蓝相液晶晶格结构调控及显示/防伪器件研究

蓝相液晶是存在于手性向列相与各向同性相之间的液晶相，具有自组装立方晶格三维光子晶体结构，同时具有电场快速响应和光学各向同性等特性，这使得蓝相液晶在光电器件、液晶显示、防伪以及传感等领域受到越来越多的关注。无取向、均匀锚定等条件下获得的蓝相液晶通常呈现多晶或单畴结构，存在晶格结构间缺陷和错位，这极大的影响了蓝相液晶的反射率和光电调制特性。蓝相单晶，具有无缺陷的晶格结构，可以大幅度提高蓝相液晶的光电特性。然而，目前的制备方法存在时间长、耗费高等问题。因此，亟需探索简便、快速地制备蓝相液晶单晶的方法。此外，手性浓度是影响蓝相液晶晶格结构、晶格取向及相变过程的重要因素，现有的研究仍待完善。最后，在器件方面，进一步提高蓝相液晶的Bragg反射特性、制备新型蓝相液晶光电器件（如反射式显示器、防伪器件等），是促进蓝相液晶走向实际应用的重要手段。

本论文通过全息光刻技术制备亚微米量级图案化基底，制备了大尺寸（厘米量级）的蓝相液晶单晶。研究了手性浓度和液晶盒厚度对蓝相液晶相变过程、晶格取向和晶格系数的影响。基于双层双手性蓝相液晶的叠加，提高了蓝相液晶的反射率，制备了超高反射率蓝相液晶显示器。本论文还通过全息光刻技术，设计制备了蓝相液晶仿生微纳结构复合防伪器件。主要研究内容包括：

（1）基于全息光刻技术的耗时短、耗能低的大尺寸（厘米级）蓝相液晶单晶的制备及特性研究。通过全息光刻技术，制备了亚微米量级图案化基底，实现了蓝相液晶单晶的诱导和生长。建立了蓝相液晶晶格取向的仿真模型。研究了三种相变过程（各向同性相-蓝相I、蓝相II-蓝相I、及各向同性相-蓝相II）中出现的红、绿、蓝三个波段的蓝相液晶单晶。分析了蓝相液晶晶格结构之间的晶界自愈合现象，验证了蓝相液晶单晶的存在。制备得到的蓝相液晶单晶具有无缺陷的晶格结构、高反射率、窄带宽等特点。

（2）手性浓度和液晶盒厚度的变化对蓝相液晶的影响研究。研究了手性浓度、液晶盒厚度对蓝相液晶晶格结构和相变的影响，研究了各向同性相-蓝相I和各向同性-蓝相II的中间态的晶格取向，研究了液晶盒厚度对蓝相液晶晶格取向的影响。通过调节手性浓度和液晶盒厚度，制备得到了均匀的液晶蓝相II [011]晶格取向。

（3）基于蓝相液晶薄膜的电场可调控的超高反射率显示器的制备和特性研究。通过双层双手性蓝相液晶聚合物模板的叠加，制备了超高反射率蓝相液晶显示器，使得蓝相液晶的反射率达到89%（红）、82%（绿）、68%（蓝）。研究了蓝相液晶三原色的电场可调控特性，通过电场强度的改变，控制了蓝相液晶的反射率。电场强度为1V/μm时，蓝相液晶的最高反射率可达： 94%（红）、86%（绿）、和72%（蓝）。随后，反射率随电场增强而降低，为蓝相液晶提供了灰阶显示。

（4）基于全息光刻和蓝相液晶薄膜的仿生微纳结构复合防伪器件研究。制备了一种具有超高热稳定性（-50˚C至260˚C）和优异Bragg反射光学特性（反射率44%）的固态蓝相液晶薄膜。同时，根据孔雀尾羽的仿生微纳结构，设计了可以在三维空间实现多角度复合图像传输的光子晶体结构。通过全息光刻技术，实现了双层微纳结构蓝相液晶复合器件的制备。与手机扫描二维码的应用场景相结合，扩展了复合防伪器件的应用场景，通过多角度扫描，实现了信息保护或进入许可两种结果。

As a kind of self-assembly three dimensional photonic crystals, blue phases exist between chiral nematic phases and isotropic phases, which have good application in sensors and structural color displays due to its properties of saturated colors in visible range, free of polarizers and fast response of electric field. However, blue phase liquid crystals exhibit polycrystalline structures which affect the reflectance and electro-optical properties. Through electric field and anchoring condition, blue phase liquid crystals have fixed orientation and exists good reflectivity. However, due to the chirality of blue phase liquid, the reflectance is less than 50%. At the meantime, chirality has important influence on the lattice structures on blue phases. However, optical properties of blue phases caused by small changes of chirality are missed, yet. Besides, through temperature and patterned substrates, single crystalline blue phases have been achieved, which largely improves the properties of blue phases. However, the fabrication methods are time-cost and small-scale. Therefore, controlling the orientation of blue phase lattice structures, improving the Bragg reflectivity are still challenging.

Based on the researches, blue phase liquid crystals are fabricated to achieve large scale single crystalline blue phases through holographic lithography. The properties of orientation and lattice structures of blue phases caused by chirality and cell thickness are proposed. Electrically-switchable hyper-reflective blue phase displays are fabricated. Besides, based on holographic lithography and blue phase liquid crystal films, bio-inspired multiplexing anti-counterfeiting is proposed. In this paper, the main points are shown below:

(1) based on patterned nanostructured substrates, large scale single crystalline blue phases was fabricated through holographic nanolithography for the first time, each size of single crystalline blue phases is over 1cm². A new phenomenon – diffusion of crystal boundary– was observed as the scale of single crystals grow for the first time, which gives a further demonstration of the existence of single-crystal blue phase. At the meantime, single crystalline blue phases were fabricated in three kinds of phase transitions, which are isotropic phase to blue phase I, blue phase II to blue phase I, and isotropic phase to blue phase II. The fabricated blue phases were defects-free and hyper-reflective.

(2) Based on the simulation of diffraction of lattice structures, study of the influence of temperature, chirality and cell thickness were researched. For the first time, uniform lattice orientation of blue phase II [011] was aligned through parallel anchoring; and found a fresh phase transition of isotropic phase to coexisted blue phase I and II. Through parallel anchoring, three kinds of lattice orientation, which are blue phase I [011], blue phase II [011] and blue phase II [001], can be aligned by different cell thickness.

(3) Besides, electrically tunable hyper-reflective blue phase liquid crystal film based on bilayer opposite-chirality structures was fabricated, which had hyper reflectance of 89%, 82% and 68% for red, green and blue, respectively. And it would reach the highest reflectance of 94%, 86% and 72%, respectively, under electric field of 1V/μm.

(4) And at the meantime, based on the washing out-refilling blue phase liquid crystal film and liquid crystal monomer, a high thermo-stable and reflectance solid blue phase liquid crystal film was proposed, offers potential application of blue phase liquid crystals. A new kind of bio-inspired multiplexing anti-counterfeiting film based on solid blue phase liquid crystal film and holographic lithography was fabricated, which transmitted multi-images in free space via multi-angles. And it can be combined with the situation of scanning quick response code with smartphones leading to multiple encryptions with information protection or access permission.

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