Fabrication of high dimensional structured nanoceramic by the liquid phase deposition method

利用金属-氟络合物在水溶液中的平衡反应，研究了液相沉积法制备金属氧化物薄膜的方法。各种金属氧化物可以在具有多种结构有序性的衬底上以良好的阶跃覆盖率沉积。采用液相浸渗法在模板衬底上制备了高维结构的金属氧化物薄膜。该方法在制备过程中具有低能耗、低成本的溶液反应、高粘附性和阶跃覆盖性能等优点。我们开发了一种直接合成具有高度有序周期结构的二维金属氧化物薄膜的新技术。采用LPI法在室温下直接在衬底上沉积了具有高度纳米有序结构的二氧化钛薄膜。通过在用Deep-RIE方法设计的硅片上填充空洞，制备了直径在100~1000 nm之间的几种金属氧化物棒的二维阵列。基于LPI方法，发展了一种新的软溶液直接合成大面积有序周期结构聚苯乙烯胶体晶体氧化物的方法。金属氧化物薄膜被直接沉积到纳米空间中，从而使纳米空间完全被金属氧化物渗透。在这种体系中，金属氧化物的结晶度高于在平面衬底表面制备的常规薄膜。结果表明，在液相沉积反应中，有限的反应区域阻碍了溶解物种的扩散和晶体生长过程中的高结晶度。LPI工艺为具有高度有序结构的金属氧化物薄膜提供了一条直接的制备路线，使得能够对光子晶体的光学性质进行纳米级的修饰。

Liquid Phase Deposition (LPD) method has been studied for the fabrication of metal oxide thin films using equilibrium reaction of metal-fluoro complex in aqueous solution systems. Various kinds of metal oxide can be deposited with a good step coverage on substrates having various and high structure ordering. The high dimensional structured metal oxide thin films were fabricated among the template substrate by the Liquid Phase Infiltration (LPI) method. This method has a various advantages in fabrication process, such as low energy, low cost solution reaction, high adhesive and step coverage performance, etc.We developed a novel technique for the direct synthesis of two-dimensional metal oxide films with highly ordered periodic structure. TiO2 films with highly nano-ordered architectures were directly deposited on substrates at room temperature by LPI method. 2D arrays of several kinds of metal oxide rods with diameters ranging from ca. 100 to 1000 nm are fabricated by filling the holes in a Si wafer designed by Deep-RIE method. A novel soft solution process for the direct synthesis of large-area well-crystallized oxides with 3D ordered periodic structure of polystyrene colloidal crystal has been developed based on the LPI method. Metal oxide thin films were deposited directly into the nanospace, and thus the nanospace was completely infiltrated with metal oxide. In such systems, the crystallinity of the metal oxide is higher than conventional thin films prepared on the surface of the planer substrate. It is suggested that the limited reaction region caused the hindrance of diffusion of the dissolving species and high crystallinity during the crystal growth in the Liquid Phase Deposition reaction. The LPI process provides a direct fabrication route for metal oxide films with highly ordered structures, enabling nanoscale modification of optical properties of photonic crystals.