| 摘要: | 由於先進奈米製程技術在未來奈米元件發展中扮演著關鍵的角色，而近年，中空結構之金屬奈米材料無論是在光電、化學感測以及觸媒上皆發現有相當大的應用潛力。因此如何大量製備與分析其特性即成了研究的重點。 本實驗的研究即整合以聯胺為還原劑之無電鍍鎳薄膜技術與移除模板法的方式，成功地大量製備出純鎳金屬之空心奈米材料。為了合成出ㄧ維之鎳金屬奈米管，模板部分首度採用具有均勻表面、高長寬比及熱穩定性良好之氧化矽奈米線來做為模板。經過APTMS官能基、活化、以及聯胺為還原劑之無電鍍鎳等步驟後，均勻氧化矽奈米線/純鎳金屬之核-殼奈米線結構即可完成。最後利用氫氟酸水溶液溶除中心氧化矽奈米線模板後，首度成功的製備出大面積純鎳金屬空心奈米管。金屬奈米管之內徑約30-150 nm，長度可達數十微米尺寸。此外，中空奈米球之合成，可利用均ㄧ粒徑之聚苯乙烯微奈米圓球來作為模板，藉由以聯胺為還原劑之無電鍍鎳薄膜技術並移除內部球核後，成功的製備出大面積之純鎳金屬空心球結構材料。 對於上述製備出之鎳金屬空心奈米材料，其表面形貌、晶體結構以及化學組成等，本研究利用SEM、TEM、EDS、SAED與HRTEM做有系統的鑑定分析。由所得之研究結果顯示，對於以均ㄧ粒徑之膠體粒子和高長寬比之氧化矽奈米線來作為模板，結合APTMS和聯胺所改進之無電鍍技術，可預期將可用以製備出其它各式高純度金屬中空奈米材料。 The advanced nanoscale fabrication technology is expected to play a key role in the applications of future nanodevices. Recently, the metal nanomaterials with hollow interiors have already been found their potential application in advanced optoelectronics, chemical sensors, and catalysts. Therefore, many research efforts have been dedicated to the large-scale syntheses of hollow nanomaterials. In the present study, a new and facile route for the large-scale synthesis of high-purity hollow Ni metal nanomaterials has been developed by using the hydrazine-modified electroless Ni deposition processes with sacrificial templates. For the synthesis of the one-dimensional (1D) Ni metal nanotubes, amorphous silicon oxide (a-SiOx) nanowires are used as the sacrificial templates because it possesses the smooth surface, high aspect ratio, and good thermal stability. After the 3-aminopropyl-trimethoxysilane (APTMS) functionalization, activation, and hydrazine modified electroless Ni plating processes, a uniform a-SiOx/pure Ni core-shell nanowire structure was produced. By etching away the inner a-SiOx nanowire templates with dilute HF solution, pure hollow Ni nanotubes were then obtain. The inner diameters of the pure Ni nanotubes were about 30-150 nm and the length was several tens of micrometers. For the synthesis of the hollow metal spheres, monodispersed colloidal polystyrene spheres of equal size were served as the templates. After the hydrazine modified electroless Ni deposition and subsequent removal the inner PS sphere cores, large quantities of pure hollow Ni metal spheres were first successfully synthesized in this study. The surface morphology, crystal structure, and chemical composition of the synthesized products were systematically characterized by SEM, TEM, SAED, EDS, and high-resolution TEM. The observed results present the exciting prospect that using the colloidal spheres of equal size and high-aspect-ratio a-SiOx nanowires as the removable templates, the noval APTMS and hydrazine modified electroless deposition technique promises to be applicable to the large-scale synthesis of a variety of high-purity hollow metal nanomaterials. |
