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.     

Photogeneration of High Pretilt Angles of Nematic Liquid Crystals by Non‐Polarized Light Irradiation of Azobenzene‐Containing Polymer Films

A vertical‐alignment (VA) cell of nematic liquid crystals (LCs) was prepared using photoirradiated thin films of a poly(methacrylate) with mesogenic moieties of 4‐trifluoromethoxyazobenzene as the side chains. Optical anisotropy was generated by oblique irradiation of the azobenzene‐containing polymer films with non‐polarized UV light, followed by annealing treatment to enhance the photodichroism, which displayed thermal stability. The combination of oblique exposure to non‐polarized UV light and subsequent annealing treatment brought about high pretilt angles of nematic LCs so that a photoaligned VA LC cell was fabricated. The photopatterned LC cell exhibited electro‐optical properties with excellent optical quality when a voltage was applied even after heating at 100 °C for several hours.     

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.     

Large Area Self‐Assembly of Nematic Liquid‐Crystal‐Functionalized Gold Nanorods

Fascinating nematic‐ and smectic‐like self‐assembled arrays are observed for gold nanorods partially capped with either laterally or terminally attached nematic liquid crystals upon slow evaporation of an organic solvent on TEM grids. These arrays can be manipulated and reoriented by applying an external magnetic field from quasi‐planar to vertical similar to a Fréedericksz transition of common organic nematic liquid crystals. Birefringence and thin film textures of these self‐assembled gold nanorod arrays observed by polarized optical microscopy are strongly reminiscent of common organic nematic liquid crystal textures between crossed polarizers and, additionally, support the formation of ordered liquid crystal‐like anisotropic superstructures. The ordering within these arrays is also confirmed in bulk samples using small angle X‐ray scattering (SAXS).     

Fabrication and Characterization of Polymer/Liquid Crystal Composite Diffractive Optics by Multiphoton Methods

Direct‐write multiphoton photolithography is used to prepare electrically switchable diffraction gratings having spacings as small as 4 μm. Surface‐relief gratings are written into poly(methyl methacrylate) films using a sample‐scanning confocal microscope and are characterized by using contact‐mode atomic force microscopy. The resulting polymeric channels are filled with nematic liquid crystals (LCs) and sandwiched between indium tin oxide‐coated coverslips to obtain functional devices. These devices exhibit diffraction efficiencies approaching 30 %. Microscopic LC organization and field‐induced reorientation dynamics within these devices are characterized by static and dynamic polarization‐dependent multiphoton excited fluorescence microscopy. LCs are found to align predominantly along the channel axis, but exhibit some disorder near the channel walls, resulting from nanometer‐scale polymer surface roughness. LC reorientation in response to an electric field is rapid (<1 ms) and uniform, whereas field‐free LC relaxation is relatively slow (>20 ms). Both reorientation and relaxation are influenced by orientationally anchored LCs near the channel walls.     

Liquid-crystal cells with special electrodes for the generation of uniform colors by optical birefringence

A new electrode-preparation technique for liquid-crystal cells has been developed. The basic process is an oblique deposition of thin films onto grooved glass surfaces. Such electrodes induce a small unidirectional pretilt in thin layers of homeotropically aligned nematic liquid crystals with negative dielectric anisotropy. This pretilt is important for the uniformity of colors generated by the electrically tunable birefringence in nematic liquid crystals.     

Plasma Modification of Fluoropolymers for Aligning Liquid Crystals

In this paper we describe methods to control liquid crystal (LC) alignment using plasma discharge on ferroelectric fluoropolymers. Two different plasma modification techniques were investigated: corona discharge and RF plasma in Ar gas. Corona discharge is a proven technique known to reorient the dipoles in poly (vinylidene fluoride) and its copolymers resulting in a strong remnant polarization. The polarization was patterned resulting in preferential LC alignment in selected regions. RF plasma in Ar gas defluorinates the polymer surface leading to planar alignment of positive dielectric anisotropy LCs. The defluorination of the alignment layer also causes low voltage switching of the LC.     

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.     

Alignment of liquid crystals on a topographically nano-patterned polymer surface prepared by a soft-imprint technique

In this study, we have fabricated polyacrylate substrates having a nano-patterned surface topography using a soft-imprint technique. The planar alignment of liquid crystals (LCs) along the direction of nanogrooves has been generated. Twisting behavior of nematic LCs has been also observed with a perpendicularly assembled LC cell and the cell parameters can be estimated by using the Soutar and Lu method. By comparing the anchoring energies obtained, accordingly, it has been demonstrated that the polymer nanogroove pattern has a comparable influence on LC alignment to the conventional rubbing process. It has been also shown that the artificial topography of the line grooves on the conventionally rubbed surface has a significant influence on the anchoring stability of the LC molecules.     

Highly Oriented Nanofibrils of Regioregular Poly(3‐hexylthiophene) Formed via Block Copolymer Self‐Assembly in Liquid Crystals

A novel method making use of block copolymer self‐assembly in nematic liquid crystals (LCs) is described for preparing macroscopically oriented nanofibrils of π‐conjugated semiconducting polymers. Upon cooling, a diblock copolymer composed of regioregular poly(3‐hexylthiophene) (P3HT) and a liquid crystalline polymer (LCP) in a block‐selective LC solvent can self‐assemble into oriented nanofibrils exhibiting highly anisotropic absorption and polarized photoluminescence emission. An unusual feature of the nanofibrils is that P3HT chains are oriented along the fibrils' long axis. This general method makes it possible to use LCs as an anisotropic medium to grow oriented nanofibrils of many semiconducting polymers insoluble in LCs.     

液晶材料介电常数的毫米波频率特性研究

利用矩形波导管和向量分析仪,测量了几种液晶材料在26.5～40 GHz波段(Ka波)的介电常数.实验表明,1 kHz频率下呈现正、负介电各向异性的液晶材料,在该微波波段下都显示为正的介电各向异性.尽管这些材料的静介电常数各向异性相差很大,但是该微波波段对应的介电各向异性相差却很小,而且在26.5～38 GHz区间内几乎不随频率的增大而发生变化.     

Chiroptical Resolution and Thermal Switching of Chirality in Conjugated Polymer Luminescence via Selective Reflection using a Double‐Layered Cell of Chiral Nematic Liquid Crystal

An optically resolvable and thermally chiral‐switchable device for circularly polarized luminescence (CPL) is first constructed using a light‐emitting conjugated polymer film and a double‐layered chiral nematic liquid crystal (N*‐LC) cell. The double‐layered N*‐LC cell with opposite handedness at each layer is fabricated by adding each of two types of N*‐LCs into each of the cells, and the N*‐LCs consist of nematic LCs and chiral dopants with opposite chirality and different mole concentrations. The selective reflection band due to the N*‐LC is thermally shifted so that the band wavelength is close to the luminescence band of the racemic conjugated polymer, such as disubstituted polyacetylene (diPA), yielding CPL with opposite handedness and high dissymmetry factor values (|g_lum|) of 1.1–1.6 at low and high temperatures. The double‐layered N*‐LC cell bearing the temperature‐controlled selective reflection is useful for generating CPLs from racemic fluorescent materials and for allowing thermal chirality‐switching in CPLs, which present new possibilities for optoelectronic and photochemical applications.     

Photo‐ and Rubbing‐Alignable Brush Polyimides Bearing Three Different Chromophores

Three new photoreactive brush polyimides (PSPIs), each bearing a different type of chromophore (cinnamoyl (CA), 3‐(2‐furyl)acryloyl (FA), and methacryloyl (MA)) in their bristles (i.e., side groups), are successfully synthesized, and are found to produce good‐quality films with smooth surfaces through conventional spin‐casting and drying processes. These PSPI polymers are thermally stable up to 320 °C. This is the first quantitative investigation of the photoaligning and rubbing‐aligning processabilities of PSPI polymer films, and of the abilities of the resultant films to control the orientation and anchoring of liquid‐crystal (LC) molecules. The chromophores of both poly(1‐cinnamoyloxy‐2,4‐phenylene hexafluoroisopropylidenediphthalimide) (6F‐DAP‐CA) and poly(1‐3‐(2‐furyl)acryloyloxy‐2,4‐phenylene hexafluoroisopropylidenediphthalimide) (6F‐DAP‐FA) PSPIs are found to undergo photodimerization in thin films and, to a lesser extent, photoisomerization, resulting in insoluble, crosslinked films. The MA chromophores of 6F‐DAP‐MA PSPI are found to undergo photopolymerization in thin films, which might include photodimerization to a lesser extent, resulting in insoluble, crosslinked films. Thin films of the PSPI polymer chains are found to have excellent unidirectional orientation ability as a result of either photoexposure with linearly polarized UV light (LPUVL) or rubbing. Both the photoaligned and the rubbing‐aligned polymer chains in the PSPI films are demonstrated to effectively induce the alignment of nematic LCs along their orientation directors by anisotropic interactions between the preferentially oriented polymer chain segments and the LCs. The contribution to LC alignment of the microgrooves developed in the rubbed films is found to be very low. The anchoring energies of the LCs on the photoaligned film surfaces are comparable to those on the rubbing‐aligned film surfaces; the anchoring energies are found to be in the range 0.45–2.25 × 10^–5 J m^–2, and to depend on which film treatment process is used and which chromophore bristle is present. In summary, the new PSPIs reported in this paper are promising LC alignment‐layer candidates with rubbing‐free processing for the production of advanced LC‐display (LCD) devices, including LCD televisions with large display areas.     

Magnetic and Transparent Composites by Linking Liquid Crystals to Ferrite Nanoparticles through Covalent Networks

The fabrication of transparent, flexible, and optically homogeneous magnetic composites containing ferrite (Fe₃O₄) nanoparticles, liquid crystals (LCs), and siloxane backbones is reported. The transparent magnets are achieved by covalently bonding LCs to the siloxane backbones and then linking them to dopamine‐functionalized ferrite nanocrystals. They exhibit simultaneous high transparency and strong magnetic properties. A remarkable feature of these films is that the surface morphology of the LC‐attached ferrite films can be tuned by an external magnetic field, demonstrating a striped surface in the direction of the field. We show that the LC‐attached film can act as an alignment layer to orient LCs, enabling the development of LC alignment surfaces on the basis of these nanomagnet–LC polymer composites.     

自组装法制备新型液晶垂直取向膜

用硅烷偶联剂3-氨丙基-三乙氧基硅烷,通过自组装反应在石英基板表面制备了含有二苯乙炔基的自组装单层膜。用该自组装膜作为向列相液晶的取向层制成液晶器件,在偏光显微镜下观察,发现向列相液晶获得了均匀、稳定的垂直取向效果。热稳定性试验表明,用自组装方法制备的液晶垂直取向膜有良好的热稳定性,在250℃条件下取向仍可保持。     

外加电压频率对液晶介电各向异性的影响

液晶材料的介电各向异性通常与频率有关。为进一步研究频率对液晶材料介电常数的影响,首先,使用紫外可见分光光度计(METASH UV-9000S)和表面轮廓仪(Contor GK-T)分别测量液晶盒厚度以及聚酰亚胺(PI)取向层厚度,通过精密热台(LTS 350)控制实验温度20℃,使用精密LCR表(Agilent E4980A)测定4种不同液晶材料在100～2 000Hz的频率内的平行和垂直排列向列相液晶盒电容;然后,利用液晶盒电容模型计算出不同频率下液晶的平行和垂直介电常数,并绘制频率-介电各向异性曲线;最后,分析频率对液晶介各向异性的影响。实验结果表明:温度一定,正性液晶的介电各向异性随频率的升高而减小,然后逐渐趋于平缓,负性液晶的介电各向异性随频率变化基本保持不变。此项研究对进一步分析液晶材料的介电特性具有一定的指导意义。     

香蕉形液晶中非标准的电流体效应

本文重点介绍了香蕉形液晶中的电流体效应。由于具有独特的V形分子结构,香蕉形液晶的电输运参数与传统的棒状液晶非常不同,从而引发了非标准的电流体效应。通过改变外加电场频率、幅度、极性以及温度详细研究了这种新的流体动力学行为,为将来物理模型的建立提供了良好的实验基础。     

液晶微胶囊制备宽波反射凝胶

手征向列相(N*)液晶能够选择性反射入射光,但其反射波宽一般小于150nm。利用负介电各向异性的向列相液晶SLC10V513-200与手性化合物R1011、CB15配制出5种N*液晶,其反射波长能够覆盖整个可见光波段。使用异佛尔酮二异氰酸酯(IPDI)界面聚合法制备出平均粒径为8.0μm的5种N*液晶聚脲微胶囊之后,将相同质量的5种微胶囊混入OP-10与IPDI中制备出微胶囊的凝胶。对80.0μm厚微胶囊凝胶薄膜施加交流电场,使微胶囊中的液晶处于平面织构状态,紫外固化微胶囊中的液晶性单体,固定微胶囊中N*液晶的平面织构,从而制备出可以反射可见光波段的微胶囊凝胶薄膜。     

Towards Efficient Dispersion of Carbon Nanotubes in Thermotropic Liquid Crystals

Motivated by numerous recent reports indicating attractive properties of composite materials of carbon nanotubes (CNTs) and liquid crystals (LCs) and a lack of research aimed at optimizing such composites, the process of dispersing CNTs in thermotropic LCs is systematically studied. LC hosts can perform comparably or even better than the best known organic solvents for CNTs such as N‐methyl pyrrolidone (NMP), provided that the dispersion process and choice of LC material are optimized. The chemical structure of the molecules in the LC is very important; variations in core as well as in terminal alkyl chain influence the result. Several observations moreover indicate that the anisotropic nematic phase, aligning the nanotubes in the matrix, per se stabilizes the dispersion compared to a host that is isotropic and thus yields random tube orientation. The chemical and physical phenomena governing the preparation of the dispersion and its stability are identified, taking into account enthalpic, entropic, as well as kinetic factors. This allows a guideline on how to best design and prepare CNT–LC composites to be sketched, following which tailored development of new LCs may take the advanced functional material that CNT–LC composites comprise to the stage of commercial application.     

Preparation of poly (N-vinylcarbazole)-co-poly(2-(dimethylamino)ethyl methacrylate) based hydrogen bonded side-chain liquid crystal copolymer

In this study, new side chain liquid crystalline copolymers were prepared from N-vinyl carbazole (NVC) and 2-(Dimethylamino)ethyl methacrylate) (DMAEM) as a hydrogen bond acceptor copolymer and 8-(4-cyanobiphenyl-4′-oxy)octan-1-ol (LC8) by molecular self-assembly processes via hydrogen bond formation between nitrogen of (DMAEM) and hydroxyl group of the LC8. The formation of H bond was confirmed by using FTIR spectroscopy. The liquid crystalline behavior of the copolymers and homopolymer of the (DMAEM) was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. The dielectric relaxation properties of H-bonded Side Chain LC Copolymers (HB-LCP) doped 8-(4-cyanobiphenyl-4′-oxy)octan-1-ol (LC8) and pure LC8 liquid crystals have been investigated by the dielectric spectroscopy (DS) method. The dielectric behavior of the LCs shows a dielectric relaxation process. The relaxation frequency of the LCs was changed by the addition of HB-PLC. It is evaluated that the dielectric strength and relaxation properties of LC8 and LC8/HB-PLC LCs can be controlled by 1% HB-PLC dopant.