以直流濺鍍法沉積鉬薄膜於自組裝單分子膜修飾的玻璃基板之研究

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研究生：	吳怡潔 YI-CHIEH WU
論文名稱：	以直流濺鍍法沉積鉬薄膜於自組裝單分子膜修飾的玻璃基板之研究 Study the Fabrication of Molybdenum Thin Films on Self-Assembled Monolayer Modified Glass Substrate by DC Magnetron Sputtering
指導教授：	戴龑 Yian Tai
口試委員:	陶雨台 Yu-Tai Tao 蔡大翔 Dah-Shyang Tsai 王澤元 Olivier Wang 楊志仁 Clement Yang
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	119
中文關鍵詞：	直流濺鍍、鉬、自組裝單分子膜
外文關鍵詞：	DC sputter, Molybdenum, Self-Assembled Monolayer
相關次數：	點閱：353 下載：5
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鉬在硒化銅銦鎵或銅鋅錫硫這類太陽能電池中扮演著電極的角色。若在高瓦數，高溫製程下，可使鉬薄膜有較低的電阻極好的結晶度，但卻需消耗較高的能量，且不適用於軟性基版。本研究利用直流電漿濺鍍沉積鉬薄膜於自組裝單分子層薄膜(self-assembled monolayer, SAM)修飾後的鈉玻璃基板。首先，我們於未修飾玻璃基板上沉積鉬薄膜，找到最佳參數，再藉由成長自組裝單分子薄膜改質鈉玻璃基板，使其能獲得較良好的電性及結晶度。從鉬薄膜成長發現，尾端基團硫醇基(-SH)和羧基(-COOH)，與金屬有較佳的化學鍵結，可以增加載子遷移率。此外，藉由調控帶有矽烷基和羧基的自組裝單分子薄膜濃度，觀察載子遷移率的變化。最後，在不同比例的CF3-SAM與COOH-SAM混合下，可調控載子遷移率與載子濃度，於低溫製成下得到電性良好之鉬薄膜。

In general, molybdenum thin film can be used as an electrode in CIGS or CZTS solar cells device. High power and high temperature condition is conducive to better crystallinity and resistivity, but it required numbers of energy and is not suit for flexible substrate. In this work, we studied the deposition of molybdenum thin film with DC magnetron sputter on soda lime glass substrate modified by self-assembled monolayer (SAM). First, we sputtered molybdenum on soda lime glass substrate which was not modified to find the optimization parameters. Basing on these parameters, we use SAMs to modify the soda lime glass substrate to get better crystallinity and lower resistivity of molybdenum thin films. Sputtering the molybdenum thin films at room temperature on soda lime glass substrate modified by –SH and -COOH SAMs can increase the mobility because of chemical bonding between molybdenum and SAMs. In order to observe the changing of the carrier mobility of molybdenum thin films, we control the concentration of –SH and –COOH SAMs. At last, the mobility and carrier concentration could be adjusted by changing the ratio of mixing COOH- and CF3- SAMs.

中文摘要…	………………………………………………………………I
Abstract…		…………………………………………………………………II
誌謝……………………………………………………………………III
目錄……………………………………………………………………IV
圖目錄…………………………………………….………………….…IX
表目錄		………………………………………..……………….……XVI
名詞縮寫及代號表	……………………………………….……………XIX
壹、緒論	……………………………………………………….…….…..1
1-1 前言………………………………………………….………......1
1-2  研究目的…………………………………………….…..	……..2
貳、相關理論	………………………………………………………….….4
2-1  自組裝單分子層薄膜(Self-assembled monolayer,SAM)..........4
2-1.1  自組裝單分子層薄膜簡介	……………………………4
2-2  鉬(Molybdenum, Mo)電極之簡介………………….…............7
2-3  物理氣相沉積(PVD)之方法…………………….………..…...8
2-3.1  電漿之原理	……………………………………………8
2-3.2  濺鍍之原理	…………………………………………..10
2-3.3  直流濺鍍(DC sputter)	………………………………..12
2-3.4  射頻濺鍍(RF sputter)	………………………………...13
2-3.5  熱蒸鍍(Thermal evaporation)	………………………..14
2-3.6  電子束蒸鍍(E-beam evaporation)	……………………15
2-4  薄膜成長機制…………..…………………………………...	16
参、實驗方法與步驟	……………………………………………………21
3-1  自組裝單分子薄膜製備……………………………….…	....21
3-1.1  實驗藥品及耗材	……………………………………..23
3-1.2  玻璃基板清洗程序	…………………………………..23
3-1.3  沉積鉬薄膜前之自組裝單分子層薄膜的製備	……..23
3-2  以DC-sputtering成長Mo…………………………………...24
3-2.1  實驗氣體及耗材…………………………………..…24
3-2.2  DC-sputtering實驗裝置圖	…………………………..25
3-2.3  DC-sputtering沉積Mo於已利用SAM修飾過後的玻璃基板………………………….……………………..25
3-3 實驗流程…………………………………...…………...….…	26
3-4  樣品分析量測儀器簡介……………………….……..……. 27
3-4.1  接觸角測量儀 (Contact angle)…………………..…..	27
3-4.2  場發射掃描式電子顯微鏡 (Field-Emission Scanning Electron Micro- scope)	………………………………………..27
3-4.3   小角度X-ray繞射儀(Grazing X-ray Diffraction)	….28
3-4.4   霍爾效應量測系統(Hall effect measurement system)	…………………………………………………….…30
3-4.5   X射線光電子能譜化學分析儀 (X-ray photoelectron spectrometer)	………………………………………………….33
肆、結果與討論…………………..…………….………………………..35
4-1  在不同條件下於未修飾過之玻璃基板上沉積Mo薄膜….35
4-1.1  室溫下調控不同瓦數及流量於未修飾過之玻璃基板上沉積Mo薄膜之表面型態及電性分析…..….…..35
4-1.2  不同溫度下於未修飾過之玻璃基板上沉積 Mo薄膜之分析……..……………………………………..….44
4-2  自組裝單分子層薄膜之成長與分析不同官能基自組裝單分子層薄膜之分析……….…...…………………………..52
4-2.1  自組裝單分子薄膜SH-SAM之分析……..………52
4-2.1.1  使用不同濃度SH-SAM成長於玻璃基板上…………………………………...……..52
4-2.2  自組裝單分子薄膜COOH-SAM之分析	…………...54
4-2.2.1  使用不同濃度COOH-SAM成長於玻璃基板上…………….....…………………………..54
4-2.3  自組裝單分子薄膜NH2-SAM之分析	……………...58
4-2.4  自組裝單分子薄膜CH3-SAM之分析	………………61
4-2.5  自組裝單分子薄膜CF3-SAM之分析	………...…….63
4-2.6  自組裝單分子薄膜TDFOS-SAM之分析	………..…65
4-2.7  自組裝單分子薄膜3CN-SAM之分析	……………...67
4-3  自組裝單分子薄膜修飾過後的玻璃基板所沉積之Mo薄膜分析……………………………………………………..………69
4-3.1  室溫下使用自組裝單分子薄膜修飾玻璃基板所沉積Mo薄膜結構及表面型態分析	………………………69
4-3.2  室溫下使用自組裝單分子薄膜修飾玻璃基板所沉積Mo薄膜電性分析……………………………………78
4-3.3  對室溫下使用自組裝單分子薄膜修飾玻璃基板之附著力分析..………………………………………..…..82
4-4  使用自組裝單分子薄膜濃度變化修飾之玻璃基板所沉積Mo薄膜之分析………………………………………………..…83
4-4.1  室溫下使用SH-SAM與COOH-SAM濃度變化修飾玻璃基板所沉積Mo薄膜之分析	……………………...83
         4-4.2  室溫下使用NaOH與自組裝單分子薄膜修飾玻璃基
               板所沉積Mo薄膜之分析…………………………...92
4-4.3  室溫下使用含有尾端基-COOH的自組裝單分子薄膜修飾玻璃基板之分析……………………….…..…..105
4-5  利用不同比例法成長混合自組裝單分子薄膜之分析…..112
4-5.1  Mo薄膜沉積於不同比例混合自組裝單分子薄膜修飾玻璃基板之分析………………………..….…..112
伍、結論與未來展望	…………………………..……………………….114
參考文獻	……………………………………………………………….116

                                

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