本研究利用陰極電弧蒸鍍技術（CAE）以及鋁鉻硼（AlCrB）與鋁鈦矽（AlTiSi）靶材，沉積多層氮化鋁鉻硼與氮化鋁鈦矽（AlCrBN/AlTiSiN）硬質薄膜，並且調整不同的靶材電流，鍍製出週期厚度比例為1：1的SB與1：1.7的SBR薄膜。再對沉積態的薄膜分別進行900 ºC與1000 ºC真空退火以及900 ºC氧化退火。實驗設計部分與過往研究不同處，在於針對900 ºC的真空退火，放置一、二與四小時，比較時間與溫度增加對薄膜熱穩定能力的影響。
由於添加矽與硼元素，AlCrBN/AlTiSiN薄膜在沉積過程形成纖鋅礦相（wurtzite）的AlN，導致薄膜結構屬於立方晶與纖鋅礦相組合的混合結構。此外，過去研究證明w-AlN會造成薄膜硬度降低，但同時添加矽與硼造成的晶粒細化、晶界強化與固溶強化，將其影響相互抵消，使沉積態SB與SBR薄膜硬度分別仍有28.0 ± 0.7 GPa與29.7 ± 0.2 GPa。
熱穩定能力的部分，透過奈米壓痕硬度與X光繞射進行分析。硬度部分，SB薄膜在放置於900 ºC真空環境中四小時後，觀察到本研究中硬度的峰值為29.2 ± 0.3 GPa。透過X光繞射分析中觀察到SB薄膜在退火過程中，除抑制會對機械性質帶來負面影響的h-Cr2N與w-AlN形成之外，還觀察到兩次的旋解分解，第一次為900 ºC 一小時，c-TiN與c-AlN在（200）結晶面形成，第二次為900 ºC 四小時，（111）結晶面形成c-TiN，過去文獻表示（111）結晶面的c-TiN具有較高的硬度，因此放置在900 ºC 四小時後觀察到硬度的峰值。雖然在1000 ºC 一小時，同樣有觀察第二次的旋節分解，但由於其（200）結晶面的c-TiN峰變寬，說明其晶粒成長，進而導致硬度下降至28.3 ± 0.2 GPa。然而，SBR並沒有如同SB觀察到較明顯的第二次旋節分解，歸因於調整週期厚度與Ti含量增加延緩其發生的溫度與時間。
抗氧化能力部分，透過XPS鑑定薄膜放置於900 ºC 大氣環境一小時後的表層氧化物。SB與SBR薄膜結果相同，主要有Al2O3、Cr2O3、Cr2O與SiO2形成的氧化層保護氧擴散至薄膜內部與抑制TiO2向薄膜表面擴散，所以在透過SIMS量測氧化層深度的結果，SB薄膜放置四小時後，僅128.1 nm，SBR則因為週期厚度改變與Cr含量較少，文獻指出隨著Cr含量的增加，將提升薄膜的抗氧化能力，主要是因為抗氧化能力取決於薄膜表層緻密的CrAl氧化層，限制Ti原子向表面快速擴散。因此造成SBR氧化層厚度大於SB，並且氧化速率也較SB快。但所有AlCrBN/AlTiSiN薄膜的氧化速率呈現隨著時間增加而延緩，SB薄膜由一小時的77.0 nm/h下降至四小時的 32.0 nm/h；相反地，具有最薄氧化層的AlCrN薄膜，由一小時的6.4 nm/h增加至四小時的 22.3 nm/h。

This study utilizes cathodic arc evaporation (CAE) technique with AlCrB and AlTiSi targets to deposit multilayer AlCrBN/AlTiSiN coatings. Different cathode currents are adjusted to produce coatings with a period thickness ratio of 1:1 (SB) and 1:1.7 (SBR). The as-deposited coatings are subjected to vacuum annealing at 900°C and 1000°C, as well as oxidation annealing at 900°C. The experimental design differs from previous studies in that it investigates the influence of increasing time and temperature on the thermal stability of the coatings during the 900°C vacuum annealing, with durations of one, two, and four hours.
Due to the addition of silicon and boron elements, the AlCrBN/AlTiSiN coatings form a mixture structure consisting of a cubic structure and wurtzite-phase AlN during the deposition process. Previous research has demonstrated that w-AlN reduces the hardness of the coatings. However, the grain refinement and solid solution strengthening caused by the addition of silicon and boron counteract this effect, resulted in high hardness values of 28.0 ± 0.7 and 29.7 ± 0.2 GPa for the as-deposited SB and SBR, respectively.
The thermal stability of the coatings is analyzed through nanoindentation and X-ray diffraction. In terms of hardness, the SB exhibits a peak hardness of 29.2 ± 0.3 GPa after four hours in a 900°C vacuum environment. X-ray diffraction analysis reveals that during annealing, the SB suppresses the formation of detrimental h-Cr2N and w-AlN, and exhibits two instances of spinodal decomposition. The first instance occurs at 900°C for one hour, resulted in the formation of c-TiN and c-AlN on the (200) crystal plane. The second instance occurs at 900°C for four hours, leading to the formation of c-TiN on the (111) crystal plane. Previous literature indicates that c-TiN on the (111) plane exhibits higher hardness, hence the observed peak hardness after four hours at 900°C. Although a second spinodal decomposition is also observed after one hour at 1000°C, the broadening of the c-TiN peak on the (200) crystal plane indicates grain growth and resulted in a reduced hardness of 28.3 ± 0.2 GPa. However, for the SBR, a significant second spinodal decomposition is not observed, attributed to the delayed occurrence of this process due to the increased period thickness and titanium content.
The oxidation resistance of the coatings is evaluated using XPS to analyze the surface oxides formed after one hour in a 900°C atmospheric environment. Both AlCrBN/AlTiSiN coatings demonstrate similar results, exhibiting the formation of protective oxide layers primarily composed of Al2O3, Cr2O3, Cr2O, and SiO2. These oxide layers effectively hinder the diffusion of oxygen into the coating and suppress the diffusion of TiO2 towards the surface. SIMS measurements reveal that the oxide layer depth for the SB after four hours is only 128.1 nm. However, the SBR, due to its altered period thickness and higher titanium content, exhibits a thicker oxide layer with a depth of 230.5 nm and a faster oxidation rate compared to the SB. But the oxidation rate of AlCrBN/AlTiSiN coatings decreases with increasing time. For the SB, the oxidation rate decreases from 77.0 nm/h after one hour to 32.0 nm/h after four hours. Conversely, the AlCrN, which possesses the thinnest oxide layer, shows an increase in oxidation rate from 6.4 nm/h after one hour to 22.3 nm/h after four hours.

摘要...i
Abstract...iii
誌謝...v
目錄...vi
表目錄...ix
圖目錄...x
第一章 緒論...1
1.1 前言...1
1.2 研究動機與目的...2
第二章 文獻探討...3
2.1 氮化鋁鉻與氧化鋁鈦薄膜（AlCrN and AlTiN coating）...3
2.2 添加矽（Si）與硼（B） 於氮化鋁鉻與氮化鋁鈦薄膜之效應...9
2.2.1 熱穩定能力...9
2.2.2 抗氧化能力...18
第三章 研究方法...22
3.1 實驗流程簡述...22
3.2 薄膜設計及實驗方法...23
3.2.1 前處理與鍍膜步驟...23
3.2.2 奈米漸層AlCrN薄膜製程設計...25
3.2.3 奈米多層AlTiN薄膜製程設計...26
3.2.4 奈米複合多層SB薄膜製程設計...27
3.3 高溫熱處理...28
3.4 機械性質分析...29
3.4.1 洛氏硬度試驗機（Rockwell hardness）...29
3.4.2 奈米壓痕試驗機（Nano indentation）...31
3.5 微觀結構分析...32
3.5.1 場發射掃描式電子顯微鏡（Field emission scanning electron microscope, FE-SEM）...32
3.5.2 場發射穿透式電子顯微鏡（Field emission transmission electron microscope, FE-TEM）...34
3.5.3 場發射電子微探儀（Field emission electron probe microanalyzer, EPMA）...36
3.5.4 高解析X光繞射儀（High resolution X-Ray diffractometer, HR-XRD）...37
3.5.5 化學分析電子能譜儀（Electron spectroscope for chemical analysis, ESCA）...39
3.5.6 二次離子質譜儀（Secondary ion mass spectrometer, SIMS）...40
第四章 結果與討論...42
4.1 薄膜微結構與附著性分析...42
4.1.1 SEM微結構分析...42
4.1.2 EPMA表面元素定量分析...45
4.1.3 洛氏壓痕分析...45
4.2 高溫真空退火後薄膜的熱穩定能力分析...47
4.2.1 X光繞射分析...47
4.2.2 奈米壓痕分析...52
4.2.3 TEM分析...61
4.3 高溫氧化退火後薄膜的抗氧化能力分析...66
4.3.1 SIMS 二次離子質譜儀縱深成分分析...66
4.3.2 XPS化學鍵結態與成分分析...72
第五章 結論...86
5.1 沉積態薄膜微結構與機械性質...86
5.2 薄膜熱穩定能力...86
5.3 薄膜抗氧化能力...87
第六章 未來展望...88
參考文獻...89
Extend Abstract...94

1.Yang, B., et al., Thermal and thermo-mechanical properties of Ti–Al–N and Cr–Al–N coatings. Int. J. Refract. Met. Hard Mater, 2012. 35: p. 235-240.
2.Hu, C., et al., Self-layering of (Ti,Al)N by interface-directed spinodal decomposition of (Ti,Al)N/TiN multilayers: First-principles and experimental investigations. Materials & Design, 2022. 224: p. 111392.
3.Vaz, F., et al., Thermal oxidation of Ti1 − xAlxN coatings in air. J. Eur. Ceram. Soc., 1997. 17(15): p. 1971-1977.
4.Zhou, J., et al., Effect of B-doping on the mechanical properties, thermal stability and oxidation resistance of TiAlN coatings. Int. J. Refract. Met. Hard Mater, 2021. 98: p. 105531.
5.Hu, C., L. Chen, and V. Moraes, Structure, mechanical properties, thermal stability and oxidation resistance of arc evaporated CrAlBN coatings. Surf. Coat. Technol., 2021. 417: p. 127191.
6.Chang, Y.-Y., et al., Tribological and mechanical properties of AlCrBN hard coating deposited using cathodic arc evaporation. Surf. Coat. Technol., 2022. 432: p. 128097.
7.Chang, Y.-Y. and M.-C. Cai, Mechanical property and tribological performance of AlTiSiN and AlTiBN hard coatings using ternary alloy targets. Surf. Coat. Technol., 2019. 374: p. 1120-1127.
8.Pshyk, A.V., et al., High temperature behavior of functional TiAlBSiN nanocomposite coatings. Surf. Coat. Technol., 2016. 305: p. 49-61.
9.Kuo, Y.-C., C.-J. Wang, and J.-W. Lee, The microstructure and mechanical properties evaluation of CrTiAlSiN coatings: Effects of silicon content. Thin Solid Films, 2017. 638: p. 220-229.
10.Park, I.-W., et al., Microstructures, mechanical properties, and tribological behaviors of Cr–Al–N, Cr–Si–N, and Cr–Al–Si–N coatings by a hybrid coating system. Surf. Coat. Technol., 2007. 201(9): p. 5223-5227.
11.Mercs, D., et al., Mechanical and tribological properties of Cr–N and Cr–SI–N coatings reactively sputter deposited. Surf. Coat. Technol., 2005. 200(1): p. 403-407.
12.Vepřek, S. and S. Reiprich, A concept for the design of novel superhard coatings. Thin Solid Films, 1995. 268(1): p. 64-71.
13.Liu, Z.R., et al., Effect of Si-addition on structure and thermal stability of Ti-Al-N coatings. J. Alloys Compd., 2022. 917: p. 165483.
14.Wüstefeld, C., et al., Effect of the aluminium content and the bias voltage on the microstructure formation in Ti1−xAlxN protective coatings grown by cathodic arc evaporation. Surf. Coat. Technol., 2010. 205(5): p. 1345-1349.
15.Esaka, F., et al., Depth profiling of surface oxidized TiAlN film by synchrotron radiation excited X-ray photoelectron spectroscopy. Surf. Sci., 1997. 377-379: p. 197-200.
16.Chang, Y.-Y. and C.-Y. Hsiao, High temperature oxidation resistance of multicomponent Cr–Ti–Al–Si–N coatings. Surf. Coat. Technol., 2009. 204(6): p. 992-996.
17.Chang, Y.-Y., et al., High temperature oxidation resistance of CrAlSiN coatings synthesized by a cathodic arc deposition process. J. Alloys Compd., 2008. 461(1): p. 336-341.
18.Kretschmer, A., et al., Improving phase stability, hardness, and oxidation resistance of reactively magnetron sputtered (Al,Cr,Nb,Ta,Ti)N thin films by Si-alloying. Surf. Coat. Technol., 2021. 416: p. 127162.
19.Xu, Y.X., et al., Structure and thermal properties of TiAlN/CrN multilayered coatings with various modulation ratios. Surf. Coat. Technol., 2016. 304: p. 512-518.
20.ISO 26443:2008 ,Fine ceramics (advanced ceramics, advanced technical ceramics) -- Rockwell indentation test for evaluation of adhesion of ceramic coatings. International Organization for Standardization. 2008.
21.Wu, H., et al., Nano-mechanical characterization of plasma surface tungstenized layer by depth-sensing nano-indentation measurement. Appl. Surf. Sci., 2015. 324: p. 160-167.
22.Bruslind, L., Microbiology.
23.Neumeier, J., Photophysics of Graphene Quantum Dots. 2015.
24.Wang, Y., et al., Real-time synchrotron x-ray studies of low- and high-temperature nitridation of $c$-plane sapphire. Physical Review B, 2006. 74(23): p. 235304.
25.Ferreira, R., et al., Influence of morphology and microstructure on the tribological behavior of arc deposited CrN coatings for the automotive industry. Surface & coatings technology, 2020. 397: p. 126047.
26.Rother, B. and H. Kappl, Effects of low boron concentrations on the thermal stability of hard coatings. Surf. Coat. Technol., 1997. 96(2): p. 163-168.
27.Mendez, A., et al., Effect of Al content on the hardness and thermal stability study of AlTiN and AlTiBN coatings deposited by HiPIMS. Surf. Coat. Technol., 2021. 422: p. 127513.
28.Veprek, S., et al., Composition, nanostructure and origin of the ultrahardness in nc-TiN/a-Si3N4/a- and nc-TiSi2 nanocomposites with HV=80 to ≥105 GPa. Surf. Coat. Technol., 2000. 133-134: p. 152-159.
29.Tritremmel, C., et al., Microstructure and mechanical properties of nanocrystalline Al–Cr–B–N thin films. Surf. Coat. Technol., 2012. 213: p. 1-7.
30.Chen, W., et al., Comparison of microstructures, mechanical and tribological properties of arc-deposited AlCrN, AlCrBN and CrBN coatings on Ti-6Al-4V alloy. Surf. Coat. Technol., 2020. 404: p. 126429.
31.Chen, L., et al., Influence of Zr on structure, mechanical and thermal properties of Cr–Al–N coatings. Surf. Coat. Technol., 2015. 275: p. 289-295.
32.Li, K.Q., et al., Structure, mechanical and thermal properties of CrAlBSiN coatings prepared by cathodic arc evaporation. Surf. Coat. Technol., 2023. 452: p. 129094.
33.Willmann, H., et al., Thermal stability of Al–Cr–N hard coatings. Scr. Mater., 2006. 54(11): p. 1847-1851.
34.Mayrhofer, P.H., H. Willmann, and A.E. Reiter, Structure and phase evolution of Cr–Al–N coatings during annealing. Surf. Coat. Technol., 2008. 202(20): p. 4935-4938.
35.Reiter, A.E., et al., Investigation of the properties of Al1−xCrxN coatings prepared by cathodic arc evaporation. Surf. Coat. Technol., 2005. 200(7): p. 2114-2122.
36.Endrino, J.L., et al., Spectral evidence of spinodal decomposition, phase transformation and molecular nitrogen formation in supersaturated TiAlN films upon annealing. Acta Mater., 2011. 59(16): p. 6287-6296.
37.Mayrhofer, P.H., et al., Energetic balance and kinetics for the decomposition of supersaturated Ti1−xAlxN. Acta Mater., 2007. 55(4): p. 1441-1446.
38.Moser, M., et al., Influence of Yttrium on the Thermal Stability of Ti-Al-N Thin Films. Materials, 2010. 3(3): p. 1573-1592.
39.Mayrhofer, P.H., D. Music, and J.M. Schneider, Influence of the Al distribution on the structure, elastic properties, and phase stability of supersaturated Ti1−xAlxN. J. Appl. Phys., 2006. 100(9).
40.Zhou, J., et al., Phase equilibria, thermodynamics and microstructure simulation of metastable spinodal decomposition in c–Ti1−xAlxN coatings. Calphad, 2017. 56: p. 92-101.
41.Feng, Y.-p., et al., Thermal stability and oxidation behavior of AlTiN, AlCrN and AlCrSiWN coatings. Int. J. Refract. Met. Hard Mater, 2014. 43: p. 241-249.
42.Ichijo, K., H. Hasegawa, and T. Suzuki, Microstructures of (Ti,Cr,Al,Si)N films synthesized by cathodic arc method. Surf. Coat. Technol., 2007. 201(9): p. 5477-5480.
43.Pei, F., et al., Improved properties of TiAlN coating by combined Si-addition and multilayer architecture. J. Alloys Compd., 2019. 790: p. 909-916.
44.Pang, X., et al., Annealing effects on microstructure and mechanical properties of sputtered multilayer Cr(1−x)AlxN films. Thin Solid Films, 2011. 519(18): p. 5831-5837.
45.Hu, C., et al., Structural, mechanical and thermal properties of CrAlNbN coatings. Surf. Coat. Technol., 2018. 349: p. 894-900.
46.Peng, B., et al., High-temperature thermal stability and oxidation resistance of Cr and Ta co-alloyed Ti − Al − N coatings deposited by cathodic arc evaporation. Corros. Sci., 2020. 167: p. 108490.
47.Lim, H.P., et al., A systematic investigation of the tribological behaviour of oxides formed on AlSiTiN, CrAlTiN, and CrAlSiTiN coatings. Wear, 2023. 512-513: p. 204552.
48.Hemmati, A., J. Paiva, and S.C. Veldhuis, Thermal stability and machining performance of arc evaporated Ti1-xAlxN hard PVD coatings with x=0.5 – 0.73 ratios using an integrative approach. Materialia, 2021. 17: p. 101132.
49.Ljungcrantz, H., et al., Nanoindentation studies of single‐crystal (001)‐, (011)‐, and (111)‐oriented TiN layers on MgO. J. Appl. Phys., 1996. 80(12): p. 6725-6733.
50.Sui, X., et al., Evolution behavior of oxide scales of TiAlCrN coatings at high temperature. Surf. Coat. Technol., 2019. 360: p. 133-139.
51.Chen, L., et al., Thermal stability and oxidation resistance of Ti–Al–N coatings. Surf. Coat. Technol., 2012. 206(11): p. 2954-2960.
52.Yu, D., et al., Microstructure and properties of TiAlSiN coatings prepared by hybrid PVD technology. Thin Solid Films, 2009. 517(17): p. 4950-4955.
53.Rebholz, C., et al., Hard and superhard TiAlBN coatings deposited by twin electron-beam evaporation. Surf. Coat. Technol., 2007. 201(13): p. 6078-6083.
54.Lin, J., et al., The structure, oxidation resistance, mechanical and tribological properties of CrTiAlN coatings. Surf. Coat. Technol., 2015. 277: p. 58-66.
55.Liew, W.Y.H., et al., Thermal stability, mechanical properties, and tribological performance of TiAlXN coatings: understanding the effects of alloying additions. J. Mater. Res. Technol., 2022. 17: p. 961-1012.
56.Ezura, H., et al., Micro-hardness, microstructures and thermal stability of (Ti,Cr,Al,Si)N films deposited by cathodic arc method. Vacuum, 2008. 82(5): p. 476-481.
57.Chen, W., et al., Influence of annealing on microstructures and mechanical properties of arc-deposited AlCrTiSiN coating. Surf. Coat. Technol., 2021. 421: p. 127470.
58.Kim Y.-C., P.H.-H., Chun J.S., Lee W.-J., Thin Solid Films 237, 57 (1994).
59.Olefjord I., M.H.J., Marcus P., Surf. Interface Anal. 15, 681 (1990).
60.Ayame A., K.T., Bunseki Kagaku 40, 673 (1991).
61.Chashechnikova I.T., V.V.M., Borovik V.V., Golodets G.I., Plyuto I.V., and Shpak A.P., Theor. Eksp. Khim. 28, 216 (1992).
62.Fierro J.L.G., A.L.A., Nieto J.M.L., Kremenic G., Appl. Catalysis 37, 323 (1988).
63.Blasco T., C.M.A., Corma A., Perez-Pariente J., J. Am. Chem. Soc. 115, 11806 (1993).
64.Halada G.P., C.C.R., J. Electrochem. Soc. 138, 2921, 1991.
65.Allen G.C., H.S.J., Jutson J.A., Dyke J.M., Appl. Surf. Sci. 37, 111 (1989).
66.Paparazzo E., S.E., Jimenez-Lopez A., Maireles-Torres P., Olivera-Pastor P., et al., J. Mater. Chem. 2, 1175 (1992).
67.Klimov V.D., V.A.A., Pronin I.S., Zh. Obshch. Khim. 61, 2166 (1991).
68.Hanawa T., O.M., Biomaterials 12, 767 (1991).
69.Castillo R., K.B., Ruiz P., Delmon B., J. Catal. 161, 524 (1996).
70.Finster J., K.E.-D., Heeg J., Vacuum 41, 1586 (1990).
71.Dupuie J.L., G.E., Terry F., J. Electrochem. Soc. 139, 1151 (1992).
72.Donley M.S., B.D.R., Stoebe T.G., Surf. Interface Anal. 11, 335 (1988).
73.Desimoni E., M.C., Zambonin P.G., Riviere J.C., Surf. Interface Anal. 13, 173 (1988).
74.Dementjev A.P., I.O.P., Vasilyev L.A., Naumkin A.V., Nemirovsky D.M., Shalaev D.Y., J. Vac. Sci. Technol. A 12, 423 (1994).
75.Sanjines R., T.H., Berger H., Gozzo F., Margaritondo G., and Levy F., J. Appl. Phys. 75, 2945 (1994).
76.Danek, M., et al., Influence of Cr additions on the structure and oxidation resistance of multilayered TiAlCrN films. Surf. Coat. Technol., 2017. 313: p. 158-167.
77.Hollerweger, R., et al., Guidelines for increasing the oxidation resistance of Ti-Al-N based coatings. Thin Solid Films, 2019. 688: p. 137290.
78.Xu, Y.X., et al., Thermal stability and oxidation resistance of V-alloyed TiAlN coatings. Ceram. Int., 2018. 44(2): p. 1705-1710.
79.Kim, M.J. and D.B. Lee, Oxidation of TiAlCrSiN Thin Films at 1000°C in Air. Applied Mechanics and Materials, 2015. 719-720: p. 127-131.
80.Ru, Q., et al., Properties of TiAlCrN coatings prepared by vacuum cathodic arc ion plating. Rare Met., 2008. 27(3): p. 251-256.
81.Xu, Y.X., et al., Thermal stability and oxidation resistance of sputtered TiAlCrN hard coatings. Surf. Coat. Technol., 2017. 324: p. 48-56.
82.Miyake, T., A. Kishimoto, and H. Hasegawa, Tribological properties and oxidation resistance of (Cr,Al,Y)N and (Cr,Al,Si)N films synthesized by radio-frequency magnetron sputtering method. Surf. Coat. Technol., 2010. 205: p. S290-S294.
83.Fukumoto, N., H. Ezura, and T. Suzuki, Synthesis and oxidation resistance of TiAlSiN and multilayer TiAlSiN/CrAlN coating. Surf. Coat. Technol., 2009. 204(6): p. 902-906.
84.Xu, Y.X., et al., Effect of CrN addition on the structure, mechanical and thermal properties of Ti-Al-N coating. Surf. Coat. Technol., 2013. 235: p. 506-512.