C. The formation of a layered structure in a mixture of the polymer with a smectic ferroelectric liquid crystal is also reported. 

The flexoelectric effect is a phenomenon where a space variation of the order parameter induces polarization. Chiral polar smectics are liquid crystals formed of chiral molecules and organized in layers. All phases in tilted chiral polar smectic liquid crystals have modulated structures and they are therefore good candidates for exhibiting the flexoelectric effect. The flexoelectric effect is less pronounced in the ferroelectric SmC phase and in the antiferroelectric SmC. The flexoelectric effect is more pronounced in more complex phases the three-layer SmCpu phase, the four-layer SmCFi2 phase and the six-layer SmCe a phase. 

The chapter is organized as follows The second section discusses the prototype polar smectics the ferroelectric liquid crystals. We discuss the structure of the ferroelectric phase, the theoretical explanation for it and we introduce the flexoelectric effect in chiral polar smectics. Next we introduce a new set of chiral polar smectics, the antiferroelectric liquid crystals, and we describe the structures of different phases found in these systems. We present the discrete theoretical modelling approach, which experimentally consistently describes the phases and their properties. Then we introduce the discrete form of the flexoelectric effect in these systems and show that without flexoelectricity no interactions of longer range would be significant and therefore no structures with longer periods than two layers would be stable. We discuss also a few phenomena that are related to the complexity of the structures, such as the existence of a longitudinal, i.e. parallel to the... 

Ferroelectric materials are a subclass of pyro- and piezoelectric materials (Fig. 1) (see Piezoelectric Polymers). They are very rarely foimd in crystalline organic or polymeric materials because ferroelectric hysteresis requires enough molecular mobility to reorient molecular dipoles in space. So semicrystalline poly(vinylidene fluoride) (PVDF) is nearly the only known compoimd (1). On the contrary, ferroelectric behavior is very often observed in chiral liquid crystalline materials, both low molar mass and poljuneric. For an overview of ferroelectric liquid crystals, see Reference 2. Tilted smectic liquid crystals that are made from chiral molecules lack the symmetry plane perpendicular to the smectic layer structure (Fig. 2). Therefore, they develop a spontaneous electric polarization, which is oriented perpendicular to the layer normal and perpendicular to the tilt direction. Because of the liquid-like structure inside the smectic layers, the direction of the tilt and thns the polar axis can be easily switched in external electric fields (see Figs. 2 and 3). 

The author would like to propose another method of determining the alignment layer polarity. In this method, the cell structure of the twisted FLC mode described in Ref. 35 is used. Consider the cell structure for which the rubbing directions on the top and bottom plates are set rectangularly, as shown in Fig. 5.2.9. A ferroelectric liquid crystal of 45° tilt angle, showing no smectic... 

On a macroscopic scale, the spontaneous polarization vector in the optically active phase spirals about an axis perpendicular to the smectic layers (Fig. 20), and sums to zero. This macroscopic cancellation of the polarization vectors can be avoided if the helical structure is unwound by surface forces, by an applied field, or by pitch compensation with an oppositely handed dopant. The surface stabilized ferroelectric liquid crystal display utilizes this structure and uses coupling between the electric field and the spontaneous polarization of the smectic C phase. The device uses a smectic C liquid crystal material in the so-called bookshelf structure shown in Fig. 21a. This device structure was fabricated by shearing thin (about 2 i,m) layers of liquid crystal in the... 

It is possible to use a liquid crystal material in various ways depending on the application in flexible display. In order to stabilize the substrate spacing, polymer walls and fibers allow also the application of ferroelectric liquid crystal, whose molecular alignment structure is conventionally known to be fragile and called as smectic layers. 

They found that an asymmetric carbon atom and a dipole moment in the molecular structure lead to a liquid crystal smectic C phase in which the molecular long axes are tilted from the layer normal of the smectic phase. Hence, ferroelectricity was expressed. The ferroelectric behavior definitely was confirmed by various measurements, including the D-E hysteresis [2]. 

Fujikake H, Aida T, Takizawa K, Kikuchi H, Fuji T, Kawakita M (1999) Study of smectic layer structure of polymer-stabilized ferroelectric liquid crystal with grayscale memory. Electron Commun Jpn 82(8) 1-8... 

The experimental observations could be consistently explained if the general tilt structure (SmCo) inside the layers is assumed. For most bent-core smectics the polar vector is perpendicular to the tilt plane, defined by the layer normal and averaged long axis direction, just as polarization in the ferroelectric rod-like liquid crystalline systems. However, since in the bent-core liquid crystals the polar order is decoupled from the tilt order, the polar director can in general have any direction in space thus it can also have a non-zero component along the layer normal. This can be achieved by a combination of tilting (rotation around the polar director) and leaning (rotation around the direction perpendicular to the polar director) of... 

Once the helical structure of the Sc phase is unwound, ferroelectricity is displayed (see Chapter 6 for the details). In recent years, many experimental studies have revealed that some liquid crystal compounds show new types of smectic phases with complex tilt and dipole order, such as the anti-ferroelectric smectic C phase, Sca phase, and the ferrielectric smectic C phase, Sc7 phase. For instance, in the Sca phase, the spontaneous polarization Ps is opposite for successive layers. It was found experimentally that the chiral So phase is in fact similar to the anti-ferroelectric Sca phase. 

The occurrence of ferroelectricity in the chiral smectic C phase was already predicted by Meyer in 1975 [21]. From symmetry arguments, he concluded a polarization of a smectic layer perpendicular to the layer normal and to the director. Unwinding of the helicoidal structure causes macroscopic ferroelectric properties of the phase [22], [23]. Unlike low molar mass liquid crystals or linear liquid crystal polymers, the unwinding of the helicoidal structure is performed by applying an electric field or by surface effects. 

The tilting of molecules in the B2 phase is clearly confirmed from the observation that the spherulites emerging from the isotropic phase show an electric field dependence of the position of the optical extinction lines (Fig. 9.26). Because of the tilting of banana molecules to the layer, chirality is spontaneously generated in addition to the polarity this fact sounds shocking but is so simple to be understood [132, 133]. If the molecule is rotated around their polar axis (the orientation of the bent in the molecules), which is akin to tilting the molecules in the layer, the rotation operation cannot be achieved by a simple translation (see Fig. 9.27). That is, these two states are in a mirror relation with left-handed and right-handed chirality. This is called the layer chirality. When the chirality couples with the polarity of the molecules, one would consider various smectic liquid crystal structures. There are two homochiral phases in which either (—) or (-I-) chiral molecules stack in the layers and a racemic phase in which layers are alternately stacked with layers of (—) and (-I-) chiral molecules. Each of those phases can be either ferroelectric or antiferroelectric, so that in total six different phases are present... 

Liquid crystal molecules usually tilt in the same direction over the smectic layers (synclinic [212]) in the smectic C (SmC) phase. However, in one of the smectic A (SmA) phases, called de-Vries phase [213,214], molecules tilt but the tile direction is random so that the overall molecular tilt cannot be recognized optically. Frustration can be produced between aligning and random orders [215]. There is another style of tilt, in which the tilting direction is aligning in one direction in each smectic layer however, tilting direction alternates between the adjacent layers (anticlinic [212]). It has been well known that the introduction of chirality into the synclinic and anticlinic stmctures produces the ferroelectric and antiferroelectric properties, respectively. Frustration between the ferroelectric and antiferroelectric properties produces the ferroelectric structure in which the spontaneous polarization is partially canceled by the different magnitude between plus and minus polarization directions [216, 217]. The anticlinic order, NOT the antiferroelectric order, has been reported to be created by achiral systems [218, 219], indicating that the frustration between synclinic and anticlinic structures occurs, without any polar effects. The clinicity is determined by the style of the molecular order between the adjacent smectic layers, and therefore, the molecular structures at the peripheral... 

---