臺灣博碩士論文加值系統

本實驗為蝕刻鋁釹合金(Al:98wt﹪，Nd:2wt﹪)，蝕刻液包括磷酸、醋酸、硝酸與水，藉由改變蝕刻液的體積組成、蝕刻時蝕刻液的攪拌與否和蝕刻溫度，量測蝕刻速率與樣本片的表面AFM、XPS分析，推論各個酸的作用情形、反應的機制、蝕刻反應的反應式、蝕刻反應的速率式、以及速率式中的各個常數，包括速率常數、反應級數、活化能與頻率因數等等。
由本實驗推論出醋酸並非主要的蝕刻因子，在磷酸、醋酸與水的蝕刻液中，醋酸的添加與否並未對蝕刻速率造成影響；對表面粗糙造影響亦不大。蝕刻液為磷酸加水時蝕刻反應為反應控制（reaction control），反應為二級反應，對氫離子與磷酸二氫根離子各為一級反應。因為金屬鋁表面會形成氧化鋁的鈍化層，除了磷酸外，此鈍化層不易與其他酸發生反應；磷酸二氫根及氫離子接者與鋁發生反應，產生磷酸二氫鋁 之錯合物及氫氣。因為產生的氫氣無法快速順利的排除，因此使反應變慢。故添加硝酸，硝酸同時扮演了氧化劑與促進劑。以硝酸當氧化劑的作用在於氧化被吸附之表面氫原子，促使反應快速；以硝酸當促進劑的作用在於加速鋁表面之錯合物層的溶解，進而使處在此錯合物中的氫氣快速擴散至邊界層內。當磷酸添加硝酸且磷酸濃度低於36vol﹪時，蝕刻反應受攪拌影響；當磷酸添加硝酸且磷酸濃度高時，蝕刻反應為反應控制（reaction control），不受攪拌影響。
本實驗推論了蝕刻反應的基本方程式及速率式，希望能在學術上，使我們更能了解蝕刻反應的確實發生情形。

This thesis focuses on the survey of etching (Al 98wt % / Nd 2wt %) alloy. Etching solution includes H3PO4, CH3COOH, HNO3 and deionized water. By changing concentration, stir condition and etching temperature, we measure the etching rate and analyze the surface condition by AFM and XPS. In order to infer the effect of each acid, reaction mechanism, reaction equation, and rate equation, we calculate all kinds of constants of rate equation, including rate constant, reaction order, activation energy and frequency factor etc…
From experimental results, we investigate that CH3COOH doesn’t make the main contribution of etching reaction. In the mixing etching solution of H3PO4, CH3COOH and water, CH3COOH addition doesn’t have influences upon etching rate and the sample’s surface roughness, when we use H3PO4 and water as etching solution, etching reaction is reaction control and second order reaction which is first order reaction each for H+ and . On account of forming passivation film of Al2O3, this passivation film hardly react with other acids, except H3PO4, and H+ react with Al one by one to form complex compound of and hydrogen. The forming hydrogen can’t be eliminated quickly that will reduce the etching rate, We use HNO3 as both oxidizing agent and promoter. Using HNO3 as oxidizing agent is to oxidize adsorbed hydrogen atoms on Al surface. To enhance the reaction rate, on the other hand, using HNO3 as promoter is to accelerate the dissolvation rate of complexing layer in order to make the adsorbed hydrogen on complex layer diffuse into boundary layer move quickly. Experimental results also show that when HNO3 addition with H3PO4 and the H3PO4 concentration is low, etching reaction is affected by stirring. But when H3PO4 concentration is high, the etching reaction control not relating to stirring or not.
From the experiments, we have found the fundamental equation and rate equation of the etching reaction. So that we can get future understanding of etching mechanism academically.

摘要 Ⅰ
目錄 Ⅲ
圖表目錄 Ⅴ
第一章 緒論…………………………………………………………..……………..1
1.1 濕式蝕刻簡介…………...…...…………………………..………………….1
1.2 研究目的…………………………………………………………………….1
第二章 文獻回顧……………………………………………………………………5
2.1 鋁及鋁合金的簡介………………………………………………………….5
2.2 氧化鋁的蝕刻……………………………………………………………….5
2.3 鋁之蝕刻…………………………………………………………………….9
第三章 基本原理…………………………………………………………………..19
3.1 電化電池與蝕刻反應……………………………….……………………..19
3.2過渡態學說（Transition-state Theory）…………….……………………..21
3.3 阿瑞尼士方程式 （Arrhenious equation）……………………………….23
3.4 反應速率常數與反應溫度間的關係………………...……………………24
3.5 尖細角( taper angle )的定義……………………………………………….25
第四章 實驗設備及方法…………………………………………………………..28
4.1 實驗設備與藥品…………………………………………………………...28
4.2 實驗方法…………………………………………………………………...29
4.3 儀器原理……….…………………………...……………………………...31
第五章 結果與討論………………………………………………………………..37
5.1 以磷酸為蝕刻液時加入醋酸，醋酸對蝕刻的影響………………………37
5.2 蝕刻液為磷酸時，磷酸對蝕刻鋁釹合金的影響………………………….38
5.3 蝕刻液為磷酸時，加入硝酸後的影響……………………………………46
5.4 蝕刻鋁釹合金(Al:98wt%，Nd:2 wt%)，發生在邊界層內的情形……….52
5.5 磷酸加硝酸蝕刻鋁釹合金(Al:98 wt%，Nd:2 wt%)的速率式…………….54
第六章 結論………………………………………………………………………..97
6.1 醋酸的影響………………………………………………………………...97
6.2 蝕刻液為磷酸與水的組成……………….………………………………..97
6.3 蝕刻液為磷酸、硝酸與水的組成………………………………..………..98
符號附錄…………………………………………………………………………....100
參考文獻……………………………………………………………………………102

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顏溪成，沈坤伸，”非晶形ITO薄膜濕式蝕刻之研究”， 台大化工所碩士學位
論文(2002)，台北。