一种新型液晶垂直取向膜

采用离子沉积法在玻璃基板表面制备了十四烷基磺酸盐自组装膜,用带有该自组装膜的基板制成的液晶器件呈现出垂直取向效果。通过自组装反应过程分析,认为自组装膜表面的纵向沟纹引起了液晶的垂直排列。实验发现,当自组装膜烷烃碳链长度大于11个C原子就可获得垂直取向。这种取向膜制作过程简单、热稳定性好,非常有望应用于多畴垂直取向模式的液晶显示器。     

表面自组装反应制备液晶光控取向膜

通过聚乙烯醇薄膜表面致密的羟基基团与肉桂酰氯间的选择性酯化反应,将光敏基团连接到聚乙烯醇薄膜表面,制备出一种新型的光敏自组装单层膜.用线性偏振紫外光辐照该薄膜,与光矢量方向匹配的肉桂酸基团发生光化学反应,反应产物沿辐照光的偏振方向分布,形成表面张力各向异性的薄膜.将该薄膜作为向列相液晶的取向膜制成平行液晶器件,在偏光显微镜下观察,发现获得了均一、稳定的取向效果.这种自组装光控取向膜的制作过程简单,且具有良好的热稳定性.     

光敏自组装单层膜用于液晶光控取向的研究

用丁二酸酐和7-羟基香豆素合成了含有脂肪族羧酸基团的光敏化合物，利用脱水反应使它在玻璃(或石英)基板表面形成自组装单层膜。用偏振紫外光照射光敏性自组装膜，与光矢量方向匹配的香豆素基团发生[2 2]周环反应，反应产物沿辐照光的偏振方向分布，形成表面张力各向异性的薄膜。用它作为向列相液晶取向膜制成平行液晶器件，在偏光显微镜下观察，发现取得了均一、稳定的取向效果。并且该取向膜有良好的热稳定性。     

一种共价键结构的高稳定性自组装光控取向膜

通过两次光照法制备了一种基于共价键结构的自组装光控取向膜。首先采用重氮树脂与聚(4-丙烯酰氧基肉桂酸(4′-磺酸钠)苯酚酯)在水溶液状态下通过静电离子沉积法制备了layer-by-layer型的自组装多层膜,制备过程的紫外-可见光谱表明薄膜为逐层、均匀沉积。第一次光照将膜层间的重氮磺酸盐离子键转化为共价键结构,然后采用线性偏振紫外光进行第二次光照,获得具有各向异性的光控取向膜。紫外-可见光谱法证实了薄膜辐照过程中的光化学反应方式。这种液晶光控取向膜可以水平均匀取向向列相液晶,而且具有良好的热稳定性,可达到150℃。     

向列相液晶在自组装膜上取向的研究

通过在具有微米级沟槽(一个沟槽周期5μm)的玻璃基底上进行平面镀金,制备了具有相同沟槽周期的Au膜;并在Au膜上制备Cu2 修饰的巯基十一酸自组装敏感膜。向列相液晶5CB在Au膜基底上呈平行于Au膜沟槽的沿面排列;5CB在自组装敏感膜表面上的取向排列方式为垂直排列。通过检测甲基膦酸二甲酯时液晶织构的变化,表明5CB的取向排列方式由垂直排列转变为倾斜排列,并阐明了液晶型化学传感器的作用机理。首次证实以微米级沟槽状Au膜为基底制作的液晶型化学传感器可以用于检测目标化合物。     

Au纳米颗粒对向列相液晶取向性能的影响

液晶分子的初始排列在液晶显示器中起着关键的作用。纳米粒子掺杂到液晶体系可扰乱液晶分子的排列,从而改变液晶的自组装特性,进而影响液晶的各项性能。将制备的Au八面体纳米颗粒掺杂到向列相液晶4-氰基-4′-正戊基联苯(5CB)中,灌入液晶盒后,通过使用偏光显微镜对液晶盒的观察发现,掺杂的八面体Au纳米颗粒诱导5CB液晶分子发生了垂直取向,而球形Au纳米颗粒不能诱导液晶分子垂直取向。这归因于八面体Au纳米颗粒的表面能比较小,液晶分子间的作用力比较大,使液晶分子易于垂直取向。随着O-Au NPs的浓度增大,液晶分子的取向效果先变好又逐渐变差。这是因为O-Au NPs的浓度越高,可诱导越多的液晶分子垂直取向排列,但随着纳米粒子浓度的增加,纳米粒子团聚,减少了与液晶分子的作用,使取向效果变差。动态过程实验显示,0.1%的八面体金纳米颗粒可诱导向列相液晶5CB在2 min内快速完成垂直取向,表明O-Au NPs具有优异的诱导5CB取向的动态效果。     

聚酰亚胺液晶垂直取向膜的制备与性质

虽然传统的平行取向技术已广泛应用于液晶显示器的生产,但其存在窄视角、低对比度和慢响应时间等问题,因此液晶分子的垂直取向技术在国外已经被广泛研究。在实验中,一种含有液晶结构侧链的聚酰亚胺通过均苯四羧酸二酐(PMDA),4,4′-二胺基二苯甲烷(MDA)和4-己氧基联苯酚-3′,5′-二胺基苯甲酸酯(C6BBDA,实验室自制)共聚被制备,并且被用作液晶取向膜,研究其取向性能。试验发现,该种聚酰亚胺作为取向膜可以诱导液晶分子垂直取向,即使在摩擦之后依然可以获得大于89°的预倾角;使用正交偏光显微镜观察所制得液晶盒中的液晶取向效果,发现垂直取向均匀良好;为了测试该垂直取向的热稳定性,将制备的液晶盒在120℃下烘烤12h后,偏光显微镜下观察发现垂直取向仍然良好均匀,表明该取向膜具有良好的热稳定性。     

一种新型光敏小分子用于光控取向的研究

通过在3,5-二羟基苯甲醇分子中的双酚基基团上引入双肉桂酰酯光敏基团的酯化反应,合成了一类新型的分子顶部为羟基极性基团,整个分子构型类似于树枝状的光敏小分子化合物。将此种光敏材料配成一定浓度的溶液,旋涂在玻璃基板上成膜,经过线性偏振紫外光辐照后发生交联反应,制备成光控取向膜。以此种取向膜制成向列相液晶的平行液晶器件,在偏光显微镜下观察,发现取得了均一、稳定的取向效果,并且该取向膜具有良好的热稳定性能。     

侧链含稠环的新型聚酰亚胺液晶垂直取向剂的制备及表征

以3,5-二硝基苯甲酰氯、雌二醇及溴代正辛烷为原料合成了含有稠环结构的新型功能性二胺(H8-c)。用1,2,3,4-环丁烷四甲酸二酐(CBDA)、对苯二胺(PDA)及H8-c共聚制备了一种聚酰亚胺(PI)液晶垂直取向剂。该PI膜作为取向层制得的液晶盒,在120℃下烘烤12h仍可垂直取向,拥有良好的垂直取向热稳定性。热重分析(TGA)测试表明其具有良好的热稳定性,在氮气中,这种PI的5%热失重温度(T5)和10%热失重温度(T10)分别高达400℃和480℃。紫外可见光谱(UV-vis)显示此PI膜在400nm以上具有高的透过率,可达95%以上。     

极性自组装单层膜取向铁电液晶器件

采用极性自组装单层膜和摩擦的方法制备了非对称的液晶盒.在铁电液晶相变的过程中不施加电场,得到了排列均一的铁电液晶器件.实验表明:极性自组装单层膜极性越大器件的对比度越高.经过分析得出该器件液晶分子取向机理为:基板附近的铁电液晶通过偶极和极性自组装膜的作用,使得靠近自组装膜表面处的偶极和靠近摩擦表面的偶极的指向相同,通过分子的相互作用使得体内分子排列方向一致.     

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.     

基于光敏自组装多层膜的液晶光控取向膜

采用layer-by-layer(LBL)的方法，将基板依次在具有光敏双键的季铵盐水溶液和聚乙烯基苯磺酸钠水溶液中浸泡，石英基板表面形成了自组装多层沉积膜。经线性偏振紫外光辐照后，LBL多层膜表现出明显的紫外吸收各向异性。将两片带有各向异性薄膜的基板做成平行液晶器件。在正交的偏光显微镜下观察，发现取得均一、稳定的取向效果。该种光控取向膜有望用作LCoS微显示的取向层。     

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.     

Thermal imprint lithography using sub-micron sized nickel template coated with thin SiO2 layer

Nickel template is very suitable for thermal imprinting process since it has high mechanical durability and can easily be duplicated using electroforming technique. However nickel has a poor anti-sticking property; in addition, proper and stable releasing layer on nickel surface is not yet available.In this study, thin layer of SiO₂ film was deposited on nickel surface and silane based hydrophobic self-assembled monolayer (SAM) was formed on SiO₂ film, coated on nickel. Since the silane based SAM layer can be stably formed on SiO₂ layer coated nickel template, it can be used anti-sticking layer for thermal imprint process using thermoplastic polymer resin or thermally curable prepolymer resin.     

Large enhancement of hole injection in pentacene by modification of gold with conjugated self-assembled monolayers

Planar diodes with gold electrodes and a pentacene semiconductor layer were made and electrically characterized. The gold electrodes were modified with self-assembled monolayers of biphenylthiol and biphenylthiol substituted with a terminal fluorine atom (fluorobiphenylthiol). Atomic force microscopy of the pentacene layer reveals large morphological similarities when the film is grown on gold modified with either of the two kinds of self-assembled monolayer. This is at variance with the significant increase of the current observed when the gold electrodes are treated with fluorobiphelylthiol, with a bulk mobility rising up to 1 cm²/V s, while the treatment with biphelylthiol leads to a substantial decrease of the current. These results are interpreted in terms of adjustment of the injection barrier height as a result of the interface dipole induced by the self-assembled monolayer.     

Stable and robust low-voltage pentacene transistor based on a hybrid dielectric

We report here that an ultra-thin oxide layer formed in the gate metal by plasma oxidation can serve the same role as self-assembled monolayer (SAM) dielectric, yielding the device performance similar to that for SAM-based organic thin film transistors. In addition, this simple plasma oxidation, unlike the case of SAM dielectrics, allows a smooth coating of the oxide dielectric with a thin (∼ 20 nm) polymer dielectric of poly (vinyl phenol) (PVPh). This organic transistor with the bilayer dielectric is robust. It has a subthreshold swing of 110 mV per decade, which is the best subthreshold voltage reported for an organic transistor.     

钝化剂自组装单层膜在铜铜键合工艺中的应用

解决铜铜键合工艺中的铜氧化问题对于三维集成技术具有重要意义。选用1-己硫醇做临时钝化剂,通过自组装形式形成单层膜附着于铜表面,以防止铜在存放时与空气接触而发生氧化,键合前再使用乙醇等有机溶剂去除该单层膜。为了评估1-己硫醇的钝化效果,采用接触角作为主要指标对实验结果进行评价。研究表明,样片表面经过1-己硫醇处理后,接触角极大增加,并在空气中长时间保持稳定,说明1-己硫醇具有良好的钝化效果,采用此方法得到了高质量的铜铜热压键合样片。