臺灣博碩士論文加值系統

本論文主要在研究使用雷射化學氣相沉積法(Laser Chemical Vapor Deposition, LCVD)以W(CO)6沉積W薄膜之特性。實驗方法是使用351 nm波長的半導體激發式Nd：YLF雷射以W(CO)6沉積W薄膜。固定雷射輸出功率0.38 mw垂直照射在玻璃基板上，比較以相同的沉積速度4 um/sec下以不同W(CO)6氣體流量及玻璃基板溫度下所沉積出W薄膜。
由X光繞射光譜與阻值相驗證得知所沈積的薄膜為α-W與β-W相共存，且為富α-W相。鎢薄膜呈顆粒狀結構，其有別於一般由CVD所沈積出的柱狀結構。且由EDS分析結果顯示，薄膜中各組成成分不會因溫度及流量的改變而有所變化。在相同的W(CO)6氣體流量下所沉積的W薄膜表面的結晶顆粒隨chamber溫度增加亦愈大顆。在相同的W(CO)6氣體流量下所沉積的W薄膜厚度隨chamber溫度增加而增加。且增加的薄膜厚度以70℃的約2000 Å至80℃約3000 Å最為快速。但在相同的Chamber溫度下W膜厚並不隨著W(CO)6氣體流量的增加而有所明顯的增加。隨Chamber溫度增加約每上升一℃所沉積的W薄膜的阻值約下降2.5%左右，尤其W(CO)6氣體流量在300~ 400 sccm間，當chamber溫度升至70℃時已降至1 Ω/um以下，已達薄膜品質的最佳狀況。隨著流量的增加，阻值也會微幅下降。以所沉積的薄膜表面形態，厚度，及阻值上來看，在雷射能量0.38 mw、chamber溫度約70℃及流量300 sccm的條件下能沉積出好的鎢金屬線薄膜品質。

In this study, the Laser Chemical Vapor Deposition (LCVD) was used to deposit W-film on glass substrate with gas of W(CO)6. The semiconductor laser material is Nd:YLF, and its wavelength is 351 nm. The output power of laser is fixed of 0.38 mw to radiate vertically on the glass substrate, and the speed of laser is 4 μm/sec. The gas flow of W(CO)6 is varied from 100 to 400 sccm, and the glass baseboard temperature is 50, 60, 70 and 80℃.
The X-ray diffractometer and resistance-test indicate that the W film is consisted of both α-W and β-W phase and is features a rich α-W phase. The W film shows a grain-shaped structure which is different from pillar-shaped maybe is caused by a CVD process. The results show that at the same gas flow of W(CO)6, the crystal particles on the deposited W film is bigger as the chamber temperature increase. As the chamber temperature and gas flow of W(CO)6 increase, there are not any variations of the composition for W film by the EDS analysis. At the same gas flow of W(CO)6, the thickness of W film increase with increasing the chamber temperature, and the fastest temperature is from 70℃ (about 2000Å) to 80℃ (about 3000Å). In addition, at the same Chamber temperature, the thickness of W film does not increase obviously as the gas flow of W(CO)6 increases. When the W(CO)6 gas flow is between 300 and 400 sccm, the chamber temperature rises to 70℃, the resistance of W film reduces to less than 1Ω/um, which reaches the best quality of the film. Based on the results mentioned above, the optimum conditions for depositing W film using LCVD technology are 0.38 mw for laser energy, 70℃for chamber temperature and 300 sccm for gas flow.

中文摘要...................................................i
英文摘要..................................................ii
誌謝.....................................................iii
目錄......................................................iv
表目錄....................................................vi
圖目錄...................................................vii
第一章 緒論................................................1
1.1 前言...................................................1
1.2 鎢(Tungsten)的性質.....................................2
1.3 六羰鎢 (W(CO)6)之性質..................................2
1.4 LCVD所使用之先驅物.....................................3
1.5 研究動機與目的.........................................3
第二章 半導體激發固態雷射基本理論.........................11
2.1 簡介..................................................11
2.2 Nd:YLF晶體特性 .......................................11
2.3 Nd:YLF雷射工作機理....................................12
第三章 雷射化學氣相沉積法的基本原理.......................17
3.1 化學氣相沉積的原理....................................17
3.2 薄膜沉積的原理 ................................................17
3.3 雷射化學氣相沉積......................................18
第四章 實驗方法與量測方式.................................30
4.1 實驗流程..............................................30
4.2 實驗設備..............................................30
4.3 實驗步驟..............................................31
4.4 薄膜量測..............................................32
第五章 結果與討論.........................................38
5.1 鎢金屬線薄膜晶格結構之分析............................38
5.2 不同溫度與流量對鎢金屬線薄膜表面型態之影響............38
5.3 不同溫度與流量對鎢金屬線薄膜之EDS成份分析.............39
5.4 不同溫度與流量對鎢金屬線薄膜厚度之影響................40
5.5 不同溫度與流量對鎢金屬線薄膜之電性分析................41
第六章 結論...............................................58
參考文獻..................................................59
英文論文大綱..............................................63
簡歷......................................................66


表目錄
表1.1 鎢的基本特性.........................................7
表1.2 α-W（04-0806）與β-W（47-1319）之 JCPDS 檔案繞射角度及波峰強度之資料（Cu kα1，λ?= 1.5406 Å......................8
表1.3 六羰鎢及相關金屬羰基化合物的基本特性的基本特性.......9
表1.4 Metal Hexacarbonyl 所形成的金屬薄膜特性.............10
表1.5 LCVD Metal Source的優缺點...........................10
表2.1 Nd:YLF 晶體特性表...................................15
表3.1 化合物的能階及發生Photolytic反應時適合之雷射波長....27
表3.2 不同雷射的光子能量..................................28
表4.1 Nd:YLF雷射規格......................................35


圖目錄
圖1.1 鎢的晶體結構.........................................5
圖1.2 A15體心（Cubic）結構.................................5
圖1.3 六羰鎢 W(CO)6 的分子結構圖...........................6
圖1.4 八面體配合物ML6的分子軌道............................6
圖2.1 雷射基本構成........................................13
圖2.2 Nd:YLF 雷射晶體對不同波長得吸收光譜圖...............14
圖2.3 Nd:YLF 雷射的受激發射能級示意圖.....................16
圖3.1 基板表面氣流圖圖....................................24
圖3.2 顯示沉積薄膜的五個步驟（a）成核（b）晶粒成長 （c）晶粒聚結(d)縫隙填補（e）薄膜成長圖............................25
圖3.3 光解過程............................................26
圖3.4 Cr(CO)6 Mo(CO)6 W(CO)6 之能階圖...................27
圖3.5 熱解過程............................................28
圖3.6 LCVD沉積薄膜的過程(a)第1步驟：反應開始[光解反應 > 熱解反應](b)第2步驟：原子層氣相沉積 [光解反應 > 熱解反應](c)第3步驟：薄膜增厚 [光解反應 < 熱解反應](d)第4步驟：金屬線沉積 [光解反應 < 熱解反應].....................................29
圖4.1 實驗流程............................................33
圖4.2 實驗裝置............................................34
圖4.3 開放式反應腔體(chamber).............................36
圖4.4 chamber下之LCVD沉積薄膜的過程.......................37
圖5.1 LCVD在chamber 70℃，流量300sccm所沉積出鎢薄膜之X光繞射圖譜......................................................42
圖5.2 溫度與阻值的關係....................................42
圖5.3 金屬W薄膜之SEM截面影像圖，雷射能量：0.38 mW，氣體流量：300 sccm，chamber溫度為(a)50℃，(b)60℃，(c)70℃，(d)80℃......................................................43
圖5.4 金屬W薄膜SEM 低倍率表面形態圖，雷射能量：0.38 mW，氣體流量：100 sccm，chamber 溫度為(a)50℃，(b)60℃，(c)70℃，(d)80℃......................................................44
圖5.5 金屬W薄膜SEM 低倍率表面形態圖，雷射能量：0.38 mW，氣體流量：200 sccm，chamber 溫度為(a)50℃，(b)60℃，(c)70℃，(d)80℃......................................................45
圖5.6 金屬W薄膜SEM 低倍率表面形態圖，雷射能量：0.38 mW，氣體流量：300 sccm，chamber 溫度為(a)50℃，(b)60℃，(c)70℃，(d)80℃......................................................46
圖5.7 金屬W薄膜SEM 低倍率表面形態圖，雷射能量：0.38 mW，氣體流量：400 sccm，chamber 溫度為(a)50℃，(b)60℃，(c)70℃，(d)80℃......................................................47
圖5.8 金屬W薄膜SEM 高倍率表面形態圖，雷射能量：0.38 mW，氣體流量為100 sccm，chamber 溫度為 (a)50℃，(b)60℃，(c)70℃，(d)80℃...................................................48
圖5.9 金屬W薄膜SEM 高倍率表面形態圖，雷射能量：0.38 mW，氣體流量為200 sccm，chamber 溫度為 (a)50℃，(b)60℃，(c)70℃，(d)80℃...................................................49
圖5.10 金屬W薄膜SEM 高倍率表面形態圖，雷射能量：0.38 mW，氣體流量為300 sccm，chamber 溫度為 (a)50℃，(b)60℃，(c)70℃，(d)80℃...................................................50
圖5.11 金屬W薄膜SEM 高倍率表面形態圖，雷射能量：0.38 mW，氣體流量為400 sccm，chamber 溫度為 (a)50℃，(b)60℃，(c)70℃，(d)80℃...................................................51
圖5.12 EDS 成份分析圖，雷射能量：0.38 mW，氣體流量：100 sccm，chamber 溫度為 (a)50℃，(b)60℃，(c)70℃，(d)80℃...52
圖5.13 EDS 成份分析圖，雷射能量：0.38 mW，氣體流量：200 sccm，chamber 溫度為 (a)50℃，(b)60℃，(c)70℃，(d)80℃...53
圖5.14 EDS 成份分析圖，雷射能量：0.38 mW，氣體流量：300 sccm，chamber 溫度為 (a)50℃，(b)60℃，(c)70℃，(d)80℃...54
圖5.15 EDS 成份分析圖，雷射能量：0.38 mW，氣體流量：400 sccm，chamber 溫度為 (a)50℃，(b)60℃，(c)70℃，(d)80℃...55
圖5.16 流量與薄膜厚度的關係..............................56
圖5.17 溫度與薄膜厚度的關係..............................56
圖5.18 流量與阻值的關係..................................57

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