Abstract
In the flip-chip (FC) solder joint, solder alloys usually connect with Ni and Cu based under bump metallurgies (UBMs) at chip-side and substrate-side, respectively. The material selection for solder alloys and UBM material is a critical issue to affect the microstructure, phase formation, and the reliability of the solder joints. In this study, the interfacial reaction, microstructure variation, and impact reliability of Sn-based Pb-free solder joints with Ni, Cu, and novel Cu-Zn UBMs are discussed and categorized into six topics. (1) Microstructural variation and interfacial reaction in Ni/Sn-Ag-Cu/Ni assemblies with and without Ni doping Ni and Cu elements cross-interacted between the Cu and Ni UBMs during thermal aging and affected the interfacial reactions at both Cu and Ni sides. Dual-phased (Cu,Ni)6Sn5 intermetallic compounds (IMCs), which has high and low Ni concentration, formed at the solder/Ni interface. In contrast, thicker low-Ni (Cu,Ni)6Sn5 and thin (Cu,Ni)3Sn layers formed at the Cu side. The Ni doping into solder varied the microstructure of solder alloys and the formation of interfacial IMCs. The re-distribution of Ni and Cu was correlated to the formation mechanism of interfacial (Cu,Ni)6Sn5. (2) Effect of dual-phased (Cu,Ni)6Sn5 IMCs on the impact reliability of Sn-Ag-Cu/Ni solder joints By employing the high-speed shear impact test, the impact fracture morphology reveals that the interface of high-Ni (H)/low-Ni (L) (Cu,Ni)6Sn5 facilitates the crack nucleation within the IMC. It is believed that the crack propagation depends on the fracture toughness of interfacial IMCs. The indentation data shows that bulk H-(Cu,Ni)6Sn5 exhibits distinctly lower fracture toughness than bulk L-(Cu,Ni)6Sn5. In correlating the impact fracture behavior and mechanical properties of two kinds of (Cu,Ni)6Sn5, cracks tend to propagate through H-(Cu,Ni)6Sn5 due to the relatively low fracture toughness of H-(Cu,Ni)6Sn5. (3) Development of a novel Cu-Zn UBM for Pb-free solder joints To suppress the thicker IMCs and voids at the solder/Cu interface, the Cu-Zn alloy was designed for a novel UBM material. The interfacial reactions of Sn/Cu-xZn (x = 0, 15 and 30 at.%) solder joints were investigated. Interestingly, the growth of Cu-Sn IMCs was significantly reduced and no void was found in the Sn/Cu-Zn solder joints after thermal aging. Transmission electron microscopy (TEM) images and the field emission electron probe microanalyzer (FE-EPMA) analysis show that there are two types of Zn-rich phases, i.e. CuZn and Cu-Zn-Sn phases, to form in Sn/Cu-Zn joints. The formation mechanisms of IMCs were probed and proposed with regard to the thermodynamics and kinetics. (4) Liquid-state reaction of Sn-Ag-Cu solders and the novel Cu-Zn UBM During the reflow process, Cu and Zn atoms would dissolve from the Cu-Zn UBM into the molten solders, leading to the variation of the composition in the solders. Then, the composition variation further altered the microstructure of the solders. In comparison with the Sn-Ag-Cu/Cu, it was found that the coarser eutectic region and smaller Cu6Sn5 IMCs inside the solder matrix of Sn-Ag-Cu/Cu-Zn. In addition, the interfacial reaction was also affected by Zn dissolution. In this study, it was demonstrated that the microstructural variation and the phase evolution in the solder joints were controlled by the reflow time and the Zn concentration in the Cu-Zn UBM. (5) Characterization of the Cu6(Sn,Zn)5 intermetallic compound Cu6Sn5 is a dominant IMC at the Sn-based solder/Cu joint interface. The crystal structure of Cu6Sn5 varies with temperature. After reflow at 250 oC, the interfacial Cu6Sn5 revealed hexagonal structure (η-Cu6Sn5). During aging at 150 oC, hexagonal η-Cu6Sn5 would transform into monoclinic η’-Cu6Sn5. According to literature, the phase transformation between η’ and η would induce crack easily propagating through the Cu6Sn5 at the solder joint interface. In the novel solder/Cu-Zn joints, and Zn would dissolve into Cu6Sn5 to form the Cu6(Sn,Zn)5 IMC at the interface. X-ray diffraction and differential scanning calorimetry analyses show that doping small amounts of Zn into Cu6(Sn,Zn)5 can stabilize the hexagonal structure during the thermal aging process. Thermodynamic calculation also demonstrates that Zn can stabilize the hexagonal Cu6(Sn,Zn)5. (6) Application of Cu-Zn UBM on the Ni/Sn-Ag-Cu/Cu-Zn assemblies The feasibility of novel Cu-Zn UBM applied for the Ni/solder/Cu-Zn assemblies was also evaluated. In comparison with the Ni/Sn-Ag-Cu/Cu solder joint, Ni/Sn-Ag-Cu/Cu-Zn solder joints revealed thinner Cu6Sn5-based IMCs at both Ni/Sn-Ag-Cu and Sn-Ag-Cu/Cu-Zn interfaces after aging. (Cu,Ni)6(Sn,Zn)5/(Cu,Ni)6Sn5 dual-phase formed at the Ni side while (Cu,Ni)6(Sn,Zn)5 single-phase at the Cu-Zn side. The interfacial IMCs grew very slowly, and no void formed in these Zn-contained solder joints during thermal aging. Additionally, the dissolved Zn in the solder alloy reduced the elemental cross-interaction between the Ni and Cu-Zn substrates. The noticeable thermal stability of Ni/Sn-Ag-Cu/Cu-Zn solder joints is attributed to the Zn re-distribution retarding the reaction of Ni, Cu and Sn. Phase formation and IMCs suppression mechanisms in Ni/Sn-Ag-Cu/Cu-Zn solder joints were probed and discussed. In summary, novel Cu-Zn UBM shows lots of advantages for soldering, including: (I) reduction of Cu-Sn IMCs, (II) suppression of voids at the interface, (III) formation of the a hexagonal Cu6(Sn,Zn)5, and (IV) retardation of the elemental cross-interaction in the Ni/solder/Cu-Zn assemblies. The Cu-Zn alloys could be a potential UBM material for the advanced electronic packaging.