奈米碳管成長機制及其作為微放電拋光電極之應用研究

博士生：苗新元 指導教授：歐陽敏盛 博士
呂助增 博士
國立清華大學 工程與系統科學系

中文摘要
關鍵字：奈米碳管、電子場發射特性、化學氣相沈積法、微放電加工。

本研究的目標是生產一維之新穎奈米材料­奈米碳管 (carbon nanotubes , CNTs); 並根據其具有特殊之物理性質，將它作為新世代工業材料之可行性研究。故本研究的中心架構與思想是，引進新材料(CNTs)，開發並生產且創造其新的工業應用價值，為新世紀機械工業貢獻心力。首先自行建構生產設備，以製造條件適用之CNTs。接著利用CNTs具有之高剛性與電子場發射特性，結合機械非傳統加工之放電加工技術，預期使CNTs能成為可執行微放電拋光加工之工具電極。
整個研究步驟是：
(1)首先研究開發新的奈米碳管(CNT)成長方式。為避免因能隙的阻隔而使電能消秏，本研究不同於以往文獻上所使用的;在矽基板上鍍催化劑薄膜的成長方式。而是創新的提出以銅合金(alloy，包含催化劑)為基板，並利用本實驗室自製的射頻輔助熱鎢絲化學氣相蒸鍍[radio frequency (RF) assisted hot filament chemical vapor deposition (HFCVD)]方式生產CNTs。期使整個生產流程，符合工作現場的規格需求，且在生產時能控制最佳化之成長參數，使得所生產的CNTs成品，特別適合於微放電加工的電性要求。
根據結果顯示，在適當的成長參數控制下，銅合金成長CNTs是可行的。並發現CNTs是成長在含催化劑含量多的樹枝晶(dendrite)上為多，在樹枝間(interdendrite) 上則成長的量極少。但，這種情形會隨著催化劑的數量增加而改變; 即當合金中除了基材(matrix)外，金屬催化劑的數量多於二元時，在相同的成長參數下，CNTs成長則並不拘限於樹枝晶上，而是在基板上呈全面性的成長。
(2) 在生產製造CNTs方面。本研究以甲烷(CH4)為碳源(carbon source)，氫氣(H2)、氨氣(NH3)為稀釋氣體(dilute gas)進行反應。反應所須的溫度由鎢絲加熱器維持，微波源(microwave cavity)則提供反應氣體在進入反應腔體前作預解離的動作。13.56 MHz的R.F. 產生器(generator)所提供的能量不但使得反應氣體得充份解離, 以利進行反應，更提供一R.F self-bias之負偏壓。此一負偏壓經實驗證實有利於CNTs之準直度的提升。
在研究中更發現，氫蝕刻 (hydrogen etching)有助於合金基板表面形成奈米級催化劑微顆粒。而經由控制氫蝕刻之時間長短，可控制催化劑顆粒被微細化之尺寸，進而控制CNT直徑之大小。此一結果是本研究在參數化成長CNTs上的另一大貢獻。
研究過程中應用掃描式電子顯微鏡(SEM)、能量散佈光譜儀(EDS)、X射線能量散佈分析儀(XRD)、微拉曼(Micro Raman)、高解析度穿透式電子顯微鏡(HRTEM)等分析儀器進行CNT表面微結構、鍵結結構、碳層結構之形貌與品質分析。本研究獨特的HFCVD設備所生產的CNTs屬多層壁奈米碳管(multi-wall carbon nanotubes, MWCNTs)，其成長機制(growth mechanism)會隨催化劑顆粒大小與稀釋氣體之不同而有差異，甚致影響生成結構與其他特性。在論文中有詳細的論述。
(3)在應用方面，以本研究所生產之多層壁奈米碳管，作為微放電加工之工具電極，並製作專用的電晶體放電電路(為能精確的計算出放電之能量)與加工機構，來進行微放電拋光加工，期許能提升並改善須極度表面平坦度要求的高科技工件表面粗糙度之問題。在本研究中以在銅合金基板上成長之多層壁奈米碳管 (約110 nm直徑、3 μm長) 為工具電極，對單面拋光、n-type (10~100 Ω-cm) 矽晶片作微拋光加工，經實驗驗證平均表面去除率可達30 nm/min。

A Study of the Growth Mechanism of Carbon Nanotubes and its Applications for the Electrodes of Micro-EDM Polishing Process

Ph. D. student：Hsin-Yuan Miao Advisors：Dr. Min-Shen Ouyang
Dr. Juh-Tzeng Lue
Department of Engineering and System Science
National Tsing Hua University

Abstract
Key words：carbon nanotubes、field emission properties、chemical vapor deposition (CVD)、micro electric discharge machining (micro-EDM)。

In this work we attempt to design and to fabricate the new one dimensional material – carbon nanotubes (CNTs) in a flourish way, and to investigate whether it is suitable for industry applications. The main thrust of this research is to develope a new growth process that results in a fertile CNTs for the exploitation of surface modification by the electric discharge.
First of all, we have developed a growth chamber equipped with facilities that can produced the well-aligned CNTs on the different substrate. Then, to utilize the properties of high rigidity and field emission of CNTs, and to combine with the idea of micro electric discharge machining (micro-EDM), it is to expect that making CNTs could as the tool electrode for precise surface polish.
The steps of this research are：
(1) Carbon nanotubes(CNTs) are successfully grown on alloys made of iron groups and metals by a microwave enhanced hot-filament method with the radio-frequency (rf) field induced self-bias. A precursor of hydrogen etching to produce catalyst nanoparticles on substrate surface is crucial for the CNTs growth. Exploiting bulk-alloy catalysts such as Cu-Ni, Cu-Fe, Cu-Co, and Cu-Ni-Fe-Co for substrates instead of using usual thin film catalysts on Si substrates enunciates a new growth mechanism which debates to the mechanism of dissolving carbons in eutectic nanoparticles and then precipitating graphite near the contact surface of the particle and the substrate.
(2) Bunched and multi-circularly wrapped carbon nanotubes (CNT) are observed to grow on alloy substrates based on iron group metals and copper by a microwave enhanced hot-filament method with a dilute gas of ammonia at a proper RF self-bias. The grown size of CNTs embodied in the grain sizes of conducting bulk alloy catalysts such as Cu-Ni, Cu-Fe, Cu-Co, and Cu-Ni-Fe-Co are controlled by a precursor time of hydrogen plasma etching. Species with different structural features and homogenization of CNTs samples are produced crucially attributed to various reactant gases and self-bias induced by the radio frequency field.
(3) In this work a miniscule electrode for pursuing the precise surface modification by exploiting multi-wall carbon nanotubes (MWCNT) as the discharge electrodes was studied. The excellent upright growth of carbon nanotubes on copper based alloy substrate by a radio frequency (RF) assisted hot filament chemical vapor deposition (HFCVD) method suggests us to implement MWCNTs as the miniature electrodes for discharge machining. The results reveal that the spoiling rates for the un-polishing of n-type Si wafer ( 10~100 Ω-cm) can up to 30 nm/min with the electrodes to be much endurable to be distorted. It is expected that that MWCNTs can be applied to non-conventional material processing especially in miniature discharge machining.

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