CuおよびCu‐Sn系化合物のSn‐Pbはんだ濡れ性解析

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1 61 Wettability of Cu and Cu-Sn Intermetallic Compound by Sn-Pb Solder Alloy Hisaaki Takao, Nobuyuki Yamamoto, Hideo Hasegawa CuCu-Sn Cu 150 C 2h55nmCu 2 O Cu Cu-Sn 5nm Cu-Sn Cu SnCu-Sn Wettability of Cu and Cu-Sn intermetallic compound was investigated in terms of its surface oxidation. Cu 2 O layer of about 55nm thick was formed on the surface of Cu during the heat treatment at 150 C for 2h in the air, which had a little influence on its wettability. On the other hand, the surface oxidation of Cu-Sn intermetallic compound caused an appreciable reduction in its wettability. The surface of the oxidized Cu-Sn intermetallic compound was covered with an amorphous layer of about 5nm thick. The galvanostatic coulometry analysis suggested that the amorphous layer was a Cu-Sn complex oxide, which was more difficult to reduce owing to its cathodic potential lower than Cu 2 O or SnO. Cu Cu-Sn Cu Cu Sn-Pb HAL ( Hot Air Levelling ) µm Cu R&D Vol. 31 No. 4 ( )

2 62 / Cu Cu-Sn ( Cu-Sn ) Cu-Sn Cu-Sn ( Sn Pb ) Cu-Sn Cu-Sn Cu-Sn ( SEM ) X ( XRD ) ( AES ) X ( XPS ) ( TEM ) Cu 150 C 2h JIS Z 3197 ( S ) (1) ( D H ) S = 100 (%) (1) D D : ( ) H : 63Sn-37Pb ( mass% ) ( Cu Cu-Sn ) ( mm ) 230 C30s JIS C 0053 ( ) ( ) ( Cu Cu ) Cu-Sn Cu ( 1N HCl ) Cu-Sn (a) ( 150 C 95h ) / Cu ( ) / Cu Cu 6 Sn 5 Cu Cu 3 Sn Cu 6 Sn 5 4µm Cu 3 Sn 1µm Fig. 2(b) Cu-Sn ( SEM ) 2 4µm Cu 6 Sn 5 Cu Cu-Sn Preparation of Cu-Sn intermetallic compound. R&D Vol. 31 No. 4 ( )

3 63 ( ) ( mm )2mm10mm/s 10s ( SEM ) X ( XRD ) ( AES ) X ( XPS ) ( TEM ) Tench, D. M. ( ph 8.4 ) Pt ( 20µA / cm 2 ) ( SCE ) ( mm ) ( 150 C 2h ) Sn ( 99.99% ) ( 150 C 2h ) Cu Cu-Sn ( S ) Cu 88% 85% Cu Cu-Sn Microstructure of Cu-Sn intermetallic compound. (a) Optical micrograph of the cross-sectional view of 63Sn-37Pb/Cu interface after heat-treatment, (b) SEM micrograph of Cu-Sn intermetallic compound after removing the solder. Typical wetting curve in meniscograph test. R&D Vol. 31 No. 4 ( )

4 64 92% Cu % 71% (a) (b) ( 150 C 2h ) Cu Cu Cu Cu (a) (b) Cu-Sn Cu-Sn Cu-Sn CuCu-Sn ( ) Wetting curves of Cu. (a) As fabricated, (b) Oxidized at 150 C for 2h in air. Solder spreading on Cu and Cu-Sn intermetallic compound. Wetting curves of Cu-Sn intermetallic compound. (a) As fabricated, (b) Oxidized at 150 C for 2h in air. R&D Vol. 31 No. 4 ( )

5 65 Cu-Sn Cu Cu Cu-Sn Cu Cu-Sn Wetting time of Cu and Cu-Sn intermetallic compound. Cu 250 C 150 C 2h 150 C 200 C 230 C 30s Cu-Sn Cu-Sn 150 C 200 C 77% 230 C 64% 150 C ( ) Cu- Wetting force of Cu and Cu-Sn intermetallic compound. Solder spreading on Cu-Sn intermetallic compound. R&D Vol. 31 No. 4 ( )

6 66 Sn 200 C30s Cu-Sn ( 25 C 40 60%RH ) Cu-Sn 92% 6 91% Cu-Sn (a) (b) ( 150 C 2h ) Cu AES Cu nm ( Fig. 10(a) ) 50nm ( Fig. 10(b) ) XRDCu 2 O (a) (b) Cu-Sn Cu ( Fig. 10 ) Cu-Sn Sn nm SEM XRD Cu Sn Cu SnCu-Sn ( 150 C 2h ) CuSn AES depth profiles of Cu. (a) As fabricated, (b) Oxidized at 150 C for 2h in air. AES depth profiles of Cu-Sn intermetallic compound. (a) As fabricated, (b) Oxidized at 150 C for 2h in air. R&D Vol. 31 No. 4 ( )

7 67 ( ) ( ) Cu ( Fig. 12(a) ) 2 ( : 0.35V 0.48V ) XRD Cu 2 O 0.48V ( ) Cu 2 O 0.35V CuO ( Cu(OH) 2 ) Cu 2 O 55nm CuO 0.3nm Sn ( Fig. 12(b) ) SnO 0.86V 15nm Cu-Sn CuSn ( Fig. 12 ) 0.71V 0.95V 2 Fig. 12 Fig. 13 Cu-Sn ( 0.35V 0.48V ) ( 0.86V ) Cu Sn Cu-Sn Cu-Sn ( 0.95V ) Cu ( Fig. 4 7 ) Sn ( Sn : 92% : 200 C ) Cu-Sn (a) (b) Cu-Sn TEM 150 C Galvanostatic coulometry curves. (a) Oxidized Cu, (b) Oxidized Sn, at 150 C for 2h in air. Galvanostatic coulometry curves for Cu-Sn intermetallic compound. (a) As fabricated, (b) Oxidized at 150 C for 2h in air. R&D Vol. 31 No. 4 ( )

8 68 2h ( Fig. 14(a) ) ( Fig. 14(b) ) Cu-Sn 3 5nm Cu-Sn nm Cu-Sn Cu-Sn XPS Cu-Sn 150 C 2h Cu C Cu Sn OCu Sn Cu-Sn Surface analysis of Cu-Sn intermetallic compound. TEM images of the surface of Cu-Sn intermetallic compound. (a) As fabricated, (b) Oxidized at 150 C for 2h in air. Sn Cu Matal Oxide O C As fabricated After oxidized Halogen flux treated after oxidized Halogen free flux treated after oxidized (at%) R&D Vol. 31 No. 4 ( )

9 69 Cu / Cu Cu-Sn CuCu-Sn (1) Cu150 C 2h 55nmCu 2 O Cu (2) Cu-Sn ( 3 5nm ) (3) Cu-SnCu SnCu-Sn Cu-Sn 1 1),,,, :, (1993), ) : Uyemura Tech. Rep., No.30(1994), ) Billot, M. and Clement, S. : Tin and its Uses, (1982), 1 3 4) Yenawine, D. L., Dunnigan, J. S. and Howarth, R. A. : 7th Soldering Technol. Seminar Proc., (1983), ) Davis, P. E., Warwick, M. E. and Kay, P. J. : Plat. and Surf. Finish., (1982), ) Davis, P. E., Warwick, P. E. and Muckett, S. J. : Plat. and Surf. Finish., (1983), ) Sunwoo, A. J., Hayashigatani, H., Morris, J. W., Jr. and Lucey, G. K., Jr. : JOM, June, (1991), ) Sunwoo, A. J., Morris, J. W., Jr. and Lucey, G. K., Jr. : Metall. Trans. A, (1992), ) Sunwoo, A. J., Morris, J. W., Jr. and Lucey, G. K., Jr. : Circuit World, (1992), ) Sunwoo, A. J., Morris, J. W., Jr. and Lucey, G. K., Jr. : J. Electro. Mat., (1992), ), : 35, (1992), ), :,, (1991), ) Tench, D. M. and Anderson, D. A. : Plat. Surf. Finish., (1990), R&D Vol. 31 No. 4 ( )

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