本研究利用陰極電弧蒸鍍技術(CAE)以鋁鈦硼(AlTiB)與不同比例的鋁鈦鈮矽(AlTiNbSi)靶材沉積單層氮化鋁鈦硼(AlTiBN)、單層氮化鋁鈦鈮矽(AlTiNbSiN)與奈米多層氮化鋁鈦鈮矽硼(AlTiBN/AlTiNbSiN)硬質薄膜，對不同比例的AlTiBN/AlTiNbSiN進行機械性質、切削性能與高溫熱穩定性的比較。
本研究使用低掠角薄膜X光繞射儀(GIXRD)分析薄膜的晶體結構與結晶相，再利用場發射掃描式電子顯微鏡(FESEM)與場發射穿透式電子顯微鏡(FETEM)來觀察薄膜的微結構，並使用場發射電子微探儀(EPMA)進行薄膜元素分析。機械性質部分使用洛氏壓痕試驗機來評斷薄膜附著力，並使用奈米壓痕試驗機與球對盤磨耗試驗機來量測薄膜的硬度與磨耗性能。最後對沉積態薄膜使用高溫管型爐在900 ºC環境下進行一到八小時的真空與氧化退火，藉此評估薄膜的熱穩定與抗氧化能力。
根據研究結果顯示，在薄膜中添加矽與硼均能使晶粒細化抑制晶粒成長，此次五種薄膜均觀察到此現象，沉積態薄膜硬度均>35 GPa。而AlTiNbSiN系列薄膜觀察到了有c-TiAlNbSiN相與c-AlTiN相的固溶結構，且隨著Al/Ti比越高其薄膜有越接近單一固溶相的趨勢，而具有高Al/Ti比的多層NSB (AlTiBN/AlTiNbSiN)薄膜在沉積態呈現了單一固溶相的結構。由磨耗試驗結果得知多層NSB薄膜雖然因為Nb元素使磨擦係數略為增加，不過具有較高的H/E*值，使薄膜具有高硬度(36.42 GPa)與低磨耗率(2.05x10-6 mm3/Nm)，綜合能力表現優秀。
在高溫真空退火後，具有較高Al/Ti比的單層AlTiNbSiN、AlTiBN與多層NSB薄膜熱穩定性優異，均未有任何單一氮化物金屬相分解的產生，尤其是多層NSB薄膜在真空退火兩小時後因晶粒尺寸減少導致硬度上升至最高38.4 GPa。氧化實驗方面，添加矽與硼的奈米晶複合結構可以阻止氧原子藉由晶界擴散至薄膜內部，且緻密的Al2O3和SiO2氧化層可以延緩氧原子擴散至薄膜內部的速率，而薄膜內部的NbN在被氧化時因與氧有高親和性會優先形成Nb2O5，當微量的Nb2O5產生時NbN會形成Nb-N(O)的結構，且會優先偏析至晶界使氧化速率降低，使多層NSB薄膜具有最佳的抗氧化性。 
根據微型銑刀PCB板切削實驗結果得知，在切削至30 m前刀具磨耗量與球對盤磨耗實驗結果相符，且低磨擦係數的AlTiBN薄膜與多層NSB博膜刀具得到較低的磨耗率。而隨著切削距離增加，薄膜的附著性扮演了更重要的角色，未含Nb的AlTiBN薄膜因薄膜脫落而使刀具磨耗急遽增加，而添加Nb的薄膜因與基材有較佳的附著性，在切削距離>30 m時，多層NSB薄膜刀具因較低的摩擦係數與高附著性，獲得最低的刀具磨耗量。切削實驗結果顯示相較於未鍍膜刀具，本次實驗的薄膜刀具使刀具壽命提升最少200 %，而具有最低刀具磨耗量的多層NSB薄膜刀具壽命提升至400 %。

This study employs the cathodic arc evaporation (CAE) technique to deposit AlTiB and different ratios of the AlTiNbSi target materials. It compares the mechanical properties, cutting performance, and high temperature thermal stability of single-layer AlTiBN, single-layer AlTiNbSiN, and nano-multilayer AlTiBN/AlTiNbSiN hard coatings.
Grazing incidence X-ray diffraction (GIXRD) was used in this study to analyze the crystal structure and crystalline phases of the films. Furthermore, field-emission scanning electron microscopy (FE-SEM) and field-emission transmission electron microscopy (FE-TEM) were employed to observe the microstructure of the films, while the field-emission electron probe microanalyzer (FE-EPMA) was utilized for elemental analysis. In terms of mechanical properties, the adhesion of the coatings was assessed using a nanoindentation tester, while hardness and wear resistance were measured using a nanoindentation tester and a ball-on-disc wear tester, respectively. Finally, the films deposited were subjected to vacuum annealing and oxidation at 900 ° C for 1 to 8 hours using a high temperature tube furnace to evaluate their thermal stability and resistance to oxidation.
Based on research results, the addition of silicon and boron to films can refine grain size and inhibit grain growth. This phenomenon was observed in all five types of films, with deposited film hardness exceeding 35 GPa. The AlTiNbSiN series films exhibited a solid solution structure with c-TiAlNbSiN and c-AlTiN phases. As the Al/Ti ratio increased, the films showed a trend toward a single solid solution phase. Multilayer NSB (AlTiBN/AlTiNbSiN) films with a high Al/Ti ratio exhibited a single solid solution phase in the deposited state. The results of the wear test showed that although the Nb element slightly increased the friction coefficient of the multilayer NSB films, their high value of H/E* resulted in high hardness (36.42 GPa) and low wear rate (2.05x10-6 mm3/Nm), demonstrating excellent overall performance.
After high-temperature vacuum annealing, single-layer AlTiNbSiN, AlTiBN, and multilayer NSB films with a high Al/Ti ratio exhibited excellent thermal stability without any decomposition of single nitride metal phases. In particular, the hardness of the multilayer NSB film increased to 38.4 GPa after two hours of vacuum annealing due to reduced grain size. In oxidation experiments, the nanocrystalline composite structure with added silicon and boron prevented oxygen atoms from diffusing into the film through grain boundaries. The dense oxide layers of Al2O3 and SiO2 slowed the rate of oxygen diffusion into the film. NbN within the film preferentially formed Nb2O5 when oxidized due to its high affinity for oxygen. As a small amount of Nb2O5 formed, NbN developed a structure of Nb-N (O) that segregated to grain boundaries, reducing the oxidation rate and providing the multilayer NSB film with the best oxidation resistance.
The results of the PCB board cutting test for micro-end milling showed that tool wear up to 30 meters matched the results of the ball-on-disk wear test, with the low friction coefficient AlTiBN and multilayer NSB film tools showing lower wear rates. As the cutting distance increased, film adhesion played a more critical role. The AlTiBN film without Nb showed a rapid increase in tool wear due to film delamination. In contrast, films with Nb had better adhesion to the substrate, resulting in the multilayer NSB film tools achieving the lowest tool wear beyond 30 meters of cutting distance due to their lower friction coefficient and high adhesion. The results of the cutting test indicated that the film-coated tools extended the tool life by at least 200% compared to the uncoated tools, with the multilayer NSB film tools extending the tool life by up to 400%.

摘要..........................................................................................i
Abstract..........................................................................................iii
誌謝..........................................................................................v
目錄..........................................................................................vi
表目錄..........................................................................................x
圖目錄..........................................................................................xi
第一章 緒論..........................................................................................1
1.1 前言..........................................................................................1
1.2 研究動機與目的..........................................................................................2
第二章 文獻回顧..........................................................................................3
2.1 印刷電路板..........................................................................................3
2.1.1 印刷電路板種類及趨勢..........................................................................................3
2.1.2 印刷電路板切削特性..........................................................................................4
2.1.3 硬質鍍膜刀具切削印刷電路板..........................................................................................5
2.2 硬質鍍膜強化機制..........................................................................................7
2.2.1 固溶強化機制(Solid-Solution Strengthening)..........................................................................................7
2.2.2 晶粒細化強化機制（Grain Refinement Strengthening）..........................................................................................8
2.2.3 奈米多層複合薄膜強化機制..........................................................................................9
2.3 二元及多元硬質鍍膜的種類..........................................................................................11
2.3.1 氮化鋁鈦(AlTiN)薄膜..........................................................................................11
2.3.2 多元合金薄膜..........................................................................................14
2.4 添加矽對於氮化物薄膜之影響..........................................................................................18
2.5 多元與多層硬質鍍膜熱穩定性與耐高溫氧化特性..........................................................................................22
2.5.1 多元與多層硬質鍍膜熱穩定性..........................................................................................22
2.5.2 多元與多層硬質鍍膜耐高溫氧化特性..........................................................................................26
2.6 添加鈮對於氮化物薄膜之影響..........................................................................................32
2.7 添加硼對於氮化物薄膜之影響..........................................................................................36
第三章 實驗方法..........................................................................................39
3.1 實驗流程..........................................................................................39
3.2 薄膜設計與實驗方法..........................................................................................40
3.2.1 前處理與製程步驟..........................................................................................40
3.2.2 單層AlTiBN薄膜製程設計..........................................................................................42
3.2.3 單層AlTiNbSiN與TiAlNbSiN薄膜製程設計..........................................................................................43
3.2.4 多層AlTiBN/AlTiNbSiN薄膜製程設計..........................................................................................44
3.3 薄膜機械性質分析..........................................................................................45
3.3.1 洛氏硬度試驗機..........................................................................................45
3.3.2 奈米壓痕試驗..........................................................................................46
3.3.3 球對盤磨耗試驗..........................................................................................47
3.4 高溫熱處理..........................................................................................48
3.5 微觀結構分析..........................................................................................49
3.5.1 場發射掃描式電子顯微鏡（Field emission scanning electron microscope, FE-SEM）..........................................................................................49
3.5.2 場發射穿透式電子顯微鏡（Field emission transmission electron microscope, FE-TEM）..........................................................................................51
3.5.3 場發射電子微探儀（Field emission electron probe microanalyzer , FE-EPMA） ..........................................................................................53
3.5.4 高解析X光繞射儀（High resolution X-Ray diffractometer , HR-XRD）..........................................................................................54
3.5.5 化學分析電子能譜儀（Electron spectroscope for chemical analysis , ESCA） ..........................................................................................56
3.5.6 二次離子質譜儀（Secondary ion mass spectrometer, SIMS）..........................................................................................57
3.6 印刷電路板切削測試..........................................................................................58
3.6.1 印刷電路板..........................................................................................58
3.6.2 加工機台與切削方式..........................................................................................60
第四章 結果與討論..........................................................................................62
4.1 薄膜沉積態微結構分析..........................................................................................62
4.1.1 EPMA表面元素定量分析..........................................................................................62
4.1.2 SEM微結構分析..........................................................................................63
4.1.3 X光繞射分析..........................................................................................65
4.1.4 奈米多層氮化物薄膜之TEM分析..........................................................................................68
4.2 薄膜沉積態機械性質分析..........................................................................................72
4.2.1 洛氏壓痕分析..........................................................................................72
4.2.2 奈米壓痕分析..........................................................................................73
4.2.3 磨耗試驗分析..........................................................................................74
4.3 薄膜高溫真空退火後之熱穩定性分析..........................................................................................78
4.3.1 奈米壓痕分析..........................................................................................78
4.3.2 X光繞射分析..........................................................................................80
4.3.3 TEM分析..........................................................................................91
4.4 薄膜經高溫氧化退火後之抗氧化能力分析..........................................................................................96
4.4.1 SIMS二次電子質譜儀縱深成分分析..........................................................................................96
4.4.2 XPS化學鍵結態與成分分析..........................................................................................106
4.5 切削印刷電路板實驗..........................................................................................132
第五章 結論..........................................................................................137
5.1 薄膜微結構分析..........................................................................................137
5.2 薄膜沉積態機械性質分析..........................................................................................137
5.3 薄膜熱穩定性分析..........................................................................................138
5.4 薄膜抗氧化性分析..........................................................................................139
5.5 切削印刷電路板實驗結果..........................................................................................139
第六章 未來展望..........................................................................................140
參考文獻..........................................................................................141
Extended Abstract..........................................................................................146

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