All-optical 3D blue phase photonic crystal switch with photosensitive dopants.

Blue phase (BP) liquid crystals (LC) have lately become the focus of extensive research due to their peculiar properties and structure. BPs exhibit a highly organized 3D structure with a lattice period in the hundreds of nm. Owing to such structure, BPs are regarded as 3D photonic crystals. The unique properties of this complex LC phase are achieved by the self-assembly of the LC molecules into periodic cubic structures, producing bright selective Bragg reflections. Novel applications involving 3D photonic crystals would certainly benefit from enhanced ground-breaking functionalities. However, the use of BPs as 3D has been traditionally curtailed by the BP crystals trend to grow as random polycrystals, making it difficult to develop practical BP-based photonic devices. The possibility of generating mm-sized BP monocrystals was recently demonstrated. However, besides increasing the scarce number of 3D photonic structural materials, their applications as 3D photonic crystals do not show apparent advantages over other solid materials or metamaterials. Having a tunable BP monocrystal, where crystals could be switched, modulating simultaneously some of their properties as 3D photonic crystals, they would constitute a new family of materials with superior performance to other existing materials, opening up a plethora of new applications. In this work, an all-optical switchable 3D photonic crystal based on BPs doped with tailored photoactive molecules is demonstrated. Two switching modes have been achieved, one where the BP reversibly transitions between two BP phases, BPI and BPII, (two different cubic crystal systems) while maintaining the monocrystallinity of the whole system. The second mode, again reversible, switches between BPI and isotropic state. None of these modes are related to the regular thermal transitions between LC phases; switching is triggered by light pulses of different wavelengths. This all-optical approach allows for a seamless fast remotely controlled optical switch between two 3D photonic crystals in different cubic crystal systems and between a photonic crystal and an isotropic matrix. Applications of switchable BPs for adaptive optics systems or photonic integrated circuits would make great advances using 3D photonic crystal switches. All-optical photonic systems such as these hold great promise for the development of tunable and efficient photonic devices such as dynamic optical filters and sensors, as they enable light-driven modulation and sensing applications with unprecedented versatility.

Design and Self-Assembling Behaviour of Calamitic Reactive Mesogens with Lateral Methyl and Methoxy Substituents and Vinyl Terminal Group.

Smart self-organising systems attract considerable attention in the scientific community. In order to control and stabilise the liquid crystalline behaviour, and hence the self-organisation, the polymerisation process can be effectively used. Mesogenic units incorporated into the backbones as functional side chains of weakly cross-linked macromolecules can become orientationally ordered. Several new calamitic reactive mesogens possessing the vinyl terminal group with varying flexible chain lengths and with/without lateral substitution by the methyl (methoxy) groups have been designed and studied. Depending on the molecular structure, namely, the type and position of the lateral substituents, the resulting materials form the nematic, the orthogonal SmA and the tilted SmC phases in a reasonably broad temperature range, and the structure of the mesophases was confirmed by X-ray diffraction experiments. The main objective of this work is to contribute to better understanding of the molecular structure-mesomorphic property relationship for new functional reactive mesogens, aiming at further design of smart self-assembling macromolecular materials for novel sensor systems.

Deuteron NMR investigation on orientational order parameter in polymer dispersed liquid crystal elastomers.

Polymer-dispersed liquid crystal elastomers have been recently introduced as a thermomechanically active composite material, consisting of magnetically oriented liquid crystal elastomer particles incorporated in a cured polymer matrix. Their thermomechanical properties are largely governed by the degree of imprinted particle alignment, which can be assessed by means of deuterium perturbed 2H-NMR. Spectra of samples with various degrees of imprinted particle alignment were recorded and the results simulated using the discrete reorientational exchange model developed for determining the dispersion of liquid crystal elastomer's domain orientational distribution. We show that the model can be applied to measure the orientational distribution of embedded liquid crystal microparticles and successfully determine the orientational order parameter in the composite system. Thermomechanical measurements correlate well with the obtained results, thus additionally confirming the validity of the applied method.

Self-Assembling Behavior of Smart Nanocomposite System: Ferroelectric Liquid Crystal Confined by Stretched Porous Polyethylene Film.

The control and prediction of soft systems exhibiting self-organization behavior can be realized by different means but still remains a highlighted task. Novel advanced nanocomposite system has been designed by filling of a stretched porous polyethylene (PE) film with pore dimensions of hundreds of nanometers by chiral ferroelectric liquid crystalline (LC) compound possessing polar self-assembling behavior. Lactic acid derivative exhibiting the paraelectric orthogonal smectic A* and the ferroelectric tilted smectic C* phases over a broad temperature range is used as a self-assembling compound. The morphology of nanocomposite film has been checked by Atomic Force Microscopy (AFM). The designed nanocomposite has been studied by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), small and wide-angle X-ray scattering and broadband dielectric spectroscopy. The effect of a porous PE confinement on self-assembling, structural, and dielectric behavior of the chiral LC compound has been established and discussed. While the mesomorphic and structural properties of the nanocomposite are found not to be much influenced in comparison to that of a pure LC compound, the polar properties have been toughly suppressed by the specific confinement. Nevertheless, the electro-optic switching was clearly observed under applied electric field of low frequency (210 V, 19 Hz). The dielectric spectroscopy and X-ray results reveal that the helical structure of the ferroelectric liquid crystal inside the PE matrix is completely unwound, and the molecules are aligned along stretching direction. Obtained results demonstrate possibilities of using stretched porous polyolefins as promising matrices for the design of new nanocomposites.

Laser-induced formation of "craters" and "hills" in azobenzene-containing polymethacrylate films.

Functional organic polymer materials with an ability to change their surface topography in response to external contactless stimuli, like light irradiation, have attracted considerable attention. This work is devoted to the study of contactless control of the surface topography and the formation of the surface features in the amorphousized and liquid crystalline films of two azobenzene-containing polymers. The investigated polymers are side-chain polymethacrylates containing azobenzene chromophores with two lateral methyl substituents in ortho-positions and differing in the length of flexible spacer with six and ten methylene units. Two lateral methyl substituents at the azobenzene chromophore ensure high photoresponses of these polymeric samples in the whole visible spectral range. Irradiation of the polymethacrylate films by focused polarized light of green (532 nm) and red (633 nm) lasers induces a specific photodeformation of the film surface. In the case of the green light formation of circular "craters" with anisotropic borders was found, whereas for the red light highly asymmetric "hills" were observed. The possible mechanisms of the surface topography formation and their features are discussed.

Design of polar self-assembling lactic acid derivatives possessing submicrometre helical pitch.

Several new lactic acid derivatives containing the keto linkage group far from the chiral part and short alkyl chains have been synthesized and characterised by polarising optical microscopy, differential scanning calorimetry, as well as electro-optic and dielectric spectroscopy. The materials possess a self-assembling behaviour on the nanoscale level as they form polar smectic liquid crystalline mesophases, namely the orthogonal paraelectric SmA* and the tilted ferroelectric SmC* phases, in a broad temperature range down to room temperature. A short helical pitch (≈120-320 nm), relatively high spontaneous polarisation (≈150 nC/cm2) and reasonable tilt angle values have been determined within the temperature range of the tilted ferroelectric SmC* phase. The obtained results make the new materials useful for the advanced mixture design and for further utilisation in electro-optic devices based on the deformed helix ferroelectric effect.

Photoinduced Changes of Surface Topography in Amorphous, Liquid-Crystalline, and Crystalline Films of Bent-Core Azobenzene-Containing Substance.

Recently, photofluidization and mass-transfer effects have gained substantial interest because of their unique abilities of photocontrolled manipulation with material structure and physicochemical properties. In this work, the surface topographies of amorphous, nematic, and crystalline films of an azobenzene-containing bent-core (banana-shaped) compound were studied using a special experimental setup combining polarizing optical microscopy and atomic force microscopy. Spin-coating or rapid cooling of the samples enabled the formation of glassy amorphous or nematic films of the substance. The effects of UV and visible-light irradiation on the surface roughness of the films were investigated. It was found that UV irradiation leads to the fast isothermal transition of nematic and crystalline phases into the isotropic phase. This effect is associated with E-Z photoisomerization of the compound accompanied by a decrease of the anisometry of the bent-core molecules. Focused polarized visible-light irradiation (457.9 nm) results in mass-transfer phenomena and induces the formation of so-called "craters" in amorphous and crystalline films of the substance. The observed photofluidization and mass-transfer processes allow glass-forming bent-core azobenzene-containing substances to be considered for the creation of promising materials with photocontrollable surface topographies. Such compounds are of principal importance for the solution of a broad range of problems related to the investigation of surface phenomena in colloid and physical chemistry, such as surface modification for chemical and catalytic reactions, predetermined morphology of surfaces and interfaces in soft matter, and chemical and biochemical sensing.

Brief overview on 2H NMR studies of polysiloxane-based side-chain nematic elastomers.

This is a brief overview on recent studies on liquid crystalline elastomers (LCEs) based on polysiloxane chain, in the form of monodomain films, selectively (2)H-labeled in different parts of the LCE samples, i.e. on the crosslinker or mesogenic units. (2)H NMR spectroscopic techniques were used to measure the temperature dependence of the quadrupolar splittings, line widths and relaxation times, T(1) and T(2). From these data, several information about the orientational order parameter, S, of various LCE fragments, thermodynamic features of the isotropic-nematic transition and main motional processes could be generalized for this type of elastomers.

Thermotropic and lyotropic behaviour of new liquid-crystalline materials with different hydrophilic groups: synthesis and mesomorphic properties.

Several new calamitic liquid-crystalline (LC) materials with flexible hydrophilic chains, namely either hydroxy groups or ethylene glycol units, or both types together, have been synthesized in order to look for new functional LC materials exhibiting both, thermotropic and lyotropic behaviour. Such materials are of high potential interest for challenging issues such as the self-organization of carbon nanotubes or various nanoparticles. Thermotropic mesomorphic properties have been studied by using polarizing optical microscopy, differential scanning calorimetry and X-ray scattering. Four of these nonchiral and chiral materials exhibit nematic and chiral nematic phases, respectively. For some molecular structures, smectic phases have also been detected. A contact sample of one of the prepared compounds with diethylene glycol clearly shows the lyotropic behaviour; namely a lamellar phase was observed. The relationship between the molecular structure and mesomorphic properties of these new LCs with hydrophilic chains is discussed.

Orientational and structural properties of ferroelectric liquid crystal with a broad temperature range in the SmC(*) phase by (13)C NMR, x-ray scattering and dielectric spectroscopy.

Thermotropic liquid crystalline materials laterally substituted by a methyl group on the aromatic ring of the alkoxybenzoate unit far from the chiral centre exhibit a very broad temperature range in the ferroelectric smectic C* (SmC(*)) phase on cooling (including supercooling) with a very high spontaneous polarization (∼210 nC cm(-2)) and tilt angle (∼43°) at saturation. We are presenting a detailed study of the physical properties of a ferroelectric compound, representative of this category of liquid crystals, by means of solid state (13)C-NMR, small angle x-ray scattering, dielectric spectroscopy and optical methods of the tilted SmC(*). Values of the spontaneous tilt angle measured optically are compared to those determined from the x-ray data and discussed. In addition, the viscosity has been determined in the SmC(*) phase by different experimental methods. (13)C NMR data allowed us to get information about the degree of orientational order of the SmC(*) phase and revealed the complete unwinding of the helical axis at the magnetic field of 9.4 T. This result is discussed in the framework of recent publications on the effect of the magnetic field on the supra-molecular structure of the SmC(*) phase.

Structural and orientational properties of the ferro, antiferroelectric, and re-entrant smectic C phases of ZLL7/ by deuterium NMR and other experimental techniques.

In this work, two selectively deuterium-labeled isotopomers of the (S)-2-methylbutyl- [4'-(4' '-heptyloxyphenyl)-benzoyl-4-oxy-(S)-2-((S)-2')-benzoyl)-propionyl)]-propionate (ZLL 7/), one labeled on the phenyl ring (ZLL 7/-phe-D2) and the other one on the biphenyl fragment (ZLL 7/-biphe-D2), have been investigated by deuterium NMR (DNMR) spectroscopy and other experimental techniques. These compounds possess the paraelectric SmA, the ferroelectric SmC, the antiferroelectric SmC(A), the re-entrant ferroelectric SmC(re), and the ferroelectric hexatic phases down to room temperature. The orientational ordering properties of the two labeled fragments have been determined by means of DNMR, and the mesophase behavior at two magnetic fields is discussed. In particular, the effect of the magnetic field on the supramolecular structure of the SmC and SmC(re) phases is commented. This study revealed to be useful to understand the structural and conformational properties of the ferroelectric/antiferroelectric/re-entrant/hexatic smectic phases. Mesomorphic properties, spontaneous tilt angle, polarization, and layer spacing have been studied for the labeled materials and compared with those obtained for the nonlabeled compound. The two self-consistent set of data, from optical and DNMR measurements and X-ray results, allow us to associate at the transition from the SmC to the SmC(A) phase a change of the molecular conformation.