銅錳合金通常被應用於低電阻且低電阻溫度係數(TCR)的電阻材料，然而目前的研究與開發主要集中在以濺鍍法(sputter)沉積之薄膜材料，也因其真空設備的限制而導致製造成本居高不下，所以亟需開發其它製程以突破目前困境。本論文將以各種電化學沉積法製備銅錳合金，並以掃描式電子顯微鏡(SEM)、X光繞射分析儀(XRD)、化學分析電子光譜儀(XPS)、拉曼光譜分析儀(Raman)與四點探針量測分別應用於觀察表面型態、分析材料結構、確認化學能態、判斷原子鍵結與量測電性等各方面進行討論。

在論文中，我們在氧化鋁基板上以網版印刷法準備鋁厚膜以作為犧牲層，接著在80度下以置換法將鋁厚膜轉換成銅厚膜，實驗結果顯示在75分鐘的條件下可將鋁幾乎換為銅。再來使用了電鍍法將錳沉積到了置換完的銅厚膜上，從掃描式電子顯微鏡與X光繞射分析儀的結果可知，以1.6V的電壓沉積10分鐘可獲得高品質且銅錳比接近9:1的錳膜。最後以化鍍法再次披覆一層銅於表面，並完成銅錳銅的三明治結構。第二階段會以在常壓下退火使銅錳之間互相擴散成合金相，然而氮氣退火會造成錳氧化並隨著溫度提高而逐漸嚴重，因此最後採用氮氫氣作為退火氣氛。從化學分析電子光譜儀和拉曼光譜分析儀都確認了氮氫退火可大幅度地降低錳氧化的可能性。電性量測表明，以氮氣退火的樣品顯示出接近銅的電阻與電阻溫度係數，而在氮氫環境下退火的樣品會從退火溫度的提高而降低電阻溫度係數和提高電阻，而在900度退火條件下可達到150ppm的電阻溫度係數。

Copper-manganese (Cu-Mn) alloys are usually used in resistance materials with low resistance and low temperature coefficient of resistance (TCR). However, current research and development are mainly focused on thin film materials deposited by sputtering method, which is also restricted the cost due to its vacuum equipment. As a result, the manufacturing cost remains high, so there is an urgent need to develop other manufacturing processes to break through the current morass. We would manufacture copper-manganese alloys by various electrochemical deposition methods, and use scanning electron microscope (SEM), X-ray diffraction analyzer (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectrometer and four-point probe measurement, which are used to observe the surface morphology, analyze the material structure, confirm the chemical energy state, judge the atom bonding, and measure electrical properties, respectively.

In the study, we prepared the Al thick film as the sacrificial layer by screen printing on the Al2O3 substrate, and then transformed the Al thick film into the Cu thick film by the replacement method at 80C. The experimental results showed that the Al could almost be replaced by copper after 75minutes. Then the electroplating method was used to deposit Mn on the as-replaced Cu film. Based on the results of SEM and XRD, it could be seen that high quality and desired Cu-Mn 9:1 ratio could be obtained by depositing at 1.6V for 10 minutes. Finally, another Cu layer was coated on the surface again by electroless plating to complete the sandwich structure of Cu-Mn-Cu. In the second stage, annealing under normal pressure would make Cu and Mn interdiffusion into the alloy phase. However, nitrogen atmosphere will cause oxidation of Mn and gradually become more serious as the temperature rises. Therefore, nitrogen and hydrogen are used as the annealing atmosphere. Both XPS and Raman confirmed that nitrogen-hydrogen annealing could extremely reduce the possibility of manganese oxidation. Electrical measurements show that the sample annealed with nitrogen shows a resistance and temperature coefficient close to that of copper, while the sample annealed in a nitrogen-hydrogen environment will decrease the temperature coefficient of resistance and increase the resistance from an increase in the annealing temperature, and at 900C. The TCR of 150 ppm could be reached under the given annealing condition.

[1] Savov, L., & Janke, D. (2000). Evaporation of Cu and Sn from induction-stirred iron-based melts treated at reduced pressure. ISIJ international, 40(2), 95-104.
[2] Mech, K., Kowalik, R., & Żabiński, P. (2011). Cu thin films deposited by DC magnetron sputtering for contact surfaces on electronic components. Archives of Metallurgy and materials, 56(4), 903-908.
[3] Nicols, C. A. (1996). Ionized physical vapor disposition of Cu for high aspect ratio Damascene trench fill application. J. Vac. Sci. Technol. B, 14, 3270.
[4] Lee, C. H., Shen, K. H., Ku, T. K., Luo, C. H., Tao, C. C., Chou, H. W., & Hsia, C. (2000, June). CVD Cu technology development for advanced Cu interconnect applications. In Proceedings of the IEEE 2000 International Interconnect Technology Conference (Cat. No. 00EX407) (pp. 242-244). IEEE.
[5] Baghi, R., Peterson, G. R., & Hope-Weeks, L. J. (2013). Thermal tuning of advanced Cu sol–gels for mixed oxidation state Cu/Cu x O y materials. Journal of Materials Chemistry A, 1(36), 10898-10902.
[6] Cheng, H. Y., Tran, D. P., Tu, K. N., & Chen, C. (2021). Effect of deposition temperature on mechanical properties of nanotwinned Cu fabricated by rotary electroplating. Materials Science and Engineering: A, 811, 141065.
[7] Wu, C. Y., Wu, C. T., Lee, W. H., Chang, S. C., & Wang, Y. L. (2012). A study on annealing mechanisms with different manganese contents in CuMn alloy. Journal of alloys and compounds, 542, 118-123.
[8] Lee, H. Y., He, C. W., & Lee, Y. C. (2019). The Effect of Yttrium Addition on the Microstructures and Electrical Properties of CuMn Alloy Thin Films. Advances in Materials Science and Engineering, 2019.
[9] Chuang, K. C., & Lee, W. H. (2021). Improvement on Conductivity for Thick Film Aluminum Paste. Journal of nanoscience and nanotechnology, 21(9), 4726-4734.
[10] Kuo, T. C., Kuo, C. R., & Lee, W. H. (2021). A Novel Method to Fabricate a Thick-Film Cu Electrode Fired in Air Through Printing Al Electrode and Reduction-Oxidation Substitution Reaction. IEEE Transactions on Components, Packaging and Manufacturing Technology, 11(3), 485-492.
[11] Fang, J. S., Sun, S. L., Cheng, Y. L., Chen, G. S., & Chin, T. S. (2016). Cu and Cu (Mn) films deposited layer-by-layer via surface-limited redox replacement and underpotential deposition. Applied Surface Science, 364, 358-364.
[12] Ding, L., Chen, C., Li, Q., Yuan, J., Li, H., Xue, Y., ... & Niu, Y. (2021). Process and theoretical research on electroplating Cu–Sn alloys of low Sn. Journal of Applied Electrochemistry, 1-13.
[13] Chen, S. T., & Chen, G. S. (2004). Characterization of ultrathin electroless barriers grown by self-aligned deposition on silicon-based dielectric films. Journal of the Electrochemical Society, 151(10), D99.
[14] Wu, Y. Q., & Sun, S. K. (2012). Microwave Assisted Eletroless Copper Plating on Carbon Nanotubes. In Advanced Materials Research (Vol. 399, pp. 741-746). Trans Tech Publications Ltd.
[15] Chen, Y. C., Liu, R. L. H., Chen, X. L., Shu, H. J., & Ger, M. D. (2011). Microwave-assisted activation for electroless nickel plating on PMMA microspheres. Applied surface science, 257(15), 6734-6740.
[16] Papaderakis, A., Mintsouli, I., Georgieva, J., & Sotiropoulos, S. (2017). Electrocatalysts prepared by galvanic replacement. Catalysts, 7(3), 80.
[17] Moon, G. D., Ko, S., Min, Y., Zeng, J., Xia, Y., & Jeong, U. (2011). Chemical transformations of nanostructured materials. Nano Today, 6(2), 186-203.
[18] Vuruna, M., Bucko, M., Radović, L., & Bajat, J. (2015). Manganese electrodeposition from urea-rich electrolyte. Macedonian Journal of Chemistry and Chemical Engineering, 34(2), 277-285.
[19] Sun, W., Kitchaev, D. A., Kramer, D., & Ceder, G. (2019). Non-equilibrium crystallization pathways of manganese oxides in aqueous solution. Nature communications, 10(1), 1-9.
[20] Jacobs, J. H., Hunter, J. W., Churchward, P. E., & KNOCKERBOCKER, R. (1946). Operation of the electrolytic manganese pilot plant at Boulder City, Nevada. US Bur. Mines Bull, 463.
[21] Haerifar, M., & Zandrahimi, M. (2013). Effect of current density and electrolyte pH on microstructure of Mn–Cu electroplated coatings. Applied surface science, 284, 126-132.
[22] Nacamulli, L., & Gileadi, E. (1983). Electrochemical properties of graphite fibre/epoxy composite electrodes. Journal of Applied Electrochemistry, 13(1), 73-78.
[23] von der Heiden, A., Bornhöfft, M., Mayer, J., & Martin, M. (2019). Oxygen diffusion in amorphous and partially crystalline gallium oxide. Physical Chemistry Chemical Physics, 21(8), 4268-4275.
[24] Liang, Y. C., & Chang, C. W. (2019). Preparation of orthorhombic WO3 thin films and their crystal quality-dependent dye photodegradation ability. Coatings, 9(2), 90.
[25] Mariappan, R., Ponnuswamy, V., & Suresh, P. (2012). Effect of doping concentration on the structural and optical properties of pure and tin doped zinc oxide thin films by nebulizer spray pyrolysis (NSP) technique. Superlattices and Microstructures, 52(3), 500-513.
[26] Dey, S., & Dhal, G. C. (2020). Synthesis of Hopcalite catalysts by various methods for improved catalytic conversion of carbon monoxide. Materials Science for Energy Technologies, 3, 377-389.
[27] Iijima, J., Fujii, Y., Neishi, K., & Koike, J. (2009). Resistivity reduction by external oxidation of Cu–Mn alloy films for semiconductor interconnect application. Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena, 27(4), 1963-1968.
[28] Misják, F., Nagy, K. H., Lobotka, P., & Radnóczi, G. (2014). Electron scattering mechanisms in Cu-Mn films for interconnect applications. Journal of Applied Physics, 116(8), 083507.
[29] Chiang, W. S., Huang, J. Q., Chen, P. C., Wu, P. W., Joi, A., & Dordi, Y. (2018). Pulse electrodeposition of copper-manganese alloy in deep eutectic solvent. Journal of Alloys and Compounds, 742, 38-44.