| Summary: | 博士 === 國立臺灣大學 === 化學研究所 === 94 === As the improvement in the nanoscience and nanotechnology, the synthesis and technology for the fabrication of nanosized materials have great development and become more complete than the past few years. In addition, it also has more structural changes in its dimensionality and size. In this thesis, four kinds of different one-dimensional semiconducting nanomaterials have been successfully fabricated using different physical or chemical synthetic methods and these nanomaterials are single-crystalline silicon nanowires, amorphous silicon dioxide nanotubes, single-crystalline tin dioxide nanobelts and single-crystalline copper indium diselenides nanorods.
By mixing the pure silicon powders and the catalysts (including metal or silicon dioxide powders) and with assistance for the laser ablation technology, the single-crystalline silicon nanowires (SiNWs) can be fabricated with the diameters reach 5-40 nm and the lengths extend to tens of micrometers. While the metal powders (like Fe, Ru and Pr) are used as the catalysts for the syntheses of SiNWs, the most stable Si {111} facets are grown and the growth direction for the SiNWs is parallel to the facets growth direction, i.e., the wire growth direction is <111> for the metal-catalyzed SiNWs. Such SiNWs are grown via the typical vapor-liquid-solid (VLS) growth mechanism that existing the eutectic liquid droplet formation during the synthesis. On the other hand, as the silicon dioxide (SiO2) used as the catalysts for the fabrication of SiNWs, the Si {111} facets also grow; however, the wire growth direction, as the <112> direction, is perpendicular to the lattice plane growth direction. The SiNWs catalyzed by SiO2 follow an oxide-assisted (OA) growth mechanism during their growths. Furthermore, based on the different chamber pressure used during the experiments, it can be found that with the increasing of the pressure, the diameters for SiNWs enlarge and the lengths for SiNWs shorten. The Raman spectra for the different diameter SiNWs are measured and the most intense F2g phonon mode, which is located ~ 520 cm-1, can be found that with decreasing for the diameter of SiNWs, the red-shifted behavior of the F2g mode is clearly seen from the corresponding Raman spectra.
By using the chemical vapor deposition method, the one-dimensional silicon dioxide nanotubes (SiO2NTs) are produced on the silicon substrate coated with Au nanoparticles which are preannealed at high temperature. The SiO2NTs can reach to 40-100 nm in diameters and extend to few micrometers in lengths. According to the electron diffraction (ED) pattern for the SiO2NTs, it can be confirmed that these nanotubes are amorphous. Besides this, the nanotubes can be separated into two groups, as thick- and thin-walled SiO2NTs, based on their different synthesis temperatures. Moreover, with the different reaction temperatures, the different shapes of Au nanoparticles are grown and this causes the different thicknesses of the SiO2NTs. With detailed analysis on the SiO2NTs, it can be figured out that the SiO2 species are diffused from the Au {111} facets and the walls of SiO2NTs are along the <022> direction of the thick-walled SiO2NTs while the <200> direction of the thin-walled SiO2NTs. Moreover, with the higher reaction temperature, the amorphous silicon dioxide nanowires (SiO2NWs) are synthesized on the silicon substrate. The Raman spectra of SiO2NTs and micro-crystallite SiO2 powders are taken and used for the characterization and both have the intense Raman peak (Si-O phonon mode) at ~ 467 cm-1.
With the thermal evaporation-condensation method, the high purity single-crystalline tin dioxide nanobelts (SnO2NBs) are fabricated via the thermal heating of tin monoxide (SnO) powders in high temperature. The SnO2NBs have their belt width for 30-90 nm, the belt thickness for 20-30 nm and the belt length for tens of micrometers. Based on the X-ray diffraction (XRD) measurements of the SnO2NBs, it can be confirmed that the nanobelts are the pure rutile tetragonal structures. From the high-resolved transmission electron microscopic images, the {111} lattice planes are clearly seen and the SnO2 nanobelt grows along the <130> direction indexed from the corresponding ED pattern. The growth of the SnO2NBs can be attributed to the self-disproportion reaction of SnO bulk powders via the vapor-solid (VS) growth mechanism. In the Raman spectrum measurement, the rutile SnO2NBs have good signal to noise ratio and the peaks at 475.9, 635.5, and 777.2 cm-1 are resolved which are corresponding to the Eg, A1g, and B2g phonon modes, respectively.
The last part in this thesis is the fabrication of the copper indium diselenide nanorods (CuInSe2NRs) which are commonly used in the solar cell technology. During the synthesis works, two ways are used for producing the CuInSe2 nanostructures, including the laser ablation/anodic aluminum oxide (AAO) membranes and the solvothermal methods. In the laser ablation/AAO membranes method, the AAO membranes have the highly uniform pore distribution and the CuInSe2 species can diffuse into the hollow channels to form the eutectic composites with the metal catalysts coated on the membranes and grow the one-dimensional CuInSe2 nanorods. The diameters of the CuInSe2NRs can reach 150-200 nm, however, the lengths of the can only extend ~2 micrometers. On the other hand, the CuInSe2NRs can also be synthesized by the solvothermal method, but the total reaction time is needed for at least 36 hours. Due to the long reaction time, the better aspect ratio and the product yield for the CuInSe2NRs can be acquired. The CuInSe2NRs fabricated by the solvothermal method have the diameter size of 50-100 nm and the lengths can extend to tens of micrometers. Moreover, from the high resolution image, the {112} lattice planes are found in the nanorods and can be indexed that the nanorods grow along the <331> direction. The Raman spectrum for CuInSe2NRs is taken and can be found that the most intense A1 phonon mode located at 175.1 cm-1 is clearly verified. This is another evidence tells us that the nanorods are purely with the CuInSe2 structures for the chemical composition.
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