本論文主要分為兩大部分：第一部份為一維奈米材料的合成包括垂直矽奈米線及P型垂直矽奈米線的成長。我們在化學氣相沉積反應器內放置濺鍍Au觸媒的Si (111)基板，且通入SiCl4氣體進行VLS機制成長矽奈米線，在最適化條件下包括H2退火移除表面的氧化層，磊晶矽奈米線的直徑150～200 nm，且沿著四個<111>族群的方向成長，1個方向垂直和3個方向傾斜於Si (111)基板表面。因此，使用Ramp-cooling程序企圖以液相磊晶(LPE)的機制成長高程度有序僅沿著 [111]方向的矽奈米線陣列在Au觸媒/Si (111)基板上，首先Au觸媒/Si (111)基板在650℃下進行H2退火形成Au-Si合金的奈米粒子，然後降溫控制沉澱析出的速率以LPE機制磊晶Si晶種在Si (111)基板上，這個基板在SiCl4/H2氣氛下逐漸加熱到850℃以VLS機制在Si晶種上成長矽奈米線。因此，在Au觸媒沒有使用模板或圖案的情況下近似100%垂直矽奈米線僅沿著[111]方向再現成長在Si (111)基板上，這高密集度的垂直矽奈米線可以應用在太陽能電池及奈米元件上有更好的發展潛力。
第二部分為有關奈米線基礎的太陽能電池製作，若關注於經濟面及量產能力，以熱壁式化學氣相沉積系統適合於生產大面積及低成本的矽奈米線太陽能電池，使用熱壁式化學氣相沉積法以SiCl4氣體源及200 ppm BCl3當作P型硼摻雜的氣體源，初期成長有較大的高寬比值P型垂直矽奈米線陣列在Au/Si (111)基板上，接著以低壓化學氣相沉積法(高溫爐)在高溫850℃及10%矽甲烷(SiH4)為本質層先驅物沉積多晶矽薄膜厚度約50〜200 nm在p-SiNWs /p-Si (111)基板上，再次成長的矽薄膜本質層進行分析結構及電性應用在太陽能電池的研究。因此，我們的研究以徑向P-N及P-i-N結構製作矽奈米線基礎的太陽能電池，我們將詳細探討P-N接面元件製作的程序，改變不同矽奈米線陣列的長度、直徑、摻雜濃度分佈及本質層厚度探討光的吸收特性在太陽能電池轉換效率的影響，徑向P-N接面太陽能電池在照光源AM 1.5G與入射光強度100 mW/cm2的條件下可以提供Voc=0.399 V；Jsc=10.49 mA/cm2；F.F=27.36%及轉換效率η=1.15%。開發徑向P-N及P-i-N接面的太陽能電池是有前瞻性的奈米線半導體技術，有潛力大幅提升太陽能電池的轉換效率。

There are two main subjects have been studied in this essay. The first part is the synthesis of one-dimensional nanomaterials including vertically-aligned SiNWs and P-type silicon nanowires. We have grown silicon nanowires (SiNWs) on Si (111) substrates by gold-catalyzed vapor-liquid-solid (VLS) process using tetrachlorosilane (SiCl4) in a hot-wall chemical vapor deposition reactor (CVD). Even under the optimized conditions including H2 annealing to reduce the surface native oxide, epitaxial SiNWs of 150-200 nm in diameter often grew along all four <111> family directions with one direction vertical and three others inclined to the surface. Therefore, the growth of high degree ordered SiNW arrays along [111] only was attempted on Au-coated Si (111) by a ramp-cooling process utilizing the liquid phase epitaxy (LPE) mechanism. The Au-coated Si substrate was first annealed in H2 at 650℃ to form Au-Si alloy nanoparticles, and then ramp-cooled at a controlled rate to precipitate epitaxial Si seeds on the substrate based on LPE mechanism. The substrate was further heated in SiCl4/H2 to 850℃ for the VLS growths of SiNWs on the Si seeds. Thus, almost 100% vertically- aligned SiNWs along [111] only could be reproducibly grown on Si (111), without using a template or patterning the metal catalyst. The high density vertically-aligned SiNWs have good potentials for solar cells and nano-devices.
The second part is about the fabrication of NW-based solar cell. In respect to the economic consideration and scale-up ability, a hot wall CVD system is suitable for producing a large-area and low cost Si NW-based solar cell. High aspect ratio p-type silicon nanowire (p-SiNW) arrays were initially grown on gold-coated Si (111) substrates by hot-wall CVD using SiCl4 as the source gas and 200 ppm trichloro borane (BCl3 ) gas as the p-type dopant source. We report on the deposition of 50-200 nm thick polycrystalline silicon films on p-SiNWs /p-Si (111) substrates in a low pressure CVD furnace at high temperatures (850℃) and using 10% silane (SiH4) gas as precursor. The re-grown silicon layers were analyzed structurally and electrically to investigate their suitability for cell processing. Therefore, we study to fabricate Si NW-based solar cells by using radial P-N and P-i-N structure. We will explore details of the growth mechanism to make such a junction. Various length and diameter of nanowire arrays will be utilized to relate light absorption characteristics to efficiency of solar cells. The radial P-N junction cell can provide a Voc of 0.399 V, a Jsc of 10.49 mA/cm2, a F.F. of 27.36%, and an energy conversion efficiency (η) of 1.15% under the AM 1.5 illumination with an incident light intensity of 100 mW/cm2. The development of the radial P-N junction and P-i-N junction SiNWs photovoltaic device suggests that semiconducting NWs are a promising technology for improving solar cell efficiencies.

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