Nematic Phases in 1,2,4‐Oxadiazole‐Based Bent‐Core Liquid Crystals: Is There a Ferroelectric Switching?

Four series of new 1,2,4‐oxadiazole derived bent‐core liquid crystals incorporating one or two cyclohexane rings are synthesized and investigated by optical polarizing microscopy, differential scanning calorimetry (DSC), X‐ray diffraction (XRD), electro‐optical, and dielectric investigations. All the compounds exhibit wide ranges of nematic phases composed of tilted smectic (SmC‐type) cybotactic clusters with strongly tilted aromatic cores (40–57°) and show a distinct peak in the current curves observed under a triangular wave field. Dielectric spectroscopy of aligned samples corroborates the previously proposed polar structure of the cybotactic clusters and the ferroelectric‐like polar switching of these nematic phases. Hence, it is shown that this is a general feature of the nematic phases of structurally different 3,5‐diphenyl‐1,2,4‐oxadiazole derivatives. In these uniaxial nematic phases there is appreciable local biaxiality and polar order in the cybotactic clusters. As a second point it is shown that electric field induced fan‐like textures, as often observed for the nematic phases of bent‐core liquid crystals, do not indicate the formation of a smectic phase, rather they represent special electro‐convection patterns due to hydrodynamic instabilities.     

Electro‐optical Materials: Switching of Electrically Responsive,Light‐Sensitive Colloidal Suspensions of Anisotropic Pigment Particles (Adv. Funct. Mater. 3/2011)

An unusual electro‐optical behavior of colloidal suspensions of dichroic, elongated (rod‐shaped) pigment particles is reported. These suspensions exhibit nematic liquid crystal order at low volume fraction of the suspended particles (<15 wt%) and show a strong electric and optical response to an external electric field. Additionally, the characteristics of the optical response can be reversibly manipulated by illuminating the sample with light in its absorption band. The suspensions show a number of interesting phenomena like homeotropic‐planar orientational transitions and light‐induced pattern formation.     

Switching of Electrically Responsive,Light‐Sensitive Colloidal Suspensions of Anisotropic Pigment Particles

An unusual electro‐optical behavior of colloidal suspensions of dichroic, elongated (rod‐shaped) pigment particles is reported. These suspensions exhibit nematic liquid crystal order at low volume fraction of the suspended particles (<15 wt%) and show a strong electric and optical response to an external electric field. Additionally, the characteristics of the optical response can be reversibly manipulated by illuminating the sample with light in its absorption band. The suspensions show a number of interesting phenomena like homeotropic‐planar orientational transitions and light‐induced pattern formation.     

Large Electrocaloric Effect in a Dielectric Liquid Possessing a Large Dielectric Anisotropy Near the Isotropic–Nematic Transition

The recent findings of large electrocaloric effects (ECEs) in ferroelectric polymers and in ferroelectric ceramic thin films have attracted great interest for developing new cooling cycles that are environmental friendly and have the potential to reach better efficiency than the existing vapor‐compression approach. Compared with these solid state ECE materials, a dielectric fluid with a large ECE can be more interesting because it may lead to new cooling cycles with simpler structures than these based on solid state ECE materials. Here it is shown that a large ECE can be realized in the liquid crystal (LC) 5CB near its nematic–isotropic (N‐I) phase transition. 5CB has a large dielectric anisotropy, which facilitates the electric‐field‐induced large polarization change. As a result, a large ECE, i.e., an isothermal entropy change of more than 23.6 J kg^?1 K^?1 is observed just above the N‐I transition.     

Spatially Resolved Electric‐Field Manipulation of Magnetism for CoFeB Mesoscopic Discs on Ferroelectrics

Electric‐field control of magnetism in ferromagnetic/ferroelectric multiferroic heterostructures is a promising way to realize fast and nonvolatile random‐access memory with high density and low‐power consumption. An important issue that has not been solved is the magnetic responses to different types of ferroelectric‐domain switching. Here, for the first time three types of magnetic responses are reported induced by different types of ferroelectric domain switching with in situ electric fields in the CoFeB mesoscopic discs grown on PMN‐PT(001), including type I and type II attributed to 109°, 71°/180° ferroelectric domain switching, respectively, and type III attributed to a combined behavior of multiferroelectric domain switching. Rotation of the magnetic easy axis by 90° induced by 109° ferroelectric domain switching is also found. In addition, the unique variations of effective magnetic anisotropy field with electric field are explained by the different ferroelectric domain switching paths. The spatially resolved study of electric‐field control of magnetism on the mesoscale not only enhances the understanding of the distinct magnetic responses to different ferroelectric domain switching and sheds light on the path of ferroelectric domain switching, but is also important for the realization of low‐power consumption and high‐speed magnetic random‐access memory utilizing these materials.     

Controlling the Self‐Assembly of Periodic Defect Patterns in Smectic Liquid Crystal Films with Electric Fields

Large‐area periodic defect patterns are produced in smectic A liquid crystals confined between rigid plate electrodes that impose conflicting parallel and normal anchoring conditions, inducing the formation of topological defects. Highly oriented stripe patterns are created in samples thinner than 2 μm due to self‐assembly of linear defect domains with period smaller than 4 μm, whereas hexagonal lattices of focal conic domains appear for thicker samples. The pattern type (1d/2d) and period can be controlled at the nematic–smectic phase transition by applying an electric field, which confines the defect domains to a thin surface layer with thickness comparable to the nematic coherence length. The pattern morphology persists in the smectic phase even after varying the field or switching it off. Bistable, non‐equilibrium patterns are stabilized by topological constraints of the smectic phase that hinder the rearrangement of defects in response to field variations.     

对向列相液晶反转壁中+1缺陷处挠曲电效应的理论分析

基于Pramoda Kumar等人文章中关于向列相液晶反转壁中+1缺陷处挠曲电效应的实验现象,我们利用Landau-de Gennes理论给出相应的理论分析。当对弱锚定的平行排列向列相液晶盒施加垂直基板的直流电压,在反转壁中的±1缺陷会发生旋转。对于其中的+1缺陷,我们给出了外加电场作用下液晶分子的自由能表达式并通过模拟描述指向矢的方位角和极角的变化情况给出相应的缺陷处电场驱动的结构变化。模拟结果给出的挠曲电效应引起的方位角的变化角度与Pramoda Kumar等人的实验得到的在+1缺陷处消光刷的变化情况是一致的。     

LaPO4 Mineral Liquid Crystalline Suspensions with Outstanding Colloidal Stability for Electro‐Optical Applications

Mineral liquid crystals are materials in which mineral's intrinsic properties are combined with the self‐organization behavior of colloids. However, the use of such a system for practical application, such as optical switching, has rarely been demonstrated due to the fundamental drawbacks of colloidal systems such as limited dispersion stability. Studying colloidal suspensions of LaPO₄ nanorods, it is found that drastic improvement of colloidal stability can be obtained through a transfer of particles from water towards ethylene glycol, thus enabling the investigation of liquid crystalline properties of these concentrated suspensions. Using polarization microscopy and small‐angle x‐ray scattering (SAXS), self‐organization into nematic and columnar mesophases is observed enabling the determination of the whole phase diagram as a function of ionic strength and rod volume fraction. When an external alternative electric field is applied, a very efficient orientation of the nanorods in the liquid‐crystalline suspension is obtained, which is associated with a significant optical birefringence. These properties, combined with the high colloidal stability, are promising for the use of such high transparent and athermal material in electro‐optical devices.     

A Strain‐Mediated Magnetoelectric‐Spin‐Torque Hybrid Structure

Magnetization dynamics induced by spin–orbit torques in a heavy‐metal/ferromagnet can potentially be used to design low‐power spintronics and logic devices. Recent computations have suggested that a strain‐mediated spin–orbit torque (SOT) switching in magnetoelectric (ME) heterostructures is fast, energy‐efficient, and permits a deterministic 180° magnetization switching. However, its experimental realization has remained elusive. Here, the coexistence of the strain‐mediated ME coupling and the SOT in a CoFeB/Pt/ferroelectric hybrid structure is shown experimentally. The voltage‐induced strain only slightly modifies the efficiency of SOT generation, but it gives rise to an effective magnetic anisotropy and rotates the magnetic easy axis which eliminates the incubation delay in current‐induced magnetization switching. The phase field simulations show that the electric‐field‐induced effective magnetic anisotropy field can reduce the switching time approximately by a factor of three for SOT in‐plane magnetization switching. It is anticipated that such strain‐mediated ME‐SOT hybrid structures may enable field‐free, ultrafast magnetization switching.     

Design and Integration in Electro‐Optic Devices of Highly Efficient and Robust Red‐NIR Phosphorescent Nematic Hybrid Liquid Crystals Containing [Mo6I8(OCOCnF2n+1)6]2− (n = 1, 2, 3) Nanoclusters

By combining [Mo₆I₈(C _n F_2n+1COO)₆]^2‐ (n = 1, 2, 3) nanocluster units with liquid crystalline ammonium cations, a new series of hybrid materials is developed that show a nematic liquid crystal phase, the most fluid of all LC phase, on a large range of temperatures including room temperature. The photophysical studies performed in the LC state show that these self‐assembled hybrid materials emit in the red‐NIR with absolute quantum yields up to 0.7 and show a very good photostability under continuous irradiation. They are further integrated up to 20 wt% in E7, a well‐known nematic commercial LC mixture. Mixtures are investigated in terms of homogeneity and stability to select the best suitable candidate for the design of electro‐controlled devices. Studies of optical switching, contrast, viscosity, and behavior toward an electrical stimulus demonstrate the high potential of these hybrid materials in the fields of photonic or optoelectronic.     

Universal Behavior and Electric‐Field‐Induced Structural Transition in Rare‐Earth‐Substituted BiFeO3

The discovery of a universal behavior in rare‐earth (RE)‐substituted perovskite BiFeO₃ is reported. The structural transition from the ferroelectric rhombohedral phase to an orthorhombic phase exhibiting a double‐polarization hysteresis loop and substantially enhanced electromechanical properties is found to occur independent of the RE dopant species. The structural transition can be universally achieved by controlling the average ionic radius of the A‐site cation. Using calculations based on first principles, the energy landscape of BiFeO₃ is explored, and it is proposed that the origin of the double hysteresis loop and the concomitant enhancement in the piezoelectric coefficient is an electric‐field‐induced transformation from a paraelectric orthorhombic phase to the polar rhombohedral phase.     

Ultrahigh Tunability of Room Temperature Electronic Transport and Ferromagnetism in Dilute Magnetic Semiconductor and PMN‐PT Single‐Crystal‐Based Field Effect Transistors via Electric Charge Mediation

Multiferroic heterostructures composed of complex oxide thin films and ferroelectric single crystals have aroused considerable interest due to the electrically switchable strain and charge elements of oxide films by the polarization reversal of ferroelectrics. Previous studies have demonstrated that the electric‐field‐control of physical properties of such heterostructures is exclusively due to the ferroelectric domain switching‐induced lattice strain effects. Here, the first successful integration of the hexagonal ZnO:Mn dilute magnetic semiconductor thin films with high performance (111)‐oriented perovskite Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ (PMN‐PT) single crystals is reported, and unprecedented charge‐mediated electric‐field control of both electronic transport and ferromagnetism at room temperature for PMN‐PT single crystal‐based oxide heterostructures is realized. A significant carrier concentration‐tunability of resistance and magnetization by ≈400% and ≈257% is achieved at room temperature. The electric‐field controlled bistable resistance and ferromagnetism switching at room temperature via interfacial electric charge presents a potential strategy for designing prototype devices for information storage. The results also disclose that the relative importance of the strain effect and interfacial charge effect in oxide film/ferroelectric crystal heterostructures can be tuned by appropriately adjusting the charge carrier density of oxide films.     

Electric‐Field‐Controlled Alignment of Rod‐Shaped Fluorescent Nanocrystals in Smectic Liquid Crystal Defect Arrays

Periodic micro‐arrays of straight linear defects containing nanoparticles can be created over large surface areas at the transition from the nematic to smectic‐A phase in a nanoparticle–liquid crystal (LC) composite material confined under the effect of conflicting anchoring conditions (unidirectional planar vs normal) and electric fields. Anisomeric dichroic dye molecules and rod‐shaped fluorescent semiconductor nanocrystals (dot‐in‐rods) with large permanent electric dipole and high linearly polarized photoluminescence quantum yield align parallel to the local LC molecular director and follow its reorientation under application of the electric field. In the nano‐sized core regions of linear defects, where the director is undefined, anisotropic particles align parallel to the defect whereas spherical quantum dots do not show any particular interaction with the defect. Under application of an electric field, ferroelectric semiconductor nanoparticles in the core region align along the field, perpendicular to the defect direction, whereas dichroic dyes remain parallel to the defect. This study provides useful insights into the complex interaction of anisotropic nanoparticles and anisotropic soft materials such as LCs in the presence of external fields, which may help the development of field‐responsive nanoparticle‐based functional materials.     

Unprecedented Dual Alignment Mode and Freedericksz Transition in Planar Nematic Liquid Crystal Cells Doped with Gold Nanoclusters

We demonstrate that alkylthiol‐capped gold nanoclusters doped into nematic liquid crystals (N‐LCs) with positive dielectric anisotropy give rise to an unprecedented dual alignment mode and electro‐optical response, which has a potential impact on current liquid crystal (LC) display technologies and N‐LC optical‐biosensor design. By fine‐tuning experimental conditions (temperature, electric field, and alignment), N‐LCs doped with gold nanoclusters can be aligned and electrically reoriented either like N‐LCs with a positive dielectric anisotropy in a planar cell or, alternatively, as N‐LCs with a negative dielectric anisotropy in a homeotropic cell, both at lower threshold voltages than the pure N‐LC.     

Inside Front Cover: Unprecedented Dual Alignment Mode and Freedericksz Transition in Planar Nematic Liquid Crystal Cells Doped with Gold Nanoclusters (Adv. Funct. Mater. 2/2008)

On p. 212, Torsten Hegmann and co‐workers describe nematic liquid crystals (N‐LCs) confined in planar liquid crystal cells after doping with small quantities of gold nanoclusters. These give rise to a dual alignment mode and electro‐optic response (Freedericksz transition). By fine‐tuning of experimental conditions, N‐LCs doped with gold nanoclusters can be electrically reoriented and aligned either like N‐LCs with a positive dielectric anisotropy (used in twisted nematic displays) in a planar cell or alternatively as N‐LCs with a negative dielectric anisotropy (used in large LCD TVs based on the vertical alignment mode). We demonstrate that alkylthiol‐capped gold nanoclusters doped into nematic liquid crystals (N‐LCs) with positive dielectric anisotropy give rise to an unprecedented dual alignment mode and electro‐optical response, which has a potential impact on current liquid crystal (LC) display technologies and N‐LC optical‐biosensor design. By fine‐tuning experimental conditions (temperature, electric field, and alignment), N‐LCs doped with gold nanoclusters can be aligned and electrically reoriented either like N‐LCs with a positive dielectric anisotropy in a planar cell or, alternatively, as N‐LCs with a negative dielectric anisotropy in a homeotropic cell, both at lower threshold voltages than the pure N‐LC.     

Criticality: Concept to Enhance the Piezoelectric and Electrocaloric Properties of Ferroelectrics

Compositional engineering with a focus on structural phase transitions has been considered as the most important approach for enhancement of the functional properties of ferroelectric materials due to the critical fluctuation of physical properties. Of special interest are electric‐field‐induced phase transitions, which can terminate in a liquid–vapor‐type critical point with a strong enhancement of functional properties. Whereas the critical point in liquid–vapor space considers changes in temperature and pressure, the critical point in this study is placed in electric field–temperature diagrams. In single crystals, temperature and electric field of a critical point are sharply defined and therefore not appealing for practical applications. However, in ceramics, it is demonstrated that the orientational dependence of the critical point leads to a broadened temperature and electric field range. The presence of a diffuse critical point in ceramics provides a conceptually novel approach for the enhancement of functional properties, such as piezoelectric and electrocaloric (EC) responses, as validated here on the example of the 0.75Bi_1/2Na_1/2TiO₃‐0.25SrTiO₃ lead‐free relaxor ferroelectric ceramics. The realization of a broad criticality range will further facilitate the development of the piezoelectric and EC materials and provide an alternative concept to manipulate the functional properties by application of an electric field.     

Synthesis of Predesigned Ferroelectric Liquid Crystals and Their Applications in Field‐Sequential Color Displays

A series of low transition temperature and fast response chiral smectic C (SmC*) liquid crystals is designed and synthesized. The phase transition behaviors and electrooptical properties of the synthesized compounds are investigated and compared with reported values. The ferroelectric phase of the liquid crystals is characterized by means of differential scanning calorimetry, polarizing optical microscopy, wide‐angle X‐ray scattering (WAXS), and electrooptical measurements. The wide SmC* phase is achieved via the induction of achiral trisiloxane and a chiral methyl‐lateral substituent onto the terminuses of the molecules. The optimized packing arrangement model is studied based on the exceptionally high apparent tilt angles (≈41°) and smectic layer spacing observed using WAXS. A fast response time of 0.3 ms in an electric field of 10 V µm^?1 provides an opportunity to use the synthesized materials for field‐sequential color liquid crystal displays (FSCLCDs). An FSCLCD sample cell is fabricated using the synthesized ferroelectric liquid crystals via a red (R), green (G), and blue (B) backlight. A color‐frame frequency of more than 500 Hz (i.e., a frame frequency more than 166 Hz) is achieved. As a single material liquid crystal display cell, the synthesized ferroelectric liquid crystals show great performances at room temperature.     

Nematic Anisotropic Liquid‐Crystal Gels—Self‐Assembled Nanocomposites with High Electromechanical Response

The uniqueness of liquid crystals (LCs) lies in the large anisotropies of their properties, which can be utilized to generate high electromechanical responses. In a properly oriented LC polymer system, an external electric field can induce reorientation of the mesogenic units possessing a dielectric anisotropy, which, when coupled with the shape anisotropy of the mesogenic units, can in turn produce large mechanical strain. Anisotropic LC gels, which can be obtained by in‐situ photopolymerization of the reactive LC molecules in the presence of non‐reactive LC molecules in an oriented state, are an example of such liquid‐crystal polymer systems. It is shown here that a homeotropically aligned LC gel in its nematic phase exhibits high electrically induced strain (> 2 %) with an elastic modulus of 100 MPa and a high electromechanical conversion efficiency (75 %) under an electric field of 25 MV/m. These anisotropic LC polymeric materials could provide a technologically compatible system for such applications as artificial muscles and as microelectromechanical devices.     

掺杂铁电纳米粉的液晶的电光特性

铁电纳米粒子悬浮在向列相液晶母体中，增强介电各向异性，而且对施加的电场信号敏感。本文也展示了纳米粒子对所述复合材料可实现的总的相变的作用。这种方法也许可应用于设计新型显示材料。     

Symmetry Modulation and Enhanced Multiferroic Characteristics in Bi1‐xNdxFeO3 Ceramics

BiFeO₃ is recognized as the most important room temperature single phase multiferroic material. However, the weak magnetoelectric (ME) coupling remains as a key issue, which obstructs its applications. Since the magnetoelectric coupling in BiFeO₃ is essentially hindered by the cycloidal spin structure, here efforts to improve the magnetoelectric coupling by destroying the cycloidal state and switching to the weak ferromagnetic state through symmetry modulation are reported. The structure is tuned from polar R3c to polar Pna2₁, and finally to nonpolar Pbnm by forming Bi_1‐xNd_xFeO₃ solid solutions, where two morphotropic phase boundaries (MPBs) are detected. Greatly enhanced ferroelectric polarization is obtained together with the desired weak ferromagnetic characteristics in Bi_1‐xNd_xFeO₃ ceramics at the compositions near MPBs. The change of magnetic state from antiferromagnetic (cycloidal state) to ferromagnetic (canted antiferromagnetic) is confirmed by the observation of magnetic domains using magnetic force microscopy. More interestingly, combining experiments and first‐principles‐based simulations, an electric field‐induced structural and magnetic transition from Pna2₁ back to R3c is demonstrated, providing a great opportunity for electric field‐controlled magnetism, and this transition is shown to be reversible with additional thermal treatment.