Effects of Cu contents in Pb-free solder alloys on interfacial reactions and bump reliability of Pb-free solder bumps on electroless Ni-P under-bump metallurgy

Using the screen-printed solder-bumping technique on the electroless plated Ni-P under-bump metallurgy (UBM) is potentially a good method because of cost effectiveness. As SnAgCu Pb-free solders become popular, demands for understanding of interfacial reactions between electroless Ni-P UBMs and Cu-containing Pb-free solder bumps are increasing. It was found that typical Ni-Sn reactions between the electroless Ni-P UBM and Sn-based solders were substantially changed by adding small amounts of Cu in Sn-based Pb-free solder alloys. In Cu-containing solder bumps, the (Cu,Ni)₆Sn₅ phase formed during initial reflow, followed by (Ni,Cu)₃Sn₄ phase formation during further reflow and aging. The Sn3.5Ag solder bumps showed a much faster electroless Ni-P UBM consumption rate than Cu-containing solder bumps: Sn4.0Ag0.5Cu and Sn0.7Cu. The initial formation of the (Cu,Ni)₆Sn₅ phase in SnAgCu and SnCu solders significantly reduced the consumption of the Ni-P UBM. The more Cu-containing solder showed slower consumption rate of the Ni-P UBM than the less Cu-containing solder below 300°C heat treatments. The growth rate of the (Cu,Ni)₆Sn₅ intermetallic compound (IMC) should be determined by substitution of Ni atoms into the Cu sublattice in the solid (Cu,Ni)₆Sn₅ IMC. The Cu contents in solder alloys only affected the total amount of the (Cu,Ni)₆Sn₅ IMC. More Cu-containing solders were recommended to reduce consumption of the Ni-based UBM. In addition, bump shear strength and failure analysis were performed using bump shear test.     

Morphology and growth kinetics of intermetallic compounds in solid-state interfacial reaction of electroless Ni-P with Sn-based lead-free solders

A comparative study of solid/solid interfacial reactions of electroless Ni-P (15 at.% P) with lead-free solders, Sn-0.7Cu, Sn-3.5Ag, Sn-3.8Ag-0.7Cu, and pure Sn, was carried out by performing thermal aging at 150°C up to 1000 h. For pure Sn and Sn-3.5Ag solder, three distinctive layers, Ni₃Sn₄, SnNiP, and Ni₃P, were observed in between the solder and electroless Ni-P; while for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders, two distinctive layers, (CuNi)₆Sn₅ and Ni₃P, were observed. The differences in morphology and growth kinetics of the intermetallic compounds (IMCs) at the interfaces between electroless Ni-P and lead-free solders were investigated, as well as the growth kinetics of the P-enriched layers underneath the interfacial IMC layers. With increasing aging time, the coarsening of interfacial Ni₃Sn₄ IMC grains for pure Sn and Sn-3.5Ag solder was significantly greater than that of the interfacial (CuNi)₆Sn₅ IMC grains for Sn-0.7Cu and Sn-3.8Ag-0.7Cu solders. Furthermore, the Ni content in interfacial (CuNi)₆Sn₅ phase slightly increased during aging. A small addition of Cu (0.7 wt.%) resulted in differences in the type, morphology, and growth kinetics of interfacial IMCs. By comparing the metallurgical aspects and growth kinetics of the interfacial IMCs and the underneath P-enriched layers, the role of initial Cu and Ag in lead-free solders is better understood.     

Morphology and kinetic study of the interfacial reaction between the Sn-3.5Ag solder and electroless Ni-P metallization

This work summarizes the interfacial reaction between lead-free solder Sn-3.5Ag and electrolessly plated Ni-P metallization in terms of morphology and growth kinetics of the intermetallic compounds (IMC). Comparison with pure Ni metallization is made in order to clarify the role of P in the solder reaction. During reflow, the IMCs formed with the Ni-P under-bump metallization (UBM) exist in chunky crystal blocks and small crystal agglomerates, while the ones with the sputtered Ni UBM exhibit uniformly scallop grains with faceted surfaces. The IMC thickness increases with reflow time following approximately a t^1/3 power law for both systems. The IMC growth rate is higher with the Ni-P UBM than the Ni UBM. The thickness of the Ni₃Sn₄ layer increases linearly with the square root of thermal aging time, indicating that the growth of the IMCs is a diffusion-controlled process. The activation energy for Ni₃Sn₄ growth in solid-state reaction is found to be 110 kJ/mol and 91 kJ/mol for the Ni-P and sputtered Ni UBMs, respectively. Kirkendall voids are detected inside the Ni₃P layer in the Sn-3.5Ag/Ni-P system. No such voids are found in the Sn-3.5Ag/Ni system.     

A study on interfacial reactions between electroless Ni-P under bump metallization and 95.5Sn-4.0Ag-0.5Cu alloy

Even though electroless Ni-P and Sn-Ag-Cu solders are widely used materials in flip-chip bumping technologies, interfacial reactions of the ternary Cu-Ni-Sn system are not well understood. The growth of intermetallic compounds (IMCs) at the under bump metallization (UBM)/solder interface can affect solder-joint reliability, so analysis of IMC phases and understanding their growth kinetics are important. In this study, interfacial reactions between electroless Ni-P UBM and the 95.5Sn-4.0Ag-0.5Cu alloy were investigated, focusing on identification of IMC phases and IMC growth kinetics at various reflowing and aging temperatures and times. The stable ternary IMC initially formed at the interface after reflowing was the (Cu,Ni)₆Sn₅ phase. However, during aging, the (Cu,Ni)₆Sn₅ phase slowly changed into the quaternary IMC composed of Cu, Ni, Sn, and a small amount of Au. The Au atoms in the quaternary IMC originated from immersion Au plated on electroless Ni-P UBM. During further reflowing or aging, the (Ni,Cu)₃Sn₄ IMC started forming because of the limited Cu content in the solder. Morphology, composition, and crystal structure of each IMC were identified using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Small amounts of Cu in the solder affect the types of IMC phases and the amount of the IMC. The activation energies of (Cu,Ni)₆Sn₅ and (Ni,Cu)₃Sn₄ IMCs were used to estimate the growth kinetics of IMCs. The growth of IMCs formed in aging was very slow and temperature-dependent compared to IMCs formed in reflow because of the higher activation energies of IMCs in aging. Comparing activation energies of each IMC, growth mechanism of IMCs at electroless Ni-P/SnAgCu solder interface will be discussed.     

Optimal phosphorous content selection for the soldering reaction of Ni-P under bump metallization with Sn-Ag-Cu solder

Nickel plating has been used as the under bump metallization (UBM) in the microelectronics industry. The electroplated Ni-P UBM with different phosphorous contents (7 wt.%, 10 wt.%, and 13 wt.%) was used to evaluate the interfacial reaction between Ni-P UBM and Sn-3Ag-0.5Cu solder paste during multiple reflow. (Cu,Ni)₆Sn₅ intermetallic compounds (IMC) formed in the SnAgCu solder/Ni-P UBM interface after the first reflow. For three times reflow, (Ni,Cu)₃Sn₄ IMC formed, while (Cu,Ni)₆Sn₅ IMC spalled into the solder matrix. With further increasing cycles of reflow, the Ni-Sn-P layer formed between (Ni,Cu)₃Sn₄ IMC and Ni-P UBM for Ni-10wt.%P and Ni-13wt.%P UBM. However, almost no Ni-Sn-P layer was revealed for the Ni-7wt.%P UBM even after ten cycles of reflow. In consideration of the wettability of Ni-P UBM, the interfacial reaction of SnAgCu/Ni-P, and dissolution of Ni-P UBM, the optimal phosphorous selection in Ni-P UBM was proposed and also discussed.     

Reliability of In-48Sn solder/Au/Ni/Cu BGA packages during reflow process

The interfacial reactions and shear properties of In-48wt.%Sn/Au/Ni/Cu solder joints were investigated in terms of reflow conditions, i.e., reflow temperature and duration time. The thickness of an AuIn₂ intermetallic compound (IMC) layer, formed at the solder/substrate interface, slightly increased with the duration time. The spalling of the AuIn₂ intermetallics in the solder led to the formation of a Ni₃(Sn,In)₄ IMC layer between the solder and exposed Ni layer. The longer duration time resulted in the spalling and grain growth of Ni₃(Sn,In)₄ intermetallics. The higher reflow temperature accelerated the interfacial reactions between the solder and substrate. From the ball shear test results, the formation and growth of a continuous plate-shaped AuIn₂ IMC layer increased the shear force of the solder joints, whereas the spalling and grain growth of cubic-shaped AuIn₂ intermetallics significantly decreased the shear force. The formation and spalling of cubic-shaped Ni₃(Sn,In)₄ intermetallics increased the shear force, whereas the spalling and grain growth of polyhedron-shaped Ni₃(Sn,In)₄ intermetallics decreased the shear force. The crack propagated at the Au-rich/AuIn₂/solder interface in the initial reflow stage, then toward the AuIn₂ intermetallics dispersed in the solder matrix, and finally along the Ni₃(Sn,In)₄ intermetallics spalling off in the solder.     

The nanoindentation characteristics of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript>, Cu<Subscript>3</Subscript>Sn,and Ni<Subscript>3</Subscript>Sn<Subscript>4</Subscript> intermetallic compounds in the solder bump

In general, formation and growth of intermetallic compounds (IMCs) play a major role in the reliability of the solder joint in electronics packaging and assembly. The formation of Cu-Sn or Ni-Sn IMCs have been observed at the interface of Sn-rich solders reacted with Cu or Ni substrates. In this study, a nanoindentation technique was employed to investigate nanohardness and reduced elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ IMCs in the solder joints. The Sn-3.5Ag and Sn-37Pb solder pastes were placed on a Cu/Ti/Si substrate and Ni foil then annealed at 240°C to fabricate solder joints. In Sn-3.5Ag joints, the magnitude of the hardness of the IMCs was in the order Ni₃Sn₄>Cu₆Sn₅>Cu₃Sn, and the elastic moduli of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ were 125 GPa, 136 GPa, and 142 GPa, respectively. In addition, the elastic modulus of the Cu₆Sn₅ IMC in the Sn-37Pb joint was similar to that for the bulk Cu₆Sn₅ specimen but less than that in the Sn-3.5Ag joint. This might be attributed to the strengthening effect of the dissolved Ag atoms in the Cu₆Sn₅ IMC to enhance the elastic modulus in the Sn-3.5Ag/Cu joint.     

Effect of phosphorus content on Cu/Ni-P/Sn-3.5Ag solder joint strength after multiple reflows

Electroless Ni-P layers with three different P contents (6.1 wt.%, 8.8 wt.%, and 12.3wt.%) were deposited on copper (Cu) substrates. Multilayered samples of Sn-3.5Ag/Ni-P/Cu stack were prepared and subjected to multiple reflows at 250°C. A tensile test was performed to investigate the effect of P content on the solder joint strength. The low P samples exhibited the highest joint strength after multiple reflows, while the strength of medium and high P samples decreased more rapidly. From interfacial analysis, the Ni₃Sn₄ intermetallic compound (IMC) formed at the interface of low P sample was found to be more stable, while the one of medium and high P samples spalled into the molten solder. The IMC spallation sped up the consumption of electroless Ni-P, leading to the large formation of Cu-Sn IMCs. Fractographic and microstructural analyses showed that the degradation in solder joint strength was due to the formation of layers of voids and growth of Cu-Sn IMCs between the solder and the Cu substrate.     

Growth of an intermetallic compound layer with Sn-3.5Ag-5Bi on Cu and Ni-P/Cu during aging treatment

Growth kinetics of intermetallic compound (IMC) layers formed between the Sn-3.5Ag-5Bi solder and the Cu and electroless Ni-P substrates were investigated at temperatures ranging from 70°C to 200°C for 0–60 days. With the solder joints between the Sn-Ag-Bi solder and Cu substrates, the IMC layer consisted of two phases: the Cu₆Sn₅ (η phase) adjacent to the solder and the Cu₃Sn (ε phase) adjacent to the Cu substrate. In the case of the electroless Ni-P substrate, the IMC formed at the interface was mainly Ni₃Sn₄, and a P-rich Ni (Ni₃P) layer was also observed as a by-product of the Ni-Sn reaction, which was between the Ni₃Sn₄ IMC and the electroless Ni-P deposit layer. With all the intermetallic layers, time exponent (n) was approximately 0.5, suggesting a diffusion-controlled mechanism over the temperature range studied. The interface between electroless Ni-P and Ni₃P was planar, and the time exponent for the Ni₃P layer growth was also 0.5. The Ni₃P layer thickness reached about 2.5 μm after 60 days of aging at 170°C. The activation energies for the growth of the total Cu-Sn compound layer (Cu₆Sn₅ + Cu₃Sn) and the Ni₃Sn₄ IMC were 88.6 kJ/mol and 52.85 kJ/mol, respectively.     

Electromigration-Induced Interfacial Reactions in Cu/Sn/Electroless Ni-P Solder Interconnects

The effect of electromigration (EM) on the interfacial reaction in a line-type Cu/Sn/Ni-P/Al/Ni-P/Sn/Cu interconnect was investigated at 150°C under 5.0 × 10³ A/cm². When Cu atoms were under downwind diffusion, EM enhanced the cross-solder diffusion of Cu atoms to the opposite Ni-P/Sn (anode) interface compared with the aging case, resulting in the transformation of interfacial intermetallic compound (IMC) from Ni₃Sn₄ into (Cu,Ni)₆Sn₅. However, at the Sn/Cu (cathode) interface, the interfacial IMCs remained as Cu₆Sn₅ (containing less than 0.2 wt.% Ni) and Cu₃Sn. When Ni atoms were under downwind diffusion, only a very small quantity of Ni atoms diffused to the opposite Cu/Sn (anode) interface and the interfacial IMCs remained as Cu₆Sn₅ (containing less than 0.6 wt.% Ni) and Cu₃Sn. EM significantly accelerated the dissolution of Ni atoms from the Ni-P and the interfacial Ni₃Sn₄ compared with the aging case, resulting in fast growth of Ni₃P and Ni₂SnP, disappearance of interfacial Ni₃Sn₄, and congregation of large (Ni,Cu)₃Sn₄ particles in the Sn solder matrix. The growth kinetics of Ni₃P and Ni₂SnP were significantly accelerated after the interfacial Ni₃Sn₄ IMC completely dissolved into the solder, but still followed the t ^1/2 law.     

Effects of Co Addition on Bulk Properties of Sn-3.5Ag Solder and Interfacial Reactions with Ni-P UBM

The effects of Co addition on the undercooling, microstructure, and microhardness of Sn-3.5Ag solder (all in wt.% unless specified otherwise) and interfacial reactions with Ni-P under bump metallurgy (UBM) are investigated when the Co content varies from 0.01 wt.% to 0.7 wt.%. When more than 0.02 wt.% Co was added to Sn-3.5Ag solder, the undercooling of the Sn-3.5Ag solder was significantly reduced and the microstructures coarsened with the increased eutectic region. In addition, the hardness value increased as the Co content in Sn-3.5Ag increased. In the interfacial reactions with Ni-P UBM, a spalling phenomenon of intermetallic compounds (IMCs) during reflow was prevented in the Sn-3.5Ag-xCo (x ≥ 0.02 wt.%). However, when more than 0.05 wt.% Co was added to Sn-3.5Ag, the IMC morphology changed from a bulky shape to a plate-like shape. The bulky IMCs were Ni₃Sn₄ and the plate-like IMCs were Sn-Ni-Co ternary compounds. The main issues discussed include the relations between the morphological changes and the IMC phases, the effects of Co addition on the prevention of IMC spalling, and the optimum level of Co addition.     

The effect of intermetallic compound morphology on Cu diffusion in Sn-Ag and Sn-Pb solder bump on the Ni/Cu Under-bump metallization

The eutectic Sn-Ag solder alloy is one of the candidates for the Pb-free solder, and Sn-Pb solder alloys are still widely used in today’s electronic packages. In this tudy, the interfacial reaction in the eutectic Sn-Ag and Sn-Pb solder joints was investigated with an assembly of a solder/Ni/Cu/Ti/Si₃N₄/Si multilayer structures. In the Sn-3.5Ag solder joints reflowed at 260°C, only the (Ni_1−x,Cu_x)₃Sn₄ intermetallic compound (IMC) formed at the solder/Ni interface. For the Sn-37Pb solder reflowed at 225°C for one to ten cycles, only the (Ni_1−x,Cu_x)₃Sn₄ IMC formed between the solder and the Ni/Cu under-bump metallization (UBM). Nevertheless, the (Cu_1−y,Ni_y)₆Sn₅ IMC was observed in joints reflowed at 245°C after five cycles and at 265°C after three cycles. With the aid of microstructure evolution, quantitative analysis, and elemental distribution between the solder and Ni/Cu UBM, it was revealed that Cu content in the solder near the solder/IMC interface played an important role in the formation of the (Cu_1−y,Ni_y)₆Sn₅ IMC. In addition, the diffusion behavior of Cu in eutectic Sn-Ag and Sn-Pb solders with the Ni/Cu UBM were probed and discussed. The atomic flux of Cu diffused through Ni was evaluated by detailed quantitative analysis in an electron probe microanalyzer (EPMA). During reflow, the atomic flux of Cu was on the order of 10¹⁶−10¹⁷ atoms/cm²sec in both the eutectic Sn-Ag and Sn-Pb systems.     

Interface Reaction Between Electroless Ni–Sn–P Metallization and Lead-Free Sn–3.5Ag Solder with Suppressed Ni3P Formation

The voids formed in the Ni₃P layer during reaction between Sn-based solders and electroless Ni–P metallization is an important cause of rapid degradation of solder joint reliability. In this study, to suppress formation of the Ni₃P phase, an electrolessly plated Ni–Sn–P alloy (6–7 wt.% P and 19–21 wt.% Sn) was developed to replace Ni–P. The interfacial microstructure of electroless Ni–Sn–P/Sn–3.5Ag solder joints was investigated after reflow and solid-state aging. For comparison, the interfacial reaction in electroless Ni–P/Sn–3.5Ag solder joints under the same reflow and aging conditions was studied. It was found that the Ni–Sn–P metallization is consumed much more slowly than the Ni–P metallization during soldering. After prolonged reaction, no Ni₃P or voids are observed under SEM at the Ni–Sn–P/Sn–3.5Ag interface. Two main intermetallic compounds, Ni₃Sn₄ and Ni₁₃Sn₈P₃, are formed during the soldering reaction. The reason for Ni₃P phase suppression and the overall mechanisms of reaction at the Ni–Sn–P/Sn–3.5Ag interface are discussed.     

Interfacial reaction of Pb-Sn solder and Sn-Ag solder with electroless Ni deposit during reflow

The interfaces between electroless Ni-P deposit and Pb-Sn solder and Sn-Ag solder were formed by reflowing for different time periods to examine their microstructures and microchemistry. It was found that the Pb-Sn solder interface is more stable than the Sn-Ag solder interface. Sn-Ag solder reacts quickly with the electroless Ni-P deposit and forms nonadherent Ni-Sn intermetallic compounds (IMCs). Pb-Sn solder reacts slowly and forms adherent Ni-Sn IMC. A P-rich Ni layer, revealed as a dark layer under scanning electron microscopy (SEM), is formed on the electroless Ni-P deposit due to the solder reaction. For short reflow times, this P-rich Ni layer consists of only Ni₃P compound, but during prolonged reflow, new crystals of Ni₂P, Ni₅P₄, and NiP₂ are also found to be formed from the amorphous electroless Ni-P layer.     

Reactions of Sn-3.5Ag-Based Solders Containing Zn and Al Additions on Cu and Ni(P) Substrates

In this study we consider the effect of separately adding 0.5 wt.% to 1.5 wt.% Zn or 0.5 wt.% to 2 wt.% Al to the eutectic Sn-3.5Ag lead-free solder alloy to limit intermetallic compound (IMC) growth between a limited volume of solder and the contact metallization. The resultant solder joint microstructure after reflow and high-temperature storage at 150°C for up to 1000 h was investigated. Experimental results confirmed that the addition of 1.0 wt.% to 1.5 wt.% Zn leads to the formation of Cu-Zn on the Cu substrate, followed by massive spalling of the Cu-Zn IMC from the Cu substrate. Growth of the Cu₆Sn₅ IMC layer is significantly suppressed. The addition of 0.5 wt.% Zn does not result in the formation of a Cu-Zn layer. On Ni substrates, the Zn segregates to the Ni₃Sn₄ IMC layer and suppresses its growth. The addition of Al to Sn-3.5Ag solder results in the formation of Al-Cu IMC particles in the solder matrix when reflowed on the Cu substrate, while on Ni substrates Al-Ni IMCs spall into the solder matrix. The formation of a continuous barrier layer in the presence of Al and Zn, as reported when using solder baths, is not observed because of the limited solder volumes used, which are more typical of reflow soldering.     

Intermetallic reactions in Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes

The intermetallic compounds (IMCs) formed during the reflow and aging of Sn3Ag0.5Cu and Sn3Ag0.5Cu0.06Ni0.01Ge solder BGA packages with Au/Ni surface finishes were investigated. After reflow, the thickness of (Cu, Ni, Au)₆Sn₅ interfacial IMCs in Sn3Ag0.5Cu0.06Ni0.01Ge was similar to that in the Sn3Ag0.5Cu specimen. The interiors of the solder balls in both packages contained Ag₃Sn precipitates and brick-shaped AuSn₄ IMCs. After aging at 150°C, the growth thickness of the interfacial (Ni, Cu, Au)₃Sn₄ intermetallic layers and the consumption of the Ni surface-finished layer on Cu the pads in Sn3Ag0.5Cu0.06Ni0.01Ge solder joints were both slightly less than those in Sn3Ag0.5Cu. In addition, a coarsening phenomenon for AuSn₄ IMCs could be observed in the solder matrix of Sn3Ag0.5Cu, yet this phenomenon did not occur in the case of Sn3Ag0.5Cu0.06Ni0.01Ge. Ball shear tests revealed that the reflowed Sn3Ag0.5Cu0.06Ni0.01Ge packages possessed bonding strengths similar to those of the Sn3Ag0.5Cu. However, aging treatment caused the ball shear strength in the Sn3Ag0.5Cu packages to degrade more than that in the Sn3Ag0.5Cu0.06Ni0.01Ge packages.     

Characterizing metallurgical reaction of Sn3.0Ag0.5Cu composite solder by mechanical alloying with electroless Ni-P/Cu under-bump metallization after various reflow cycles

Electroless Ni-P/Cu under-bump metallization (UBM) is widely used in electronics packaging. The Sn3.0Ag0.5Cu lead-free composite solder pastes were produced by a mechanical alloying (MA) process doped with Cu₆Sn₅ nanoparticles. In this study, the detailed interfacial reaction of Sn3.0Ag0.5Cu composite solders with EN(P)/Cu UBM was investigated after reflow. A field-emission scanning electron microscope (FESEM) was employed to analyze the interfacial morphology and microstructure evolution. The intermetallic compounds (IMCs) formed at the interface between the Sn3.0Ag0.5Cu composite solders and EN(P)/Cu UBM after one and three reflows were mainly (Ni_1−x,Cu_x)₃Sn₄ and (Cu_1−y,Ni_y)₆Sn₅. However, only (Ni_1−x,Cu_x)₃Sn₄ IMC was observed after five reflows. The elemental distribution near the interfacial region was evaluated by an electron probe microanalyzer (EPMA) as well as field-emission electron probe microanalyzer (FE-EPMA). Based on the observation and characterization by FESEM, a EPMA, and an FE-EPMA, the reaction mechanism of interfacial phase transformation between Sn3.0Ag0.5Cu composite solders and EN(P)/Cu UBM after various reflow cycles was discussed and proposed.     

Interdependent Intermetallic Compound Growth in an Electroless Ni-P/Sn-3.5Ag Reaction Couple

The interfacial microstructure of electroless Ni-P/Sn-3.5Ag solder joints was investigated after reflow and high-temperature solid-state aging to understand its interdependent growth mechanism and related kinetics of intermetallic compounds (IMCs) at the interface. The reflow and aging results showed that mainly three IMC layers, Ni₃Sn₄, Ni₂SnP, and Ni₃P, formed during the soldering reaction. It was found that the Ni₃Sn₄ and Ni₃P layers grow predominantly as long as the electroless Ni-P layer is present; however, once the Ni-P layer is fully consumed, the Ni₂SnP layer grows rapidly at the expense of the Ni₃P layer. A transition in the Ni₃Sn₄ morphology from needle and chunky shape to scallop shape was observed after the solid-state aging of reflowed samples. The kinetics data obtained from the growth of compound layers in the aged samples revealed that initially the growth of the Ni₂SnP layer is controlled by diffusion, and subsequently by the rate of reaction after the Ni-P metallization is fully consumed. It was found that complete transformation of the electroless Ni-P layer into a Ni₃P layer results in the rapid growth of the Ni₂SnP layer due to the dominating reaction of Sn with Ni₃P. The apparent activation energies for the growth of Ni₃Sn₄, Ni₂SnP, and Ni₃P compound layers were found to be 98.9 kJ/mol, 42.2 kJ/mol, and 94.3 kJ/mol, respectively.     

Interfacial reactions and compound formation of Sn-Ag-Cu solders by mechanical alloying on electroless Ni-P/Cu under bump metallization

Electroless Ni-P under bump metallization (UBM) has been widely used in electronic interconnections due to the good diffusion barrier between Cu and solder. In this study, the mechanical alloying (MA) process was applied to produce the SnAgCu lead-free solder pastes. Solder joints after annealing at 240°C for 15 min were employed to investigate the evolution of interfacial reaction between electroless Ni-P/Cu UBM and SnAgCu solder with various Cu concentrations ranging from 0.2 to 1.0 wt.%. After detailed quantitative analysis with an electron probe microanalyzer, the effect of Cu content on the formation of intermetallic compounds (IMCs) at SnAgCu solder/electroless Ni-P interface was evaluated. When the Cu concentration in the solder was 0.2 wt.%, only one (Ni, Cu)₃Sn₄ layer was observed at the solder/electroless Ni-P interface. As the Cu content increased to 0.5 wt.%, (Cu, Ni)₆Sn₅ formed along with (Ni, Cu)₃Sn₄. However, only one (Cu, Ni)₆Sn₅ layer was revealed, if the Cu content was up to 1 wt.%. With the aid of microstructure evolution, quantitative analysis, and elemental distribution by x-ray color mapping, the presence of the Ni-Sn-P phase and P-rich layer was evidenced.     

Studies of electroless nickel under bump metallurgy—Solder interfacial reactions and their effects on flip chip solder joint reliability

The electroless-deposited Ni-P under bump metallurgy (UBM) layer was fabricated on Al pads for Sn containing solder bumps. The amount of P in the electroless Ni film was optimized by controlling complexing agents and the pH of plating solution. The interfacial reaction at the electroless Ni UBM/solder interface was investigated in this study. The intermetallic compound (IMC) formed at the interface during solder reflowing was mainly Ni₃Sn₄, and a P-rich Ni layer was also formed as a by-product of Ni-Sn reaction between the Ni-Sn IMC and the electroless Ni layer. One to four microns of Ni₃Sn₄ IMC and a 1800–5000 Å of P-rich Ni layer were formed in less than 10 min of solder reflowing depending on solder materials and reflow temperatures. It was found that the P-rich Ni layer contains Ni, P, and a small amount of Sn (～7 at.%). Further cross-sectional transmission electron microscopy (TEM) analysis confirmed that the composition of the P-rich Ni layer was 75 at.% Ni, 20at.%P, and 5at.%Sn by energy-dispersive x-ray spectroscopy (EDS) and the phase transformation occurred in the P-rich Ni layer by observing grain size. Kirkendall voids were also found in the Ni₃Sn₄ IMC, just above the P-rich Ni layer after extensive solder reflow. The Kirkendall voids are considered a primary cause of the brittle fracture; restriction of the growth of of the P-rich Ni layer by optimizing proper processing conditions is recommended. The growth kinetics of Ni-Sn IMC and P-rich Ni layer follows three steps: a rapid initial growth during the first 1 min of solder reflow, followed by a reduced growth step, and finally a diffusion-controlled growth. During the diffusion-controlled growth, there was a linear dependence between the layer thickness and time^1/2. Flip chip bump shear testing was performed to measure the effects of the IMC and the P-rich Ni layers on bump adhesion property. Most failures occurred in the solder and at the Ni₃Sn₄ IMC. The brittle characteristics of the Ni-Sn IMC and the Kirkendall voids at the electroless Ni UBM-Sn containing solder system cause brittle bump failure, which results in a decreased bump adhesion strength.