近年來金屬玻璃(Metallic Glass，MG)的發明在工業領域中有著多項技術應用，使得金屬玻璃的發明引起了廣泛的興趣。在所有類型的MG中，鐵基金屬玻璃(Fe-based MG)具有較高的機械強度，良好的熱穩定性,強的耐腐蝕性，優異的軟磁性能和相對其他金屬玻璃基材較低的生產成本，因此是一個獨特且具有商業競爭力的材料。本研究主要以飛秒雷射(Femtosecond laser)誘導鐵基金屬玻璃，於材料表面產生週期性表面結構，藉由改變加工參數已進行一連串的表面形貌及特徵的探討，再藉由不同的表面形貌組合而成的大面積結構，分別比較討論耐腐蝕性、色彩表現及用於翻模應用的可行性，以材料的特性配合雷射加工後的結構，解決現有模具及後加工等相關問題，以減少繁複的工序。

In recent years, metallic glass (MG) has several technical applications in the industrial field, making metallic glass aroused widespread interest. Among all types of MG, Fe-based metallic glass (Fe-based MG) is a unique and commercially competitive material, which has high mechanical strength, good thermal stability, strong corrosion resistance, excellent soft magnetic properties, and cheaper cost than other metallic glass substrates. In this study, the femtosecond laser was used to induce Fe-based MG to produce sub-wavelength periodic surface structures on the surface of the material. By changing the laser machining parame-ters, a series of surface morphology and characteristics have been discussed. On the other hand, with a large-area structure composed of different surface morphologies, we compare the corrosion resistance, color performance, and feasibility of mold application, and use the characteristics of the material to match the structure after laser processing, and solve the related problems of existing molds and post-processing to reduce complicated procedures.

[1] A. C. Lund and C. A. Schuh, "Topological and chemical arrangement of binary alloys during severe deformation," Journal of Applied Physics, vol. 95, no. 9, pp. 4815-4822, 2004, doi: 10.1063/1.1691481.
[2] J. Kramer, "Produced the first amorphous metals through vapor deposition," Annals of Physics, vol. 19, p. 37, 1934.
[3] W.-P. Sung, Y. Yan, S. Xu, and T.-Y. Han, "Preparation, properties and applications of metal glass," MATEC Web of Conferences, vol. 175, 2018, doi: 10.1051/matecconf/201817501011.
[4] C. Suryanarayana and A. Inoue, "Iron-based bulk metallic glasses," International Materials Reviews, vol. 58, no. 3, pp. 131-166, 2013, doi: 10.1179/1743280412y.0000000007.
[5] N. Yodoshi, R. Yamada, A. Kawasaki, and A. Makino, "Micro viscous flow processing of Fe-based metallic glassy particles," Journal of Alloys and Compounds, vol. 615, pp. S61-S66, 2014, doi: 10.1016/j.jallcom.2013.12.256.
[6] P. H. Tsai, A. C. Xiao, J. B. Li, J. S. C. Jang, J. P. Chu, and J. C. Huang, "Prominent Fe-based bulk amorphous steel alloy with large supercooled liquid region and superior corrosion resistance," Journal of Alloys and Compounds, vol. 586, pp. 94-98, 2014, doi: 10.1016/j.jallcom.2013.09.186.
[7] J. S. C. Jang et al., "Enhanced cutting durability of surgical blade by coating with Fe-based metallic glass thin film," (in English), Intermetallics, vol. 65, pp. 56-60, Oct 2015, doi: 10.1016/j.intermet.2015.06.012.
[8] Y. Shen, Y. Li, C. Chen, and H.-L. Tsai, "3D printing of large, complex metallic glass structures," Materials & Design, vol. 117, pp. 213-222, 2017, doi: 10.1016/j.matdes.2016.12.087.
[9] W. L. Woliński et al., "Laser-induced color marking of stainless steel," presented at the Laser Technology 2012: Applications of Lasers, 2013.
[10] L. Lavisse et al., "Pulsed laser growth and characterization of thin films on titanium substrates," Applied Surface Science, vol. 253, no. 19, pp. 8226-8230, 2007, doi: 10.1016/j.apsusc.2007.02.136.
[11] G. Li et al., "Femtosecond laser color marking stainless steel surface with different wavelengths," Applied Physics A, vol. 118, no. 4, pp. 1189-1196, 2014, doi: 10.1007/s00339-014-8868-3.
[12] J. M. Guay et al., "Laser-induced plasmonic colours on metals," Nat Commun, vol. 8, p. 16095, Jul 18 2017, doi: 10.1038/ncomms16095.
[13] J. P. Callan, "Ultrafast dynamics and phase changes in solids excited by femtosecond laser pulses," PhDT, p. 2604, 2000.
[14] H. S. Chen, H. J. Leamy, and C. E. Miller, "PREPARATION OF GLASSY
METALS," Annual Reviews, 1980.
[15] M. Chen, "A brief overview of bulk metallic glasses," NPG Asia Materials, vol. 3, no. 9, pp. 82-90, 2011, doi: 10.1038/asiamat.2011.30.
[16] A. Brenner, D. E. Couch, and E. K. Williams, "Electrodeposition of alloys of phosphorus with nickel or cobalt," J. Res. Nat. Bur. Stand, vol. 44, no. 1, p. 109, 1950.
[17] W. Klement, R. Willens, and P. Duwez, "Non-crystalline structure in solidified gold–silicon alloys," Nature, vol. 187, no. 4740, pp. 869-870, 1960.
[18] H. Liebermann and C. Graham, "Production of amorphous alloy ribbons and effects of apparatus parameters on ribbon dimensions," IEEE Transactions on Magnetics, vol. 12, no. 6, pp. 921-923, 1976.
[19] A. Inoue, "High strength bulk amorphous alloys with low critical cooling rates (overview)," Materials Transactions, JIM, vol. 36, no. 7, pp. 866-875, 1995.
[20] A. Inoue, T. Zhang, and T. Masumoto, "Production of amorphous cylinder and sheet of La55Al25Ni20 alloy by a metallic mold casting method," Materials Transactions, JIM, vol. 31, no. 5, pp. 425-428, 1990.
[21] A. Inoue, T. Nakamura, N. Nishiyama, and T. Masumoto, "Mg–Cu–Y bulk amorphous alloys with high tensile strength produced by a high-pressure die casting method," Materials Transactions, JIM, vol. 33, no. 10, pp. 937-945, 1992.
[22] Y.-K. Xu, H. Ma, J. Xu, and E. Ma, "Mg-based bulk metallic glass composites with plasticity and gigapascal strength," Acta Materialia, vol. 53, no. 6, pp. 1857-1866, 2005.
[23] A. Inoue, W. Zhang, T. Zhang, and K. Kurosaka, "Cu-based bulk glassy alloys with high tensile strength of over 2000 MPa," Journal of non-crystalline solids, vol. 304, no. 1-3, pp. 200-209, 2002.
[24] A. Inoue, B. Shen, H. Koshiba, H. Kato, and A. Yavari, "Ultra-high strength above 5000 MPa and soft magnetic properties of Co–Fe–Ta–B bulk glassy alloys," Acta Materialia, vol. 52, no. 6, pp. 1631-1637, 2004.
[25] Y. Wang, H. Li, Y. Cheng, S. Wei, and Y. Zheng, "Corrosion performances of a Nickel-free Fe-based bulk metallic glass in simulated body fluids," Electrochemistry communications, vol. 11, no. 11, pp. 2187-2190, 2009.
[26] H. Li, Z. Lu, S. Wang, Y. Wu, and Z. Lu, "Fe-based bulk metallic glasses: Glass formation, fabrication, properties and applications," Progress in Materials Science, vol. 103, pp. 235-318, 2019.
[27] S. Kim, J. Namkung, and O. Kwon, "Manufacture and industrial application of Fe-based metallic glasses," in Materials Science Forum, 2012, vol. 706: Trans Tech Publ, pp. 1324-1330.
[28] A. Inoue, Y. Shinohara, and J. S. Gook, "Thermal and magnetic properties of bulk Fe-based glassy alloys prepared by copper mold casting," Materials Transactions, JIM, vol. 36, no. 12, pp. 1427-1433, 1995.
[29] V. Ponnambalam, S. J. Poon, and G. J. Shiflet, "Fe-based bulk metallic glasses with diameter thickness larger than one centimeter," Journal of Materials Research, vol. 19, no. 5, pp. 1320-1323, 2004.
[30] A. Inoue, F. Kong, Q. Man, B. Shen, R. Li, and F. Al-Marzouki, "Development and applications of Fe-and Co-based bulk glassy alloys and their prospects," Journal of Alloys and Compounds, vol. 615, pp. S2-S8, 2014.
[31] J. Pan, Q. Chen, N. Li, and L. Liu, "Formation of centimeter Fe-based bulk metallic glasses in low vacuum environment," Journal of alloys and compounds, vol. 463, no. 1-2, pp. 246-249, 2008.
[32] H. Li, Z. Lu, and S. Yi, "Estimation of the glass forming ability of the Fe-based bulk metallic glass Fe 68.8 C 7.0 Si 3.5 B 5.0 P 9.6 Cr 2.1 Mo 2.0 Al 2.0 that contains non-metallic inclusions," Metals and Materials International, vol. 15, no. 1, p. 7, 2009.
[33] Z. Mahbooba et al., "Additive manufacturing of an iron-based bulk metallic glass larger than the critical casting thickness," Applied Materials Today, vol. 11, pp. 264-269, 2018.
[34] H. Attar, M. Bönisch, M. Calin, L.-C. Zhang, S. Scudino, and J. Eckert, "Selective laser melting of in situ titanium–titanium boride composites: processing, microstructure and mechanical properties," Acta Materialia, vol. 76, pp. 13-22, 2014.
[35] L. Wang et al., "Selective laser melting helps fabricate record-large bulk metallic glass: Experiments, simulation and demonstrative part," Journal of Alloys and Compounds, vol. 808, p. 151731, 2019.
[36] A. Inoue and A. Takeuchi, "Recent development and application products of bulk glassy alloys," Acta Materialia, vol. 59, no. 6, pp. 2243-2267, 2011.
[37] R. Hasegawa, "Applications of amorphous magnetic alloys in electronic devices," Journal of Non-Crystalline Solids, vol. 287, no. 1-3, pp. 405-412, 2001.
[38] S.-X. Liang, W. Zhang, L. Zhang, W. Wang, and L.-C. Zhang, "Remediation of industrial contaminated water with arsenic and nitrate by mass-produced Fe-based metallic glass: Toward potential industrial applications," Sustainable Materials and Technologies, vol. 22, p. e00126, 2019.
[39] J. Blink, J. Farmer, J. Choi, and C. Saw, "Applications in the nuclear industry for thermal spray amorphous metal and ceramic coatings," Metallurgical and Materials Transactions A, vol. 40, no. 6, pp. 1344-1354, 2009.
[40] A. Inoue, "Bulk glassy and nonequilibrium crystalline alloys by stabilization of supercooled liquid: fabrication, functional properties and applications (Part 2)," Proceedings of the Japan Academy, Series B, vol. 81, no. 6, pp. 172-188, 2005.
[41] Y. Zou, Z. Qiu, C. Tan, Y. Wu, K. Li, and D. Zeng, "Microstructure and mechanical properties of Fe-based bulk metallic glass composites fabricated by selective laser melting," Journal of Non-Crystalline Solids, vol. 538, p. 120046, 2020.
[42] L. Zhang and H. Huang, "Micro machining of bulk metallic glasses: a review," The International Journal of Advanced Manufacturing Technology, vol. 100, no. 1-4, pp. 637-661, 2019.
[43] H. Liu, W. Lin, and M. Hong, "Surface coloring by laser irradiation of solid substrates," APL Photonics, vol. 4, no. 5, p. 051101, 2019.
[44] D. P. Bado, D. W. Clark, and D. A. Said, "Ultrafast Laser Micromachining Handbook," 1999-2018.
[45] L. Sobotova and M. Badida, "Laser marking as environment technology," Open Engineering, vol. 7, no. 1, pp. 303-316, 2017.
[46] J. Qi, K. Wang, and Y. Zhu, "A study on the laser marking process of stainless steel," Journal of Materials Processing Technology, vol. 139, no. 1-3, pp. 273-276, 2003.
[47] X. Ma et al., "Coloring stability analysis of nanosecond pulsed laser induced surface coloring on stainless steel," Optics & Laser Technology, vol. 123, p. 105936, 2020.
[48] W. Gao et al., "Investigations on the laser color marking of TC4," Optik, vol. 182, pp. 11-18, 2019.
[49] M. M. Li, C. R. Fagan, and A. Prasad, "Laser-colored sapphire material," ed: Google Patents, 2020.
[50] I. Boyd, J. Wilson, and J. West, "Laser-induced oxidation of silicon," Thin Solid Films, vol. 83, no. 4, pp. L173-L176, 1981.
[51] M. Wautelet and L. Baufay, "Laser-induced oxidation of thin cadmium and copper films," Thin Solid Films, vol. 100, no. 1, pp. L9-L12, 1983.
[52] A. P. Del Pino, J. Fernández-Pradas, P. Serra, and J. Morenza, "Coloring of titanium through laser oxidation: comparative study with anodizing," Surface and Coatings Technology, vol. 187, no. 1, pp. 106-112, 2004.
[53] S. K. Lawrence, D. P. Adams, D. F. Bahr, and N. R. Moody, "Mechanical and electromechanical behavior of oxide coatings grown on stainless steel 304L by nanosecond pulsed laser irradiation," Surface and Coatings Technology, vol. 235, pp. 860-866, 2013.
[54] K. Łęcka et al., "Effects of laser-induced oxidation on the corrosion resistance of AISI 304 stainless steel," Journal of Laser Applications, vol. 28, no. 3, p. 032009, 2016.
[55] A. J. Antończak, D. Kocoń, M. Nowak, P. Kozioł, and K. M. Abramski, "Laser-induced colour marking—Sensitivity scaling for a stainless steel," Applied Surface Science, vol. 264, pp. 229-236, 2013.
[56] E. Amara, F. Haïd, and A. Noukaz, "Experimental investigations on fiber laser color marking of steels," Applied Surface Science, vol. 351, pp. 1-12, 2015.
[57] A. P. Del Pino, P. Serra, and J. Morenza, "Coloring of titanium by pulsed laser processing in air," Thin solid films, vol. 415, no. 1-2, pp. 201-205, 2002.
[58] C. Langlade, A. Vannes, J. Krafft, and J. Martin, "Surface modification and tribological behaviour of titanium and titanium alloys after YAG-laser treatments," Surface and Coatings Technology, vol. 100, pp. 383-387, 1998.
[59] A. R. Parker, "515 million years of structural colour," Journal of Optics A: Pure and Applied Optics, vol. 2, no. 6, p. R15, 2000.
[60] M. Birnbaum, "Semiconductor surface damage produced by ruby lasers," Journal of Applied Physics, vol. 36, no. 11, pp. 3688-3689, 1965.
[61] Z. Ou, M. Huang, and F. Zhao, "Colorizing pure copper surface by ultrafast laser-induced near-subwavelength ripples," Optics express, vol. 22, no. 14, pp. 17254-17265, 2014.
[62] A. Y. Vorobyev and C. Guo, "Colorizing metals with femtosecond laser pulses," Applied Physics Letters, vol. 92, no. 4, p. 041914, 2008.
[63] J. Yao et al., "Selective appearance of several laser-induced periodic surface structure patterns on a metal surface using structural colors produced by femtosecond laser pulses," Applied Surface Science, vol. 258, no. 19, pp. 7625-7632, 2012.
[64] M. Rohloff, A. Rosenfeld, J. KrŘger, and J. Bonse, "Dynamics of the formation of laser-induced periodic surface structures on dielectrics and semiconductors upon femtosecond laser pulse irradiation sequences," Applied Physics A, vol. 110, no. 3, pp. 553-557, 2013.
[65] G. Li et al., "Femtosecond laser color marking stainless steel surface with different wavelengths," Applied Physics A, vol. 118, no. 4, pp. 1189-1196, 2015.
[66] Z. Guosheng, P. Fauchet, and A. Siegman, "Growth of spontaneous periodic surface structures on solids during laser illumination," Physical Review B, vol. 26, no. 10, p. 5366, 1982.
[67] J. Sipe, J. F. Young, J. Preston, and H. Van Driel, "Laser-induced periodic surface structure. I. Theory," Physical Review B, vol. 27, no. 2, p. 1141, 1983.
[68] K. Ahmmed, C. Grambow, and A.-M. Kietzig, "Fabrication of micro/nano structures on metals by femtosecond laser micromachining," Micromachines, vol. 5, no. 4, pp. 1219-1253, 2014.
[69] J. F. Young, J. Preston, H. Van Driel, and J. Sipe, "Laser-induced periodic surface structure. II. Experiments on Ge, Si, Al, and brass," Physical Review B, vol. 27, no. 2, p. 1155, 1983.
[70] J. Reif, F. Costache, M. Henyk, and S. V. Pandelov, "Ripples revisited: non-classical morphology at the bottom of femtosecond laser ablation craters in transparent dielectrics," Applied Surface Science, vol. 197, pp. 891-895, 2002.
[71] A. Borowiec and H. Haugen, "Subwavelength ripple formation on the surfaces of compound semiconductors irradiated with femtosecond laser pulses," Applied Physics Letters, vol. 82, no. 25, pp. 4462-4464, 2003.
[72] M. Huang, F. Zhao, Y. Cheng, N. Xu, and Z. Xu, "Origin of laser-induced near-subwavelength ripples: interference between surface plasmons and incident laser," ACS nano, vol. 3, no. 12, pp. 4062-4070, 2009.
[73] A. Pan, W. Wang, X. Mei, H. Yang, and X. Sun, "The formation mechanism and evolution of ps-laser-induced high-spatial-frequency periodic surface structures on titanium," Applied Physics B, vol. 123, no. 1, p. 21, 2017.
[74] C. Florian, S. V. Kirner, J. Krüger, and J. Bonse, "Surface functionalization by laser-induced periodic surface structures," Journal of Laser Applications, vol. 32, no. 2, p. 022063, 2020.
[75] K. A. Willets and R. P. Van Duyne, "Localized surface plasmon resonance spectroscopy and sensing," Annu. Rev. Phys. Chem., vol. 58, pp. 267-297, 2007.
[76] J. Z. Zhang and C. Noguez, "Plasmonic optical properties and applications of metal nanostructures," Plasmonics, vol. 3, no. 4, pp. 127-150, 2008.
[77] E. Stratakis, V. Zorba, M. Barberoglou, C. Fotakis, and G. Shafeev, "Laser writing of nanostructures on bulk Al via its ablation in liquids," Nanotechnology, vol. 20, no. 10, p. 105303, 2009.
[78] V. V. Zhakhovskii, N. A. Inogamov, and K. Nishihara, "New mechanism of the formation of the nanorelief on a surface irradiated by a femtosecond laser pulse," JETP letters, vol. 87, no. 8, pp. 423-427, 2008.
[79] A. Pereira et al., "Surface nanostructuring of metals by laser irradiation: effects of pulse duration, wavelength and gas atmosphere," Applied physics A, vol. 79, no. 4-6, pp. 1433-1437, 2004.
[80] A. Y. Vorobyev and C. Guo, "Direct femtosecond laser surface nano/microstructuring and its applications," Laser & Photonics Reviews, vol. 7, no. 3, pp. 385-407, 2013.
[81] P. Fan et al., "Angle-independent colorization of copper surfaces by simultaneous generation of picosecond-laser-induced nanostructures and redeposited nanoparticles," Journal of Applied Physics, vol. 115, no. 12, p. 124302, 2014.
[82] A. Y. Vorobyev and C. Guo, "Femtosecond laser nanostructuring of metals," Optics express, vol. 14, no. 6, pp. 2164-2169, 2006.
[83] A. Vorobyev and C. Guo, "Multifunctional surfaces produced by femtosecond laser pulses," Journal of Applied Physics, vol. 117, no. 3, p. 033103, 2015.
[84] V. V. Iyengar, B. K. Nayak, and M. C. Gupta, "Ultralow reflectance metal surfaces by ultrafast laser texturing," Applied optics, vol. 49, no. 31, pp. 5983-5988, 2010.