臺灣博碩士論文加值系統

銲料在電子構裝中扮演著相當重要的角色，主要是用來連接電子元件與電路板並傳遞其訊號。然而目前是以Sn-Ag-Cu無鉛銲料最為被廣泛使用。本研究為添加0至80 wt.%的Sn-10 wt.% Cu (S10C) 於Sn-3.0 wt.% Ag-0.5 wt.% Cu (SAC) 中，以其所形成之複合銲料分別進行顯微結構觀察、熱分析、潤濕性質以及流動現象觀察，探討添加S10C對SAC之影響。
在顯微結構方面，相同的回銲次數下，隨著S10C的添加比例減少，Cu6Sn5相所佔的比例有所下降。然而相同的S10C添加比例下，隨回銲次數的上升，Cu6Sn5相的比例也有所下降，也會使Ag3Sn相的生成有所被抑制。但當SAC含量高達80%時，因SAC所占比例較多，所以對於Ag3Sn相的生成影響較為不明顯。在溶解的實驗中，可看到當片狀的S10C於230°C的SAC湯中，經過1分鐘的恆溫，其依舊可以保持片狀的形狀。當增加恆溫時間至5分鐘或是調高溫度至240°C、250°C，皆會因S10C的部分熔化，導致其Cu6Sn5相擴散。
在熱分析方面，不同S10C添加比例的升溫曲線中，對於SAC的液化溫度是沒有太明顯的影響。但在冷卻曲線下可以明顯的觀察到，當S10C所添加的比例上升時，是有助於SAC液相線溫度的提升。在同一S10C添加比例下，當回銲次數增加到第二次，會使液化溫度下降。並且發現到回銲次數上升，S10C的峰值有變小，SAC的峰值則有變大的情況。然後因為有S10C的添加，會降低SAC過冷現象的程度。在潤濕性質方面，隨S10C的增加會降低其潤濕性質。流動性方面一樣隨著S10C的含量增加，而大幅降低其流動性。然而潤濕時間和黏度之間有正相關性。
經過多方面的觀察及分析，在SAC中添加S10C可有效的提高液相線溫度，並且可以有效的降低其流動性，預期可以改善多次回銲後銲點位移的缺點。然而在潤濕性測試中，當S10C比例達50wt.%以上對其潤濕性會大幅下降。因此綜合以上結果，SAC-20S10C為此系統中最佳銲料組合。

Solder plays an important role in the electronics industry. It is mainly for connecting electronic components to boards and transmitting signals. Currently, Sn-Ag-Cu is the most widely used. In this study, the composite solders were produced by intermixing 0-80 wt.% Sn-10 wt.% Cu (S10C) into Sn-3.0 wt.% Ag-0.5 wt.% Cu (SAC). The objective of this study is to investigate the effects of the addition of S10C on composite solders' microstructure, thermal property, wettability and fluidity.
The microstructure of composite solders shows that under the same reflowing times, the content of Cu6Sn5 phase increases with increasing the content of S10C. However, at the same composite solders, the content of Cu6Sn5 decreases with increasing the reflowing times, which also causes the formation of Ag3Sn to be suppressed. When the content of SAC reaches to 80 wt.%, the impact is less for the formation of Ag3Sn. In the dissolution experiment, when the sheet-like S10C in the SAC soup is at 230 °C for 1 minute, it can keep the shape. When the time increases to 5 minutes at 230 °C or the temperature increases, S10C would partially melt, and then resulting in the diffusion of Cu6Sn5.
In the thermal analysis, the liquefaction temperature of SAC doesn’t obviously effect with increasing S10C. Under the cooling curve, the liquidus temperature of SAC increases with increasing the content of S10C. However, at the same content of S10C, when the reflowing time reaches to the second time, the liquefaction temperature decreased, and the peak value of S10C becomes small. Because of the addition of S10C, the supercooling phenomenon would decrease. In the wetting properties, the wettability becomes worse with increasing content of S10C. In the fluidity experiment, the fluidity decreased with increasing content of S10C. There is a positive correlation between wetting time and viscosity.
Overall, the addition of S10C in SAC can effectively improve the liquidus temperature, and can effectively reduce its fluidity. It is expected to improve the shortcomings of solder joint displacement after multiple reflow. In the wetting properties, when the content of S10C reaches to 50 wt.%, the wettability would decrease obviously. Based on the above results, SAC-20S10C is the best composite solders in this system.

摘要i
Abstractiii
誌謝v
目錄vii
圖目錄ix
表目錄xii
第一章、前言1
第二章、文獻回顧3
2-1 電子構裝技術3
2-1.1電子構裝簡介3
2-1.2 回銲技術5
2-2無鉛銲料7
2-2.1 無鉛銲料介紹7
2-2.2 錫(Sn)9
2-2.3 錫-銅(Sn-Cu)9
2-2.4 錫-銀-銅(Sn-Ag-Cu)10
2-3 複合銲料相關研究文獻12
2-4 複合銲料性質分析15
2-4.1 熱分析15
2-4.2 溶解性質17
2-4.3 濕潤性質18
第三章、實驗方法20
3-1 銲料製備20
3-2 熱分析21
3-3 金相處理23
3-4 複合銲料觀察與分析23
3-5 溶解分析24
3-6 濕潤性質分析25
3-7 流動現象觀察27
第四章、結果與討論29
4-1 熱分析29
4-2 不同回銲次數後金相觀察40
4-3 溶解實驗金相觀察51
4-4 潤濕性質分析55
4-4.1潤濕性分析與計算55
4-4.2 SAC-xS10C銲料潤濕性質57
4-5 SAC-xS10C銲料流動現象觀察64
第五章、結論65
第六章、參考文獻67

[1] H. Y. Hsiao, C. M. Liu, H. W. Lin, T. C. Liu, C. L. Lu, Y. S. Huang, K. N. Tu, “Unidirectional growth of microbumps on (111)-oriented and nanotwinned Copper,” Science, 336(6084) (2012) 1007-1010
[2] C. M. L. Wu, D. Q. Yu, C. M. T. Law, L. Wang, “Properties of lead-free solder alloys with rare earth element additions,” Materials Science and Engineering: R: Reports, 44(1) (2004) 1-44
[3] “WEEE Regulations” EU-Directive 96/EC, (2002)
[4] “RoHS Regulations” EU-Directive 95/EC, (2002)
[5] H. Hao, Y. Shi, Z. Xia, Y. Lei, F. Guo, “Microstructure evolution of SnAgCuEr lead-free solders under high temperature aging,” Journal of Electronic Materials, 37(1) (2008) 2-8
[6] K. W. Moon, W. J. Boettinger, U. R. Kattner, F. S. Biancaniello, C. A. Handwerker, “Experimental and thermodynamic assessment of Sn-Ag-Cu solder alloys,” Journal of electronic materials, 29(10) (2000) 1122-1136
[7] D. P. Seraphim, R. C. Lasky, C. Y. Li, “Principles of electronic packaging,” McGraw-Hill College, New York, (1989)
[8] J. H. Lau, C. P. Wong, W. Nakayama, J. L. “Prince, electronic packaging: design, materials, process, and reliability,” McGraw-Hill, New York, (1998)
[9] 田民波/著、顏怡文/教訂，「半導體電子元件構裝技術」，五南圖書出版社，台北 (2005)
[10] J. E. Morris, Workshop, “The design and processing technology of electronic Packaging,” (1997)
[11] 林定皓，「電子構裝技術概論」，台灣電路板協會，(2010)
[12] E. H. Amalua, W. K. Lau, N. N. Ekere, R. S. Bhatti, S. Mallik, K. C. Otiaba, G. Takyi, “A study of SnAgCu solder paste transfer efficiency and effects of optimal reflow profile on solder deposits,” Microelectronic Engineering, 88(7) (2011) 1610-1617
[13] M. Abtew, G. Selvaduray, “Lead-free solders in microelectronics,” Materials Science and Engineering: R: Reports, 27(5-6) (2000) 95-141.
[14] K. N. Tu, J. C. M. Li, “Spontaneous whisker growth on lead-free solder finishes,” Materials Science and Engineering: A, 409(1-2) (2005) 131-139.
[15] K. Fakpan, R. Canyook, “Effects of Sb and Zn addition on mechanical properties and corrosion resistance of Sn-Ag-Cu Solders,” Key Engineering Materials, 728 (2017) 129-134
[16] N. C. Lee, “Getting ready for lead-free solders,” Soldering & surface mount technology, 9(2) (1997) 65-69
[17] 魏弘堯，「¬在BGA製程中以銦作為UBM層對接點界面型態與機械性質之探討」，碩士論文，國立台灣科技大學材料究所，(2006)
[18] S. K. Kang, D. Y. Shih, D. Leonard, D. W. Henderson, T. Gosselin, S. I. Cho, W. K. Choi, “Controlling Ag3Sn plate formation in near-ternary-eutectic Sn-Ag-Cu solder by minor Zn alloying,” JOM, 56(6) (2004) 34
[19] I. E. Anderson, “Development of Sn-Ag-Cu and Sn-Ag-Cu-X alloys for Pb-free electronic solder applications,” Journal of Materials Science: Materials in Electronics, 18(1-3) (2007) 55-76
[20] N. Saunders, A. P. Miodownik, “ASM Handbook vol. 3 Alloy Phase Diagrams,” edited by H. Baker, Materials Park, Ohio: ASM International, (1990)
[21] I. Karakaya, W. T. Thompson, “ASM Handbook vol. 3 Alloy Phase Diagrams,” edited by H. Baker, ASM International, Materials Park, Ohio, (1987)
[22] K. S. Kim, S. H. Huh, K. Suganuma, “Effects of cooling speed on microstructure and tensile properties of Sn-Ag-Cu alloys,” Materials science and engineering: a, 333(1-2) (2002) 106-114
[23] S. H. Huh, K. S. Kim, K. Suganuma, “Effect of Ag addition on the microstructural and mechanical properties of Sn-Cu eutectic solder,” Materials Transactions, 42(5) (2001) 739-744
[24] F. Guo, “Composite-lead free electronic solders,” Journal of Materials Science: Materials in Electronics, 18(1-3) (2007) 129-145
[25] S. Y. Hwang, J. W. Lee, Z.H. Lee, “Microstructure of a lead-free composite solder produced by an in-situ process,” Journal of Electronic Materials, 31(11) (2002) 1304-1308
[26] D. C. Lin, T. S. Srivatsan, G. X. Wang, R. Kovacevic, “Microstructural development of a rapidly cooled eutectic Sn-3.5% Ag solder reinforced with copper powder,” Powder Technology, 166(1) (2006) 38-46
[27] B. I. Noh, J. H. Choi, J. W. Yoon, S. B. Jung, “Effect of cerium content on wettability, microstructure and mechanical properties of Sn-Ag-Ce solder alloys,” Journal of Alloys and Compounds, 499(2) (2010) 154-159.
[28] P. Babaghorbani, S. M. L. Nai, M. Gupta, “Reinforcements at nanometer length scale and the electrical resistivity of lead-free solders,” Journal of Alloys and Compounds, 478(1-2) (2009) 458-461
[29] A. Nadia, A. S. M. A. Haseeb, “Effect of addition of copper particles of different size to Sn-3.5Ag solder,” Journal of Materials Science Materials in Electronics, 23(1) (2012) 86-93
[30] H. T. Lee, Y. H. Lee, “Adhesive strength and tensile fracture of Ni particles enhanced Sn-Ag composite solder joint,” Materials Science and Engineering: A, 419(1-2) (2006) 172-180.
[31] M. He, N. D. Leon, V. L. Acoff, “Effect of Bi on the microstructure and tensile behavior of Sn-3.7Ag solders,” Soldering & Surface Mount Technology, 22(3) (2010) 4-9
[32] L. Zhang, W. Tao, J. Liu, Y. Zhang, Z. Cheng, C. Andersson, Y. Gao, Q. Zhai, “Manufacture, microstructure and microhardness analysis of Sn-Bi lead-free solder reinforced with Sn-Ag-Cu nano-particles,” International Conference on Electronic Packaging Technology& High Density Packaging (ICEPT-HDP), (2008) 1-5
[33] B. An, C. M. L. Wu, “Evaluation of wettability of composite solder alloy reinforced with silver and copper particles,” International Conference on Electronic Packaging Technology (ICEPT), (2007) 1-6.
[34] K. Bukat, M. Koscielski, J. Sitek, M. Jakubowska, A. Mlozniak, der “Silver nanoparticles effect on the wettability of Sn-Ag-Cu sol pastes and solder joints microstructure on copper,” Soldering & Surface Mount Technology, 23(3) (2011) 150-160.
[35] M. Koscielski, K. Bukat, M. Jakubowska, A. Mlozniak, “Application of silver nanoparticles to improve wettability of SnAgCu solder paste,” International Spring Seminar on Electronics Technology (ISSE), (2010) 473-477
[36] P. Liu, P. Yao, J. Liu, “Evolution of the interface and shear strength between SnAgCu-xNi solder and Cu substrate during isothermal aging at 150°C,” Journal of Alloys and Compounds, 486(1-2) (2009) 474-479
[37] M. M. Arafat, A. S. M. A. Haseeb, “Interfacial reaction and dissolution behavior of Cu substrate in molten Sn-3.8Ag-0.7Cu-nano Mo composite solder,” Electronics Packaging Technology Conference (EPTC) (2009) 953-956
[38] M. M. Arafat, A. S. M. A. Haseeb, Mohd Rafie Johan, “Interfacial reaction and dissolution behavior of Cu substrate in molten Sn-3.8Ag-0.7Cu in the presence of Mo nanoparticles,” Soldering & Surface Mount Technology, 23(3) (2011) 140-149
[39] V. Sivasubramaniam, N. S. Bosco, J. J. Rusch, J. Cugnoni, J. Botsis, “Interfacial intermetallic growth and strength of composite lead-free solder alloy through isothermal aging”, Journal of Electronic Materials, 37(10) (2008) 1598-1604.
[40] C. P Peng, J. Shen, W. D. Xie, J. Chen, C. P. Wu, X. C. Wang, “Influence of minor Ag nano-particles additions on the microstructure of Sn30Bi0.5Cu solder reacted with a Cu substrate,” Journal of Materials Science Materials in Electronics, 22(7) (2011) 797-806
[41] Q. Chen, G. Li, “Effect of dopants on wettability and microstructure evolution of lead-free solder joints,” International Conference on Electronic Packaging Technology & High Density Packaging (ICEPT-HDP) (2010) 314-318
[42] S. M. L. Nai, M. Gupta, J. Wei, “Development of novel lead-free solder composites using carbon nanotube reinforcements,” International Journal of Nanoscience, 4 (2005) 423-429.
[43] S. M. L. Nai, J. Wei, M. Gupta, “Multi-walled carbon nanotubes reinforced lead-free solder composites,” SIMTech technical report, 9(4) (2008) 195-199.
[44] A. Sharif , Y. C. Chan, “Dissolution kinetics of BGA Sn–Pb and Sn–Ag solders with Cu substrates during reflow,” Materials Science and Engineering: B, 106(2) (2004) 126-131
[45] M. L. Huang, T. Loeher, A. Ostmann, H. Reichl, “Role of Cu in dissolution kinetics of Cu metallization in molten Sn-based solders,” Applied Physics Letter, 86 (2005)
[46] J. W. Han, H. G. Lee, J. Y. Park, “Numerical simulation of dynamic wetting behavior in the wetting balance method,” Materials Transactions, 43(8) (2002) 1816-1820
[47] J. Y. Park, C. S. Kang, J. P. Jung, “The analysis of the withdrawal force curve of the wetting curve using 63Sn-37Pb and 96.5Sn-3.5Ag eutectic solders,” Journal of Electronic Materials, 28(11) (1999) 1256-1262
[48] F. G. Yost, “The Metal Science of Joining,” edited by M. J. Cieslak (1992)
[49] S. W. Chen, C. C. Lin, C. M. Chen, “Determination of the melting and solidification characteristics of solders using differential scanning calorimetry,” Metallurgical and Materials Transactions A, 29(7) (1998) 1965-1972
[50] M. M. Billah, K. M. Shorowordi, A. Sharif, “Effect of micron size Ni particle addition in Sn-8Zn-3Bi lead-free solder alloy on the microstructure, thermal and mechanical properties,” Journal of Alloys and Compounds, 585 (2014) 32-39
[51] K. M. Kumar, V. Kripesh, A. A.O. Tay, “Single-wall carbon nanotube (SWCNT) functionalized Sn-Ag-Cu lead-free composite solders,” Journal of Alloys and Compounds, 450 (2008) 229-237
[52] W. Zhai, W.L. Wang, D.L. Geng, B. Wei, “A DSC analysis of thermodynamic properties and solidification characteristics for binary Cu–Sn alloys,” Acta Materialia, 60 (2012) 6518–6527
[53] 傅淑玫，「¬添加多壁奈米碳管於Sn-3.0Ag-0.5Cu無鉛銲料之性質研究」，碩士論文，國立台灣科技大學材料究所，(2011)