本研究使用高功率脈衝磁控濺射鍍膜系統，以Al4Cr2NbSiTi2高熵合金靶和TiB2靶在矽晶片與304、420不銹鋼表面鍍製六種不同雙層週期厚度的高熵合金氮化物多層薄膜，並使用場發射掃描電子顯微鏡和穿透式電子顯微鏡研究薄膜的微結構，使用納米壓痕儀、刮痕試驗儀和磨耗測試儀分別評估高熵合金氮化物多層薄膜的硬度、韌性、附著力和摩擦學性能。
首先將AlCrNbSiTiN層和TiBN層的厚度比控制在1:1至1:1.42之間且氮氣與氬氣的比例為1:1，而AlCrNbSiTiN/TiBN的雙層週期厚度介於10到80 nm之間。接著將AlCrNbSiTiN層和TiBN層的厚度比控制在1:1至1:1.30之間且氮氣與氬氣的比例為1:1.5，而AlCrNbSiTiN/TiBN的雙層週期厚度介於5到50 nm之間，實驗結果顯示將氮氣通量從30 sccm上升到45 sccm，從化學成分結果可以得知氮氬比1:1的氮含量為45.5到46.5 at.%，氮氬比1:1.5的氮含量為45.6~48.49 at.%，氮含量上升了2~3 at.%，由於氮氣含量的上升使得TiBN造成薄膜的機械性質下降，從硬度與彈性係數結果中可以看到，氮氬比1:1為雙層週期厚度24 nm有最高硬度值18.4 GPa，而氮氬比1:1.5為雙層週期厚度40 nm有最高硬度值17.7 GPa，會造成兩組實驗硬度值低落，因為氮的含量偏高而生成軟質非晶之氮化硼相，造成整體硬度值的下降，從抗腐蝕試驗的結果可以看到，氮氬比1:1與氮氬比1:1.5的薄膜以雙層週期厚度9 nm的腐蝕阻抗約為304SS的9倍，雙層週期厚度25 nm約為304SS的73倍且鈍化區間大部分均高於304SS，這代表有不錯的抗腐蝕能力，其原因為結晶是在高熵合金層且有形成緻密結構而讓多層薄膜有優越的抗腐蝕能力。

In this study, six kinds of AlCrNbSiTiN/TiBN high entropy alloy multilayers with different periodic thickness were prepared on the surface of silicon wafer and 304, 420 stainless steel using high power pulsed magnetron sputtering coating system. The structure of the multilayers was studied by field emission scanning electron microscopy and penetrating electron microscopy. The nanoindentation apparatus, nanoindentation apparatus and TiB2 target were used. Scratch and wear testers were used to evaluate the hardness, toughness, adhesion and Tribological Properties of high-entropy alloy nitride multilayers. The effects of different double-layer periodic thickness on the properties of CRAlNbSiTiN/TiBN high-entropy alloy nitride multilayers were investigated.
In the first part of the experiment, the thickness ratio of AlCrNbSiTiN layer to TiBN layer was controlled from 1:1 to 1:1.42 and the ratio of nitrogen to argon was 1:1. The double-layer periodic thickness of AlCrNbSiTiN/TiBN was between 10 and 80 nanometers. The second part of the experiment is to control the thickness ratio of AlCrNbSiTiN layer to TiBN layer between 1:1:1.30 and the ratio of nitrogen to argon is 1:1.5, while the double-layer cycle thickness of AlCrNbSiTiN/TiBN is between 5 and 50 nanometers. The experimental results show that the nitrogen flux increases from 30 sccm to 45 sccm. From the chemical composition results, the nitrogen content in the first part of the experiment is 45.5 to 46.5 at.%, and the nitrogen content in the second part is 45.6 to 48.49 at.%. The mechanical properties of TiBN film are decreased due to the increase of nitrogen content by 2~3 at.%. It can be seen from the results of hardness and elastic coefficient that the first part of the experiment has a maximum hardness value of 18.4 GPa for M20 and the second part has a maximum hardness value of 17.7 GPa for S40, which results in a low hardness value for both groups. The high content of nitrogen results in a soft amorphous boron nitride phase, which results in a decrease in the overall hardness value. From the results of the corrosion resistance test, we can see that the film from the first part and the second part have excellent corrosion resistance. The corrosion resistance of M10 is about 9 times of 304SS, S30 is about 73 times of 304SS, and the passivation interval is mostly higher than 304SS. This indicates good corrosion resistance. The reason may be that crystallization is in high-entropy alloy layer with compact structure, which makes the multilayer film have superior corrosion resistance.

參考文獻
[1] Holleck, H., and Schier, A. V. (1995). Multilayer PVD coatings for
wear protection. Surface and Coatings Technology, 76, 328-336.
[2] Martinho, R. P., Silva, F. J., Alexandre, R. J. D., and Baptista, A. P.
M. (2011). TiB2 nanostructured coating for GFRP injection moulds.
Journal of Nanoscience and Nanotechnology, 11(6), 5374-5382.
[3] Baptista, A., Silva, F. J. G., Porteiro, J., Míguez, J. L., Pinto, G., and
Fernandes, L. (2018). On the physical vapour deposition (PVD):
evolution of magnetron sputtering processes for industrial
applications. Procedia Manufacturing, 17, 746-757.
[4] Dolinšek, S., Šuštaršič, B., and Kopač, J. (2001). Wear mechanisms
of cutting tools in high-speed cutting processes. Wear, 250(1-12),
349-356.
[5] Kelly, P. J., and Arnell, R. D. (2000). Magnetron sputtering: a review
of recent developments and applications. Vacuum, 56(3), 159-172.
[6] Swann, S. (1988). Magnetron sputtering. Physics in
technology, 19(2), 67.
[7] Rossnagel, S. M. (1999). Sputter deposition for semiconductor
manufacturing. IBM Journal of Research and Development, 43(1.2),
163-179.
[8] Kelly, P. J., and Arnell, R. D. (1998). The influence of magnetron
configuration on ion current density and deposition rate in a dual
unbalanced magnetron sputtering system. Surface and Coatings
Technology, 108, 317-322.111
[9] Palmero, A., Van Hattum, E. D., Arnoldbik, W. M., Vredenberg, A.
M., and Habraken, F. H. P. M. (2004). Characterization of the plasma
in a radio-frequency magnetron sputtering system. Journal of
applied physics, 95(12), 7611-7618.
[10] Behera, A., Aich, S., and Theivasanthi, T. (2022). Magnetron
sputtering for development of nanostructured materials. In Design,
Fabrication, and Characterization of Multifunctional
Nanomaterials (pp. 177-199). Elsevier.
[11] Safi, I. (2000). Recent aspects concerning DC reactive magnetron
sputtering of thin films: a review. Surface and Coatings
Technology, 127(2-3), 203-218.
[12] Gudmundsson, J. T., Brenning, N., Lundin, D. and Helmersson, U.
(2012). High power impulse magnetron sputtering
discharge. Journal of Vacuum Science and Technology A: Vacuum,
Surfaces, and Films, 30(3), 030801.
[13] Oskirko, V. O., Semenov, V. D., Solovyev, A. A., Rabotkin, S. V.,
Pavlov, A. P., and Zakharov, A. N. (2022). Arc energy minimization
in high-power impulse magnetron sputtering. Vacuum, 202, 111213.
[14] Sarakinos, K., Alami, J., and Konstantinidis, S. (2010). High power
pulsed magnetron sputtering: A review on scientific and engineering
state of the art. Surface and coatings technology, 204(11), 1661-
1684.
[15] Helmersson, U., Lattemann, M., Bohlmark, J., Ehiasarian, A. P., and
Gudmundsson, J. T. (2006). Ionized physical vapor deposition112
(IPVD): A review of technology and applications. Thin solid
films, 513(1-2), 1-24.
[16] Ehiasarian, A. P., Wen, J. G., and Petrov, I. (2007). Interface
microstructure engineering by high power impulse magnetron
sputtering for the enhancement of adhesion. Journal of applied
physics, 101(5), 054301.
[17] Ehiasarian, A. P., Hovsepian, P. E., Hultman, L., and Helmersson, U.
(2004). Comparison of microstructure and mechanical properties of
chromium nitride-based coatings deposited by high power impulse
magnetron sputtering and by the combined steered cathodic
arc/unbalanced magnetron technique. Thin solid films, 457(2), 270-
277.
[18] Reinhard, C., Ehiasarian, A. P., and Hovsepian, P. E. (2007).
CrN/NbN superlattice structured coatings with enhanced corrosion
resistance achieved by high power impulse magnetron sputtering
interface pre-treatment. Thin Solid Films, 515(7-8), 3685-3692.
[19] Ehiasarian, A. P., Wen, J. G., and Petrov, I. (2007). Interface
microstructure engineering by high power impulse magnetron
sputtering for the enhancement of adhesion. Journal of applied
physics, 101(5), 054301.
[20] Ehiasarian, A. P., Münz, W. D., Hultman, L., Helmersson, U., and
Petrov, I. (2003). High power pulsed magnetron sputtered CrNx
films. Surface and coatings technology, 163, 267-272.113
[21] Ehiasarian, A. P., Hovsepian, P. E., Hultman, L., and Helmersson, U.
(2004). Comparison of microstructure and mechanical properties of
chromium nitride-based coatings deposited by high power impulse
magnetron sputtering and by the combined steered cathodic
arc/unbalanced magnetron technique. Thin solid films, 457(2), 270-277.
[22] Yeh, J. W., Chen, S. K., Lin, S. J., Gan, J. Y., Chin, T. S., Shun, T. T.
and Chang, S. Y. (2004). Nanostructured high‐entropy alloys with
multiple principal elements: novel alloy design concepts and
outcomes. Advanced engineering materials, 6(5), 299-303.
[23] Yeh, J. W. (2006). Recent progress in high entropy alloys. Ann.
Chim. Sci. Mat, 31(6), 633-648.
[24] Zhang, W., Liaw, P. K., and Zhang, Y. (2018). Science and
technology in high-entropy alloys. Sci. China Mater, 61(1), 2-22.
[25] Lu, Z. P., Wang, H., Chen, M. W., Baker, I., Yeh, J. W., Liu, C. T.,
and Nieh, T. G. (2015). An assessment on the future development of
high-entropy alloys: Summary from a recent
workshop. Intermetallics, 66, 67-76.
[26] Gao, M. C. (2016). Design of high-entropy alloys. High-entropy
alloys: fundamentals and applications, 369-398.
[27] Sheng, G. U. O., and Liu, C. T. (2011). Phase stability in high
entropy alloys: Formation of solid-solution phase or amorphous
phase. Progress in Natural Science: Materials International, 21(6),
433-446.114
[28] Zhang, Y., Zhou, Y. J., Lin, J. P., Chen, G. L., and Liaw, P. K. (2008).
Solid‐solution phase formation rules for multi‐component
alloys. Advanced engineering materials, 10(6), 534-538.
[29] Zhang, C., Zhang, F., Diao, H., Gao, M. C., Tang, Z., Poplawsky, J.
D., and Liaw, P. K. (2016). Understanding phase stability of Al-CoCr-Fe-Ni high entropy alloys. Materials and Design, 109, 425-433.
[30] Chuang, M. H., Tsai, M. H., Wang, W. R., Lin, S. J., and Yeh, J. W.
(2011). Microstructure and wear behavior of AlxCo1. 5CrFeNi1.
5Tiy high-entropy alloys. Acta Materialia, 59(16), 6308-6317.
[31] Zhang, S., Sun, D., Fu, Y., and Du, H. (2005). Toughening of hard
nanostructural thin films: a critical review. Surface and Coatings
Technology, 198(1-3), 2-8.
[32] Han, Z. D., Chen, N., Zhao, S. F., Fan, L. W., Yang, G. N., Shao, Y.,
and Yao, K. F. (2017). Effect of Ti additions on mechanical
properties of NbMoTaW and VNbMoTaW refractory high entropy
alloys. Intermetallics, 84, 153-157.
[33] Liu, C. M., Wang, H. M., Zhang, S. Q., Tang, H. B., and Zhang, A.
L. (2014). Microstructure and oxidation behavior of new refractory
high entropy alloys. Journal of alloys and compounds, 583, 162-169.
[34] Stueber, M., Holleck, H., Leiste, H., Seemann, K., Ulrich, S., and
Ziebert, C. (2009). Concepts for the design of advanced nanoscale
PVD multilayer protective thin films. Journal of Alloys and
Compounds, 483(1-2), 321-333.115
[35] Helmersson, U., Todorova, S., Barnett, S. A., Sundgren, J. E.,
Markert, L. C., and Greene, J. E. (1987). Growth of single‐crystal
TiN/VN strained‐layer superlattices with extremely high mechanical
hardness. Journal of Applied Physics, 62(2), 481-484.
[36] Mirkarimi, P. B., Hultman, L., and Barnett, S. A. (1990). Enhanced
hardness in lattice‐matched single‐crystal TiN/V0. 6Nb0. 4N
superlattices. Applied physics letters, 57(25), 2654-2656.
[37] Kim, J. O., Achenbach, J. D., Shinn, M., and Barnett, S. A. (1992).
Effective elastic constants and acoustic properties of single-crystal
TiN/NbN superlattices. Journal of materials research, 7(8), 2248-
2256.
[38] Setoyama, M., Nakayama, A., Tanaka, M., Kitagawa, N., and
Nomura, T. (1996). Formation of cubic-A1N in TiN/A1N
superlattice. Surface and Coatings Technology, 86, 225-230.
[39] Nordin, M., Larsson, M., and Hogmark, S. (1998). Mechanical and
tribological properties of multilayered PVD TiN/CrN, TiN/MoN,
TiN/NbN and TiN/TaN coatings on cemented carbide. Surface and
coatings technology, 106(2-3), 234-241.
[40] Soe, W. H., and Yamamoto, R. (1997). Mechanical properties of
ceramic multilayers: TiN/CrN, TiN/ZrN, and TiN/TaN. Materials
Chemistry and Physics, 50(2), 176-181.
[41] Shih, K. K., and Dove, D. B. (1992). Ti/Ti‐N Hf/Hf‐N and W/W‐N
multilayer films with high mechanical hardness. Applied physics
letters, 61(6), 654-656.116
[42] Chu, X., Wong, M. S., Sproul, W. D., and Barnett, S. A. (1993).
Mechanical properties and microstructures of polycrystalline
ceramic/metal superlattices: TiN/Ni and TiN/Ni0. 9Cr0. 1. Surface
and Coatings Technology, 61(1-3), 251-256.
[43] Madan, A., Wang, Y. Y., Barnett, S. A., Engström, C., Ljungcrantz,
H., Hultman, L., and Grimsditch, M. (1998). Enhanced mechanical
hardness in epitaxial nonisostructural Mo/NbN and W/NbN
superlattices. Journal of applied physics, 84(2), 776-785.
[44] Baran, Ö., Sukuroglu, E. E., Efeoglu, İ., and Totik, Y. (2016). The
investigation of adhesion and fatigue properties of TiN/TaN
multilayer coatings. Journal of adhesion science and
Technology, 30(20), 2188-2200.
[45] Ulrich, S., Ziebert, C., Stüber, M., Nold, E., Holleck, H., Göken, M.
and Schloßmacher, P. (2004). Correlation between constitution,
properties and machining performance of TiN/ZrN
multilayers. Surface and Coatings Technology, 188, 331-337.
[46] Hsieh, J. H., Liang, C., Yu, C. H., and Wu, W. (1998). Deposition
and characterization of TiAlN and multi-layered TiN/TiAlN coatings
using unbalanced magnetron sputtering. Surface and Coatings
Technology, 108, 132-137.
[47] Santecchia, E., Cabibbo, M., Hamouda, A. M. S., Musharavati, F.,
Popelka, A., and Spigarelli, S. (2019). Investigation of the
temperature-related wear performance of hard nanostructured
coatings deposited on a S600 high speed steel. Metals, 9(3), 332.117
[48] Prengel, H. G., Jindal, P. C., Wendt, K. H., Santhanam, A. T., Hegde,
P. L., and Penich, R. M. (2001). A new class of high performance
PVD coatings for carbide cutting tools. Surface and coatings
technology, 139(1), 25-34.
[49] Berger, M., Wiklund, U., Eriksson, M., Engqvist, H., and Jacobson,
S. (1999). The multilayer effect in abrasion—optimising the
combination of hard and tough phases. Surface and Coatings
Technology, 116, 1138-1144.
[50] Yang, Q., Seo, D. Y., and Zhao, L. R. (2004). Multilayered coatings
with alternate pure Ti and TiN/CrN superlattice. Surface and
Coatings Technology, 177, 204-208.
[51] Tavares, C. J., Rebouta, L., Alves, E., Cavaleiro, A., Goudeau, P.,
Rivière, J. P., and Declemy, A. (2000). A structural and mechanical
analysis on PVD-grown (Ti, Al) N/Mo multilayers. Thin Solid
Films, 377, 425-429.
[52] Zhang, S., Sun, D., Fu, Y., and Du, H. (2005). Toughening of hard
nanostructural thin films: a critical review. Surface and Coatings
Technology, 198(1-3), 2-8.
[53] Liu, Y., Zhang, X., Tu, M., Hu, Y., Wang, H., Zhang, J., ... and Yang,
B. (2022). Structure and mechanical properties of multi-principalelement (AlCrNbSiTi) N hard coating. Surface and Coatings
Technology, 433, 128113.118
[54] Hsieh, M. H., Tsai, M. H., Shen, W. J., and Yeh, J. W. (2013).
Structure and properties of two Al–Cr–Nb–Si–Ti high-entropy
nitride coatings. Surface and Coatings Technology, 221, 118-123.
[55] Panjan, P., Drnovšek, A., Gselman, P., Čekada, M., and Panjan, M.
(2020). Review of growth defects in thin films prepared by PVD
techniques. Coatings, 10(5), 447.
[56] Zhao, J. P., Wang, X., Chen, Z. Y., Yang, S. Q., Shi, T. S., and Liu,
X. H. (1997). Overall energy model for preferred growth of TiN
films during filtered arc deposition. Journal of Physics D: Applied
Physics, 30(1), 5.
[57] Aouadi, K., Tlili, B., Nouveau, C., Besnard, A., Chafra, M., and
Souli, R. (2019). Influence of substrate bias voltage on corrosion and
wear behavior of physical vapor deposition CrN coatings. Journal of
Materials Engineering and Performance, 28, 2881-2891.
[58] Wang, Y. X., Zhang, S., Lee, J. W., Lew, W. S., and Li, B. (2012).
Influence of bias voltage on the hardness and toughness of CrAlN
coatings via magnetron sputtering. Surface and Coatings
Technology, 206(24), 5103-5107.
[59] García-González, L., Hernández-Torres, J., Mendoza-Barrera, C.,
Meléndez-Lira, M., García-Ramírez, P. J., Martínez-Castillo, J. and
Espinoza-Beltrán, F. J. (2008). Relationship between crystalline
structure and hardness of Ti-Si-NO coatings fabricated by dc
sputtering. Journal of Materials Engineering and Performance, 17,
580-585.119
[60] Chaleix, L., and Machet, J. (1997). Study of the composition and of
the mechanical properties of TiBN films obtained by DC magnetron
sputtering. Surface and Coatings technology, 91(1-2), 74-82.
[61] Nowotny, H., Benesovsky, F., Brukl, C., and Schob, O. (1961). Die
Dreistoffe: Titan—Bor—Kohlenstoff und Titan—Bor—
Stickstoff. Monatshefte für Chemie und verwandte Teile anderer
Wissenschaften, 92, 403-414.
[62] Lenz, B., Hasselbruch, H., Grossmann, H., and Mehner, A. (2020).
Application of CNN networks for an automatic determination of
critical loads in scratch tests on aC: H: W coatings. Surface and
Coatings Technology, 393, 125764.
[63] Bachani, S. K., Wang, C. J., Lou, B. S., Chang, L. C., and Lee, J. W.
(2021). Fabrication of TiZrNbTaFeN high-entropy alloys coatings
by HiPIMS: Effect of nitrogen flow rate on the microstructural
development, mechanical and tribological performance, electrical
properties and corrosion characteristics. Journal of Alloys and
Compounds, 873, 159605.
[64] Chen, X., Du, Y., and Chung, Y. W. (2019). Commentary on using
H/E and H3/E2 as proxies for fracture toughness of hard
coatings. Thin Solid Films, 688, 137265.