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A variety of lead-free solder alloys were studied for use as flip-chip interconnects including Sn-3.5Ag, Sn-0.7Cu, Sn-3.8Ag-0.7Cu, and eutectic Sn-37Pb as a baseline. The reaction behavior and reliability of these solders were determined in a flip-chip configuration using a variety of under-bump metallurgies (TiW/Cu, electrolytic nickel, and electroless Ni-P/Au). The solder micro-structure and intermetallic reaction products and kinetics were determined. The Sn-0.7Cu solder has a large grain structure and the Sn-3.5Ag and Sn-3.8Ag-0.7Cu have a fine lamellar two-phase structure of tin and Ag3Sn. The intermetallic compounds were similar for all the lead-free alloys. On Ni, Ni3Sn4 formed and on copper, Cu6Sn5Cu3Sn formed. During reflow, the intermetallic growth rate was faster for the lead-free alloys, compared to eutectic tin-lead. In solidstate aging, however, the interfacial intermetallic compounds grew faster with the tinlead solder than for the lead-free alloys. The reliability tests performed included shear strength and thermomechanical fatigue. The lower strength Sn-0.7Cu alloy also had the best thermomechanical fatigue behavior. Failures occurred near the solder/intermetallic interface for all the alloys except Sn-0.7Cu, which deformed by grain sliding and failed in the center of the joint. Based on this study, the optimal solder alloy for flip-chip applications is identified as eutectic Sn-0.7Cu.

The important issues in advanced area-array electronic packaging for semiconductor devices are materials driven. Some of the processing-driven materials issues include the effect of introducing a silicon device interface with copper pads and a low-κ dielectric, the effect of decreasing pitch and feature size on the package interconnects, the development and implementation of organic substrates, and advanced underfills for fine-pitch flip-chip applications. From a materials reliability aspect, important materials issues include enhanced solder interconnect reliability, α-particle-induced soft errors, and the introduction of lead-free solder alloys.

The presence of an intermetallic is often an indication of good wetting in a solder joint. However, excessive intermetallic growth and the brittleness of the intermetallic layer may be detrimental to joint reliability. This study examined the growth and mechanical behavior of interfacial intermetallics between copper and six solder alloys commonly used in electronics assembly. The solder alloys tested were 60Sn-40Pb, 63Sn-37Pb, 95Sn-5Sb, 96.5Sn-3.5Ag, 50Pb-50In, 50Sn-50In, and 40In-40Sn-20Pb. The 50Sn-50In and 40In-40Sn-20Pb exhibited faster solid state growth of the intermetallic layer at 100 °C as compared to the near-eutectic Sn-Pb control solder. The 50In-50Pb had a slower growth rate, relative to 63Sn-37Pb, at the aging temperature of 170 °C due to slower reaction rate kinetics of indium with copper. The 96.5Sn-3.5Ag and 95Sn-5Sb had similar intermetallic growth rates at 170 °C and 205 °C, and the aging was comparable to that of the 63Sn-37Pb alloy. The 95Sn-5Sb solder/copper intermetallic had a faster growth rate of the Cu3Sn layer than was observed in the Sn-Ag or Sn-Pb alloys. Modified fracture toughness and low load indentation tests were used to characterize the mechanical behavior of the intermetallics. The intermetallics were harder than both the base metal and the solder alloy. The fracture behavior of the joints in tension was dependent upon the strength of the solder alloy. Solders with low strengths failed in the solder by plastic deformation. The failure of solders with higher strengths was dependent upon intermetallic thickness. When the intermetallic was thin, fracture occurred in the solder or at the solder/ intermetallic interface. As the interfacial intermetallic thickened, the fracture path moved into the intermetallic layer.

We present the results of a metallurgical study of a 35Pd-30Ag-14Cu-10Au10Pt-1Zn (wt. %) alloy soldered with 60Sn-40Pb for glass-to-metal sealing applications. Mechanical tests were performed on the Pd-Ag-Cu-Au-Pt-Zn alloy and showed that it retains ductility, with an increase in strength, after heat treatments that simulate the glass-to-metal sealing temperature profile. Wetting characteristics of the alloy with 60Sn-40Pb solder were found to be adequate for pin joining applications. The formation and growth of the interfacial interme-tallic between 60Sn-40Pb and the Pd-Ag-Cu-Au-Pt-Zn alloy were characterized. The matrix of the intermetallic layer consists of PdSn4 with platinum and gold substituting for the palladium in the crystal structure. Also present were precipitates of Cu3Sn and Ag3Sn. Nano-indentation hardness tests showed that the intermetallic layer has mechanical properties similar to the base metal while retaining good ductility. The intermetallic was also found to have good wettability under solder reflow conditions. We conclude from these tests that the Pd-Ag-Cu-Au-Pt-Zn alloy is a suitable option as a pin material for glass-to-metal sealing applications.

The corrosion behavior of sputter-deposited Al, Al-Cu, and Al-Si alloy thin films in dilute hydrofluoric (HF) acid solution was investigated. These materials maintain a thin aluminum oxide film in dilute HF solutions and, consequently, are susceptible to localized corrosion. Pit densities increase for the alloys with Cu and, to a lesser extent, Si additions. Open circuit potentials (OCP) are more positive for such alloys relative to the OCP of pure Al. Metastable pits in Al-Cu alloys are formed in Cu-depleted zones at grain boundaries which are galvanically coupled to adjacent θ-Al2Cu precipitates. Metastable pits in Al-Si alloys are formed in the Al matrix which is galvanically coupled to adjacent elemental Si nodules. θ-Al2Cu has different electrochemical characteristics than Al, even though both maintain a thin Al oxide in dilute HF solutions. θ-Al2Cu has a more positive OCP than pure Al and facilitates cathodic reactions at enhanced rates relative to pure Al. Hence, its presence raises the potential of the adjacent pure Al grain boundary to potentials which increase the probability of metastable pitting. Evidence is also presented which suggests that metastable pit growth may be cathode limited. A new hypothesis describing one mechanism by which θ-Al2Cu supports cathodic electron transfer re-actions is discussed.

The grain size and grain growth kinetics in sputter deposited Al-2% Cu films on silicon substrates were determined by TEM for various film thicknesses and anneal times, temperatures and methods. Grain sizes were found to be typically lognormally distributed. The as- deposited grain size (d{sub o}) dependence on film thickness (TH) was found to be d{sub o} = C TH{sup {1/2}}, due to competitive grain growth during film formation. Annealed grain size (d) after Rapid Thermal Annealing (RTA) for time (t) at temperature (T) is described by the general equation d {minus} do = C TH{sup 0.7} {l brace}t exp ({minus}{Delta}E{sub a}/kT){r brace}{sup 1/8}, where {Delta}E{sub a} = 0.85 ev for 0.4 {mu}m films and {Delta}E{sub a} = 1.1 ev for 0.8 {mu}m films. Grain growth is largely saturated for these anneals. Grain growth is shown to be more extensive during RTA anneals than furnace annealing and more extensive in 0.4 {mu}m films than 0.8 {mu}m films for equivalent RTA cycles. The results are discussed in terms of models, simulations and previous results of grain growth in thin metal films. 21 refs., 4 figs.

The precipitation, dissolution, and reprecipitation processes of Al2Cu (θ phase) in Al-2 wt pct Cu thin films were studied. The films were characterized in the as-deposited condition, after annealing at 425 °C for 35 minutes, and after rapid thermal annealing (RTA) at 345 °C, 405 °C, and 472 °C. In the as-deposited samples, the precipitates had a fine even distribution throughout the thin film both at aluminum grain boundaries and within the aluminum grains. Annealing below the solvus temperature caused the grain boundary precipitates to grow and precipitates within the center of aluminum grains to diminish. Annealing above 425 °C caused the θ-phase precipitates to dissolve. Upon cooldown, the θ phase nucleated at aluminum grain boundaries and triple points in the form of plates.In situ heating and cooling experiments documented this process in real time. Analytical microscopy revealed that there is a depletion of copper at the aluminum grain boundaries in regions free of precipitates. The θ-phase precipitates nucleated and grew at the grain boundariesvia a collector plate mechanism and drew copper from the areas adjacent to the aluminum grain boundaries.

Thermomechanical fatigue tests were performed on two near-eutectic Sn-Pb solder alloys, 60 Sn-40 Pb and 62 Sn-36 Pb-2 Ag, to examine the effect silver additions have on solder joints. The cyclic load was found to have consistent trends between the two silver alloys (for given amounts of total strain and strain rates). It was found that a decreasing strain rate increased the life of both alloys equally in thermomechanical fatigue. At slower strain rates, the dislocation substructure recovers faster than it work-hardens, which tends to minimize subsequent recrystallization and heterogeneous coarsening of the solder joint. The microstructure of 62 Sn-36 Pb-2 Ag contained large whisker-like Ag/sub 3/Sn precipitates that nucleate and grow out from the Cu/sub 6/Sn/sub 5/ interfacial intermetallics. At this size, the Ag/sub 3/Sn precipitates have little effect on the deformation behavior of the solder. The intermetallics are not detrimental in that they do not prematurely crack, nor are they beneficial because they are too large to stabilize the microstructure. It does not appear, from a microstructural viewpoint, that adding silver to near-eutectic Sn-Pb has any significant effect on improving the thermomechanical fatigue behavior. >

The microstructural evolution of unpatterned Al-2wt.%Cu thin films has been examined to elucidate the mechanism by which copper improves electromigration resistance. After annealing at 425°C and cooling to room temperature at a rate of approximately 1°C/min., the microstructure of the Al-Cu films consisted of 1 μm aluminum grains with θ-phase Al2Cu precipitates at grain boundaries and triple points. The grain size and precipitation distribution did not change with subsequent isothermal heat treatments in the temperature range of 200° to 400°C. Al-Cu thin films annealed at 400°C, a temperature just below the Al/Al+θ solvus, exhibited microstructures in which the aluminum grain boundaries were depleted in copper except for the presence of the pre-existing large, widely dispersed AI2Cu precipitates. Al-Cu thin films annealed at 200° to 300°C were enriched with copper at the aluminum grain boundaries. The large, widely dispersed Al2Cu precipitates remained after the lower temperature anneals. From these results, it is proposed that the presence of copper in aluminum thin films improves electromigration resistance due to the precipitation of a thin film of Al2Cu, or a substoichiometric precursor, along the grain boundaries. The grain boundary phase retards grain boundary diffusion in the thin films, thereby reducing total mass transport and improving electromigration resistance.

The distribution of copper in aluminum thin films is examined with respect to how the copper can influence electromigration behavior. Al-Cu thin films annealed in the single phase region, to just below the solvustemperature, have 0-phase Al2Cu precipitates at the aluminum grain boundaries. The grain boundaries between precipitates are depleted in copper. Al-Cu thin films heat treated at lower temperatures, within thetwo phase region, also have 0-phase precipitates at the grain boundaries but the aluminum grain boundariescontinuously become enriched in copper, perhaps due to the formation of a thin coating of 0-phase at the grain boundary. Here, it is proposed that electromigration behavior of aluminum is improved by addingcopper because the 0-phase precipitates may hinder aluminum diffusion along the grain boundaries. It was also found that resistivity of Al-Cu thin films decrease during accelerated electromigration testing prior to failure. Pure Al films did not exhibit this behavior. The decrease in resistivity is attributed to theredistribution of copper from the aluminum grain matrix to the 0-phase precipitates growing at the grain boundaries thereby reducing the number of defects in the microstructure.

Al with additions of Cu is commonly used as the conductor metallizations for integrated circuits (ICs). As the packing density of ICs increases, interconnect lines are required to carry ever higher current densities. Consequently, reliability due to electromigration failure becomes an increasing concern. Cu has been found to increase the lifetimes of these conductors, but the mechanism by which electromigration is improved is not yet fully understood. In order to evaluate certain theories of electromigration it is necessary to have a detailed description of the Cu distribution in the Al microstructure, with emphasis on the distribution of Cu at the grain boundaries. In this study analytical electron microscopy (AEM) has been used to characterize grain boundary regions in an Al-2 wt.% Cu thin film metallization on Si after a variety of thermal treatments. The results of this study indicate that the Cu distribution is dependent on the thermal annealing conditions. At temperatures near the θ phase (CuAl2) solvus, the Cu distribution may be modelled by the collector plate mechanism, in which the grain boundary is depleted in Cu relative to the matrix. At lower temperatures, Cu enrichment of the boundaries occurs, perhaps as a precursor to second phase formation. Natural cooling from the single phase field produces only grain boundary depletion of Cu consistent with the collector-plate mechanism. The kinetic details of the elemental segregation behavior derived from this study can be used to describe microstructural evolution in actual interconnect alloys.

Aluminum - 2 wt.% copper alloys are commonly used in thin film form as interconnect metallization lines for integrated circuits. Experience has shown that the addition of the Cu to the Al, albeit at a decrease in conductivity, makes the metallizations more resistant to failure by electromigration. However, the mechanism by which Cu increases the resistance to electromigration has never been positively identified. One theory proposes that Cu coats the Al grain boundaries (boundaries are enriched in Cu) and retards grain boundary diffusion thereby reducing electromigration. Another theory suggests that a continuous thin layer of CuAl2 forms along the boundaries also reducing grain boundary transport and therefore the tendency to electromigrate. Recently, Frear et al. have reported on a detailed set of experiments to examine these theories from a microstructural viewpoint. Here, the details of the high spatial resolution microanalysis done to support the study of Fear, et al. are reported.Al- 2wt.% Cu was magnetron sputtered onto a borosilicate glass (BSG) coated (100) Si wafer. The Al-Cu films were sputtered at room temperature from a single source under an argon atmosphere at a deposition rate of 100 nm/min. Films 400 and 800 nm thick were prepared. The films were annealed under a 15% hydrogen forming gas (reducing) at 425°C for 35 min.