Journal of Alloys and Compounds 677 (2016) 127e138

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Void formation and its impact on CueSn intermetallic compound

formation
Glenn Ross*, Vesa Vuorinen, Mervi Paulasto-Kro
€ ckel
Department of Electrical Engineering and Automation, School of Electrical Engineering, Aalto University, Finland

a r t i c l e i n f o a b s t r a c t

Article history: Void formation in the CueSn system has been identified as a major reliability issue with small volume
Received 1 January 2016 electronic interconnects. Voids form during the interdiffusion of electrochemically deposited Cu and Sn,
Received in revised form with varying magnitude and density. Electroplating parameters include the electrolytic chemistry
15 March 2016
composition and the electroplating current density, all of which appear to effect the voiding charac-
Accepted 23 March 2016
teristics of the CueSn system. In addition, interfacial voiding affects the growth kinetics of the Cu3Sn and
Available online 25 March 2016
Cu6Sn5 intermetallic compounds of the CueSn system. The aim here is to present voiding data as a
function of electroplating chemistry and current density over a duration (up to 72 h) of isothermal
Keywords:
Void formation
annealing at 423 K (150
C). Voiding data includes the average interfacial void size and average void
Kirkendall void density. Voids sizes grew proportionally as a function of thermal annealing time, whereas the void
CueSn system density grew initially very quickly but tended to saturate at a fixed density. A morphological evolution
Micro-connects analysis called the physicochemical approach is utilised to understand the processes that occur when a
Electroplating voided Cu/Cu3Sn interface causes changes to the IMC phase growth. The method is used to simulate the
Intermetallic compound intermetallic thickness growths' response to interfacial voiding. The Cu/Cu3Sn interface acts as a Cu
Thermodynamics diffusion barrier disrupting the diffusion of Cu. This resulted in a reduction in the Cu3Sn thickness and an
Growth constants
accelerated growth rate of Cu6Sn5.
Activation energy
© 2016 Elsevier B.V. All rights reserved.
Physicochemical approach

1. Introduction electrochemical deposition (electroplating) methods. A comparison

As the focus of the electronics industry has recently shifted to
portable devices and the Internet of Things (IoT), pressure for the
development of novel interconnect technologies has increased
[1e5]. Small volume interconnects (micro-connects) are not
without their challenges, namely, understanding the micro-
structural evolution and the associated reliability implications
[6e8]. In the race to find suitable 3D vertical integration tech-
niques, a reliability related challenge has been identified that
threatens the electrical and mechanical performance of micro-
connects. Interfacial void formation, often referred to as Kirken-
dall voids (KV), have been attributed to reduced reliability [9e12].
Voids tend to form either at the interface between Cu/Cu3Sn, or
distributed throughout the Cu3Sn phase of an isothermally aged
CueSn micro-connect [13,14].
As has been reported in numerous studies [13e15], voiding of
this nature predominantly occurs in samples fabricated using
* Corresponding author. P.O. Box 13500, FIN-00076 Aalto, Finland.
E-mail address: Glenn.Ross@aalto.fi (G. Ross).
carried out [15] between pure oxygen free high conductive (OFHC)
Cu and electroplated Cu resulted in voids arising only in electro-
plated samples. This result demonstrates that processes occurring
during electroplating promote the propensity for an interface to
exhibit voiding. Electroplating parameters were studied to find
void producing mechanisms within the CueSn system. It was
ascertained that electroplating chemistries, current densities and
temperature all appear to influence voiding propensity [15e19].
Interfacial voids have been reported to not only impact joint
reliability but also the formation kinetics of intermetallic com-
pound (IMC) growth. Earlier published work by Zeng et al. [20] and
Yu et al. [14] reported reduced Cu3Sn parabolic growth rates in void
effected interfaces. These studies reported a correlation between
the growth rates of the IMCs and the location and density of voids
formed within micro-connects. The major contribution to IMC
growth at CueSn solidus temperatures is bulk diffusion [21,22]. As
the thickness of IMCs grows, the diffusion lengths for the atoms
increase,
pffiffi slowing the effective formation rate. This results in
Dxb f t , where the change in the b-phase thickness (Dxb ) is pro-
portional to the square-root of time (t) [23]. Changes in the

http://dx.doi.org/10.1016/j.jallcom.2016.03.193
0925-8388/© 2016 Elsevier B.V. All rights reserved.
128 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138
parabolic growth rate behaviour exhibited by the IMCs indicate that
there are alterations to the phase growth mechanisms of the sys-
tem with an interface that experiences interfacial voiding.
This study quantitatively reports on void formation, voiding
characteristics and IMC growth kinetic data as a function of changes
to electroplated Cu parameters, including electroplating chemis-
tries and current densities. IMC growth rates will be correlated with
average void sizes and densities as a function of isothermal ageing
at 423 K (150
C). Characteristic void formation behaviours will be
identified and examined. Additionally, an interfacial reaction
diffusion based approach will be utilised to understand the impact
of voiding on IMC growth rates.
2. Material and methods
The first step was the sample preparation, with the 4 inch Si
wafers undergoing the RCA 1 & 2 cleaning process. Next, after the
removal of surface oxides and contaminants, 100 nm of Cr followed
by 100 nm of Cu was deposited onto the Si wafers by magnetron
sputtering. The Cr film functions as a barrier layer to prevent re-
actions between Si and Cu, and the Cu acts as the seed layer for
subsequent electroplating processes. Before electroplating the
substrates were pre-treated using oxygen plasma using PVA Tepla
400 with an O2 flow rate of 3 [ml min1] at a power of 100 W for a
duration of 3 min. This process was used to clean and activate the
surface. After the plasma treatment, the substrates were thor-
oughly rinsed with DI-water for wetting of the Cu seed layer surface
before inserting into the electrolyte.
2.1. Small volume plating cell
A small volume test electroplating cell was used for the void and
IMC characterisation tests. Three litres of electrolyte was agitated
by a magnetic stirrer at a rotation speed of 500 rpm at a standard
room temperature of 296 K (23
C). The Si wafers were mounted
into a Teflon wafer holder with front side titanium contacts and
with backside protection. A 200  200  2 mm high phosphorus
containing Cu anode was used which was first soaked in alkaline
cleaner, followed by etching in a solution of (NH4)S2O8 and H2SO4.
After etching, a conditioning process of dummy plating to film the
anode prior to use was carried out. The anode-cathode spacing was
70 mm.
A 5 mm Cu layer was then electroplated onto the Cu seed layer.
Different electroplating chemistries were used to form the Cu layer.
An overview of the electroplating solutions is given in Table 1. Basic
solution A includes a generic Cu electrolyte solution with low
quality sulphuric acid. Basic solution B is also a generic Cu elec-
trolyte but with a high quality sulphuric acid. The commercial so-
lution was supplied by a typical vendor and contains an unknown
combination of additives for controlling the properties of the Cu
film. The additive solutions contain a generic combination of
commonly used additives used in electroplating including, bis-(3-
sulfopropyl)-disulfide (SPS), polyethylene glycol Mn ¼ 3350 (PEG)
and a combination of both SPS þ PEG. All solutions were electro-
plated with 3 different current densities, 5 [mA cm2], 20
[mA cm2] and 30 [mA cm2] which are labelled as low current
density (LCD), medium current density (MCD) and high current
density (HCD) respectively. After Cu electroplating, a common 5 mm
Sn electroplated film was deposited on top of the Cu. The same
solution (NB Semiplate Sn 100 from NB Technologies) at a single
current density of 15 [mA cm2] was used for the electroplating of
Sn.
Once the final structure had been formed, the Si wafers were
diced into 15  10 mm rectangles and placed in a thermal chamber
for isothermal ageing. The samples were exposed to a temperature
of 423 K (150
C) for a duration of 0, 4, 8, 24, 48 and 72 h. The
samples were subsequently moulded in epoxy and prepared for
scanning electron microscopy (SEM) imaging. A total of 10 SEM
micrographs were taken in back-scattering mode. For each micro-
graph the average void size, density and IMC thickness were
calculated. The average and standard deviation from each mea-
surement was taken. Error bars were generated with a confidence
interval (CI) of 95%.
The average void size [mm2] was determined from each micro-
graph by summing the areas of all the voids and dividing this by the
total number of the voids. The density of voids [N mm2] was
calculated by dividing the total number of voids by the total area of
the CueSn system in the micrograph. As there were slight varia-
tions in the total thickness of the CueSn layer, the thickness was
normalised to 10 mm for consistent density results. The thickness
data of the IMC was additionally determined from the micrographs.
The area of each IMC layer was measured, the area was divided by
the width of the micrograph giving the IMC thickness.
2.2. Hull cell 267 ml
A 267 ml hull cell was used for evaluation of the growth con-
stant activation energies. A hull cell is a trapezoidal vessel designed
to evaluate an electroplating solution. As the cathode is placed at an
oblique angle with respect to the anode, a range of current densities
can be analysed in a single electroplating run. The electrolyte vol-
ume was 267 ml which was agitated by a magnetic stirrer at a
rotation of 300 rpm. Hull cell tests were undertaken at room
temperature. A 70  70  5 mm high phosphorus containing Cu
anode was used with a zig zag exposed surface to improve the
anode to cathode surface area ratio. A Si wafer, diced in half was
used as a cathode and the correct current density was determined
from the thickness of the Cu deposited and by using Faraday's law.
A LCD 5 mm deposit of Cu was applied followed directly by a LCD
10 mm deposit of Sn. Due to the configuration of the hull cell, MCD
and HCD have a higher resulting thickness. A large thickness is
required to ensure no end member in the diffusion couple gets fully
consumed during isothermal annealing. The electroplating chem-
istries were the same as those used in the small volume plating cell
(see Table 1). The half wafers were subsequently diced into
8  10 mm rectangles. The samples were all isothermally annealed
at temperatures of 373 K (100
C) for 240 h, 423 K (150
C) for 120 h
and 473 K (200
C) for 72 h. Thermal annealing durations were
designed to ensure the IMCs are measureable with SEM. The same
method for characterising the IMC thickness in the small plating
cell test was utilised with these samples.
3. Theory
3.1. CueSn IMC parabolic growth constants and activation energies
The CueSn system has two stable phases at the isothermal
ageing temperature of 423 K (150
C), they are Cu3Sn (ε) and Cu6Sn
(h). From the CueSn binary phase diagram it is clear that both
phases have a narrow homogeneity range, particularly below the
temperature of 473 K (200
C). In the case of diffusion controlled
phase growth, diffusing species need to traverse the length of the
phases in order to react and grow. The parabolic growth constant kbp
of the b-phase [m2 s1], indicates the rate at which a phase grows
and is a function of phase thickness and time [23].
Interestingly, the rate at which phases form provides informa-
tion about the energy required for narrow homogeneity phases to
form. The phase formation energy can provide information about
the underlying mechanisms for phase growth. The activation en-
ergy for phase growth can be determined from thickness data
 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138 129

Table 1
List of electroplating chemicals with their corresponding sample name, concentration, chemical formula and supplier.

Sample Electroplating solution

Concentration Formula Supplier

Basic Solution A (Low Quality) 0.25 M CuSO4$5H2O Aldrich 209198

1.8 M H2SO4 Aldrich 258105
1.92 mM HCl Aldrich 40304
Basic Solution B(High Quality) 0.25 M CuSO4$5H2O Aldrich 209198
1.8 M H2SO4 Aldrich 40306
1.92 mM HCl Aldrich 40304
Commercial Solution e e NB Semiplate Cu 100
SPS 0.25 M CuSO4$5H2O Aldrich 209198
1.8 M H2SO4 Aldrich 40306
1.92 mM HCl Aldrich 40304
0.01 mM C6H12Na2O6S4 Raschig RALU®PLATE SPS
PEG 0.25 M CuSO4$5H2O Aldrich 209198
1.8 M H2SO4 Aldrich 40306
1.92 mM HCl Aldrich 40304
0.059 mM H(OCH2CH2)nOH Aldrich 202444
SPS þ PEG 0.25 M CuSO4$5H2O Aldrich 209198
1.8 M H2SO4 Aldrich 40306
1.92 mM HCl Aldrich 40304
0.01 mM C6H12Na2O6S4 Raschig RALU®PLATE SPS
0.059 mm H(OCH2CH2)nOH Aldrich 202444

recorded by diffusion experiments taken at different temperatures.

As the phase thickness greatly depends on the composition of the
end members, activation energy for phase growth is not a material
constant. Moreover, this should not be confused with the diffusion
activation energy, as in the case of multi-phase systems the diffu-
sion activation energy may not be the same as the phase growth
activation energy [23]. Thickness data is plotted as a function of
inverse temperature so that the Arrhenius equation can be fitted to
the data giving,
  Fig. 1. Illustration of the CueSn system during isothermal ageing. Interface I is Cu/
b Q Cu3Sn, II is the Cu3Sn/Cu6Sn5 and III is the Cu6Sn5/Sn interfaces. p, q, r and s are the
kp ¼ k0p exp  (1) molar fluxes of Cu and Sn in the respective phases. Kε and Kh are the Kirkendall planes
RT
of the two phases.

where, k0p is the pre-exponential growth factor [m2 s1], Q is the

phase growth activation energy [J mol1], R is the gas constant
(8.314 [J mol1 K1]) and T is the absolute temperature [K] [22,24].
Table 2 lists a literature survey of activation energies determined
from CueSn diffusion pairs under different fabrication methods.
3.2. Physicochemical approach for the voids impact to interfacial
reactions
The physicochemical approach was introduced by Ghosh and
Paul [29]. It is a reactive diffusion based approach to facilitate an
understanding of physical chemical reactions occurring at each
interface of the CueSn diffusion couple. This approached treats all
interfaces as chemical reactions, enabling an interfacial reaction
based approach to understanding IMC formation. As voids appear
to change the growth characteristics of IMCs, interfacial reactions
can be adapted to understand the underlying mechanisms that
drive the changes. Fig. 1 is a schematic of a thermally aged CueSn
diffusion couple. Indicated in the figure are the three reaction in-
terfaces, I (Cu/Cu3Sn), II (Cu3Sn/Cu6Sn5) and III (Cu6Sn5/Sn).
Presented below are the interfacial reactions (interfaces I to III
are illustrated in Fig. 1) that occur as a result of the interdiffusion of
Cu and Sn. Reactions occurring at the interfaces account for reactive
diffusion of Cu and Sn in both directions and will be used analyti-
cally during the discussion to understand the effects of voiding on
the IMC growth kinetics.
Interface I:
3qCu þ q½Snd /4qCu3=4 Sn1=4
Interface II: (Cu3Sn side)
11 20
pCu6=11 Sn5=11 þ p½Cud / pCu3=4 Sn1=4
9 9

Table 2
Literature survey of activation energy parameters for phase growth found in CueSn diffusion couples for Cu3Sn and Cu6Sn5.

Activation energy

Cu3Sn (ε) Cu6Sn5 (h) Temperature range Details Ref

[kJ mol1] [kJ mol1] [K] (
C)

73.8 81.0 423 e 623 (150e350) Incremental diffusion couples, Cu/Cu6Sn5 & Cu3Sn/Sn [22]
77.6 85.4 403 (130) Cu(99.999%)/Sn (99.9999%) diffusion couple [25]
70.4 107.1 383 e 481 (110e208) Cu/96.5Sn-3.5Ag/Cu [26]
38.7 47.3 398 e 473 (125e200) Cu(99.999% & 99.9%)/Sn (99.999%) [27]
57.0 83.8 373 e 443 (100e170) Pure Cu/dip-coated Pb-free Sn [28]
130 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138

Table 3
List of tracer diffusivity ratios from literature found in CueSn diffusion couples for Cu3Sn and Cu6Sn5.

Ratio of tracer diffusivities

 
  Temperature range Details Ref
D*Cu =D*Sn  D*Cu =D*Sn 
ε h [K] (
C)

z30 z0.35 423 e 623 (150e350) Incremental Diffusion Couples Cu/Cu3Sn and Cu3Sn/Sn [22]
z1.1 z0.63 488 (215) Cu(99.999%)/Sn(99.999%) Diffusion pair [30]
z1.9 z3.23 473 (200) Incremental Diffusion Couples Cu/Sn and Cu/Cu6Sn5 [27]
z3 z0.6 398 (125) Pure Cu/Reflow Sn Diffusion pair [31,32]

11 8 8 11
qCu6=11 Sn5=11 /q½Snd þ qCu3=4 Sn1=4 sCu3=4 Sn1=4 þ s½Snd / sCu6=11 Sn5=11
3 3 3 3
Interface II: (Cu6Sn5side) Interface III:

20 11 5 11
rCu3=4 Sn1=4 /r½Cud þ rCu6=11 Sn5=11 rSn þ r½Cud / rC Sn
9 9 6 6 6=11 5=11
This set of interfacial reactions describe the diffusion driven

Fig. 2. SEM micrographs of commercial solution samples cross-sectioned and thermally annealed at 423 K (150
C) for a) 0, b) 4, c) 8, d) 24, e) 48 and f) 72 h. Figure f) indicates the
main items within the CueSn system including the Si substrate, electroplated Cu film, both IMC layers Cu3Sn and Cu6Sn5 and electroplated Sn.
 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138 131

reactions. The p refers to the molar flux of Cu and q to the molar flux Table 4
of Sn diffusing through Cu3Sn phase per unit area [mol m2]. r and s Summarised results for the studies into the growth rates of void sizes and void
densities as a function of isothermal annealing at a temperature of 423 K (150
C).
are the moles of Cu and Sn through Cu6Sn5 phase per unit area Growth rate is the average cross-sectional area of the voids per hour, the density is
[mol m2] respectively. All molar fluxes are over a total reaction the average number of voids per unit area at the point of void saturation and the
time. The square brackets with subscript d refers to the diffusing location describes how the voids are distributed within the Cu3Sn phase. Cu3Sn
species. The total phase thickness over a total diffusion time is the represents voids that are evenly distributed throughout the Cu3Sn phase and
interface describes voids that form at the Cu/Cu3Sn interface.
product of the molar volume of the species and the sum of the
source and consumption of the fractional molar fluxes, Solution Void behaviour
  Current Growth Density Location
20 8 20 8 [mm2 h1] [N mm2]
Dxε ¼ Vmε 4q þ pþ q r s (2) Density e
9 3 9 3
Basic Solution A LCD 0.006 0.160 Cu3Sn
MCD 0.002 0.254 Cu3Sn
 
11 11 11 11 11 HCD 0.001 0.290 Cu3Sn
Dxh ¼ Vmh rþ rþ s p q (3) Basic Solution B LCD <0.001 0.146 Cu3Sn
6 9 3 9 3 MCD <0.001 0.054 Cu3Sn
HCD <0.001 0.040 Cu3Sn
h
ε and V are the molar volumes [m3 mol1] of Cu Sn and
where, Vm m 3 Commercial Solution LCD <0.001 0.233 Interface
Cu6Sn5 respectively. The phase formation rate is determined by the MCD <0.001 0.079 Interface
molar fluxes over a given total diffusion time. As the CueSn com- HCD 0.004 0.106 Interface
SPS LCD 0.001 0.329 Interface
ponents diffuse at differing rates in the IMCs, the ratio of the tracer
MCD 0.001 0.446 Interface
diffusion coefficients is equivalent to the molar flux's, HCD e e e
 PEG LCD 0.001 0.418 Cu3Sn
D*Cu  p MCD 0.001 0.271 Cu3Sn
 ¼ (4) HCD e e e
D*Sn  q SPS þ PEG LCD 0.001 0.411 Cu3Sn & Interface
ε
MCD 0.001 0.401 Cu3Sn & Interface
 HCD e e e
D*Cu  r
 ¼ (5)
D*Sn  s
h
the purity of the electroplating chemistries on the propensity for an
where, D*Cu and D*Sn are the tracer diffusivities of the Cu and Sn interface to experience voiding. As basic solution A has a sulphuric
components in the respective phases [m2 s1]. This ratio indicates acid of lower purity, it could be expected to experience a higher
the dominating diffusion species in the different phases. Table 3 is a propensity to void. Results show comparatively higher voiding
list of reported ratio of tracer diffusivities. In the CueSn system it levels (see Fig. 3) in both the average void size and in density, also
has been reported that there are difficulties in determining the the LCD had high average void size growth that led to delamination
tracer diffusivities due firstly to, in a CueSn diffusion pair, inert occurring during SEM sample preparation after 48 h (resulting in
markers do not appear in the Cu3Sn phase and secondly as the the discontinued data).
Cu3Sn/Cu6Sn5 interface is non-planar, average marker distances The growth rates for the basic solution A are presented in Fig. 3.
have been measured with reported statistically large variations The average void size and density appear to be interlinked as
[22]. Although diffusivity ratios are varied and are dependent on samples with high average void sizes experienced lower void
many factors, it is a common understanding that at solidus tem- densities. This could be due to larger voids consuming smaller voids
peratures Cu is the dominating diffusing species in Cu3Sn and Sn is thus keeping the overall void density low. Void density has an
the dominating diffusing species in Cu6Sn5. initially fast growth phase followed by saturation where there is
little to no additional void formation. The average void size appears
4. Results to grow linearly as a function of time. IMC growth rates for all the
current densities show characteristic parabolic growth rates,
4.1. Characteristic void formation and CueSn IMC thickness during although there are small growth rate variations between the
isothermal annealing samples.
In contrast to basic solution A, basic solution B is formed from
This section presents results for samples which were thermally electroplating chemicals that are of high purity. Fig. 4 is an example
aged for different durations. The results for the average void area, of an interface that experiences a low propensity to exhibit voiding.
density and IMC thickness (Dxε and Dxh ) data are presented as a If voids formed, they would typically be very small in cross-section
function of isothermal ageing and are grouped under their respective area. This result draws a direct link between the purity of the
electroplating solutions. Not only will the characteristic void behav- electrolyte used and the likelihood of an interface to experience
iour be analysed, but in addition conclusions are drawn about the interfacial voiding. For the IMC growth rates, the results show
effects that void size and density have on IMC growth rates. Variations typical parabolic growth rates as a function of thermal ageing, with
in the parabolic growth rates will be identified and discussed with an little variation between electroplating current densities. This in-
attempt to understand of the effects that voids have on IMC growth dicates that the quality of the electrolyte can influence not only the
processes. Fig. 2 illustrates the IMC and void evolution during propensity for an interface to void, but also change the IMC growth
isothermal annealing. In addition, the critical features (electroplated characteristics of an interface. The small variation in IMC growth
components, IMCs and voids) of the CueSn interface are indicated. rates between samples suggests there is little to no difference be-
Table 4 is the summary of results for the growth rates of the void sizes tween the microstructure of the as deposited Cu structure resulting
and the void densities as a function of isothermal annealing. in common growth rate parameters.

4.1.1. Basic solution A and B 4.1.2. Commercial solution

The purpose of basic solution A and B is to assess the impact of This subsection focuses on the behaviour of a common
132 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138

Fig. 3. Results for Basic solution A. Figure (a) shows the average void size (left hand side vertical axis) and void density (right hand side inverse vertical axis). Figure (b) gives the
thickness growth of the IMCs as a function of isothermal ageing of Cu3Sn (ε) and Cu6Sn5 (h) at three different current densities. Included are three SEM micrograph abstracts to
illustrate voiding characteristics.

commercial electroplating solution to determine its effect on
voiding characteristics. Commercial solutions are typically pro-
prietary and the exact combination of additives is unknown.
Nonetheless, it is important to understand the voiding character-
istics of such electroplating chemistries. It must be stated at this
point that the supplier recommended electroplating current den-
sity is 20 [mA cm2] or MCD as shown in the figures. Results show
in Fig. 5 that for the LCD and the MCD there is a small average void
size and a low to medium level of void density. For the HCD, the
cross-sectional area of the voids grows rapidly, in stark contrast to
the LCD and MCD samples. As typically commercial solutions use
high purity chemicals the mechanisms for void formation appear to
be different. Additionally, voids that formed, typically formed
within close proximity to the Cu/Cu3Sn interface. As electroplating
additives are used in commercial electroplating solutions, it is
plausible that at higher plating current densities more of the re-
sidual products from the solution breakdown and incorporate into
the deposited Cu film. Regarding the IMC growth, both the LCD and
the MCD exhibited parabolic growth rates. The exception was the
HCD sample, which after 24 h of isothermal ageing experienced a
receding Cu3Sn thickness and accelerated Cu6Sn5 thickness growth.
This behaviour of the IMC growth is fundamentally different, as the
parabolic growth of the HCD sample is not maintained for the
duration of thermal annealing. Therefore, the underlying phase
growth mechanisms appear to be different for this case. Interest-
ingly as the Cu3Sn thickness reduces, the Cu6Sn5 growth rate in-
creases suggesting Cu6Sn5 is consuming Cu3Sn.
4.1.3. Additive solutions SPS, PEG and SPS þ PEG
The results for the additive solutions showed similar charac-
teristics for both the electroplating chemistries and the current
densities. Typically voids form very quickly (<8 h) and the density
of voids saturated as no additional new voids formed. The average
void size from the additive samples was typically very low
(<0.1 [mm2]) and stayed below this level for the duration of the
thermal annealing, although the growth rate was still proportional
to the time.
An interesting observational difference between the chemistries
was the distribution of the voids with respect to the Cu/Cu3Sn
interface. The SPS additive showed a high concentration of voids
 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138 133

Fig. 4. Results for Basic solution B. Figure (a) shows the average void size (left hand side vertical axis) and void density (right hand side inverse vertical axis). Figure (b) gives the
thickness growth of the IMCs as a function of isothermal ageing of Cu3Sn (ε) and Cu6Sn5 (h) at three different current densities. Included are three SEM micrograph abstracts to
illustrate voiding characteristics.

located at the Cu/Cu3Sn interface, whereas PEG exhibited a more
evenly distributed behaviour. This behaviour is illustrated in Fig. 6.
The top SEM micrograph in Fig. 6 indicates the MCD PEG solution
after 48 h of thermal annealing where voids are more evenly
distributed within the Cu3Sn phase. The bottom two SEM micro-
graphs are the MCD SPS solution thermally aged for 8 and 48 h
where voids show a tendency to form at the Cu/Cu3Sn interface. In
the case where voids formed close to the interface, abnormal IMC
growth occurred. Cu3Sn decreased in size and Cu6Sn5 appeared to
be enhanced (similar behaviour as was observed in the Commercial
solution HCD) after 24 h of thermal annealing, as seen in Fig. 6(b).
4.2. Activation energy of IMC phases
The results of the activation energies for the phases Cu3Sn and
Cu6Sn5 are presented in Table 5. The values of the activation en-
ergies are within the range of values presented in Table 2 from a
literature survey. The Cu3Sn phase was typically at the lower end of
the values for the activation energies. Interestingly, the magnitude
of the difference in the activation energy between current den-
sities, changes depending on the electroplating chemistry. For
example in Cu3Sn, the SPS þ PEG sample has a difference between
the HCD and the LCD of 6.5 [kJ mol1] compared with the com-
mercial solution which has a difference of only 0.3 [kJ mol1]. As
electroplating current density and additives have been reported
[33,34] to effect the microstructure and textures of Cu deposits, the
difference in activation energies can be expected.
The fitted data for Cu3Sn (seen in Fig. 7(a)) and for the Cu6Sn5
(seen in Fig. 7(b)) are the results of Arrhenius plots for selected
chemistries. One notable difference when comparing the data, is
the Cu6Sn5 reduced goodness of fit. The Arrhenius behaviour for the
test temperatures does not appear to hold fully true, where at a
specific temperature the underlying diffusion/reaction mecha-
nisms change. A number of studies [23,35] have suggested
(although further study is required) that at lower temperatures (in
this experimental case <423 K (150
C)), the bulk diffusion length is
134 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138

Fig. 5. Results for the Commercial solution. Figure (a) shows the average void size (left hand side vertical axis) and void density (right hand side inverse vertical axis). Figure (b)
gives the thickness growth of the IMCs as a function of isothermal ageing of Cu3Sn (ε) and Cu6Sn5 (h) at three different current densities. Included are three SEM micrograph
abstracts to illustrate voiding characteristics.

shorter when compared with short-circuit diffusion, such as grain 5. Discussion

boundary diffusion. Additionally a recent study [36] has shown that
grain boundary diffusion of Sn in Cu6Sn5 dominates contributing to
higher growth rates in fine grained Cu6Sn5. This short-circuit
diffusion results in an increased phase formation at lower tem-
peratures. Fig. 8 is a cross-sectional focused ion beam (FIB) image of
a thermally annealed sample, illustrating the different grain sizes.
Cu and Sn grains are clearly distinguishable, Cu3Sn grains are small
but observable, whereas Cu6Sn5 grains are indistinguishable. This
suggests that the Cu6Sn5 grain sizes are particularly small in nature
enabling significant short circuit diffusion paths for Sn to react with
Cu3Sn at lower temperatures.
Admittedly, to calculate an accurate activation energy of the
Cu6Sn5 formation additional data points would be required. Addi-
tionally, the Arrhenius plot should be divided into two regions, (i)
bulk diffusion and (ii) short-circuit diffusion. Therefore, the result
for the activation energies of the Cu6Sn5 phase growth are likely to
be underestimated, thus effecting the results of the physicochem-
ical approach used in the discussion section.
Void formation during isothermal ageing exhibited common
behaviour between samples for average void size and density. Void
sizes showed linear growth as a function of time, where the rate of
growth depended on the electroplating chemistries and current
densities. The average void density exhibited different behaviour.
Voids would form quickly and reach a saturation point, typically
less than 24 h. At this point, additional voids would cease to form.
Interestingly, voids exhibited two different formation locations, (i)
at the Cu/Cu3Sn interface and (ii) distributed throughout the Cu3Sn
phase. This behaviour was a function of the electroplating chem-
istries, adding further weight to the argument that additives used
in electroplating play a role in void formation.
The results for the IMC growth rate of the CueSn system un-
equivocally showed a dependence on interfacial voiding. The main
characteristic behaviour observed during isothermal ageing was
the suppressed Cu3Sn and enhanced Cu6Sn5 growth. This was
observed in the Commercial solution HCD (see Fig. 5), SPS MCD and
 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138 135

Fig. 6. Results for the MCD additive solutions. Figure (a) shows the average void size (left hand side vertical axis) and void density (right hand side inverse vertical axis). Figure (b)
gives the thickness growth of the IMCs as a function of isothermal ageing of Cu3Sn (ε) and Cu6Sn5 (h) at three different current densities. Included are three SEM micrograph
abstracts to illustrate voiding characteristics.

Table 5
Results for the parabolic growth pre-exponential factors, phase growth activation energies and their respective fit quality for selected electroplating chemistries.

Current Phase growth parameters

Solution density
Cu3Sn (ε) Cu6Sn5 (h)

k0p Q R2 k0p Q R2
[m2 s1] [kJ mol1] e [m2 s1] [kJ mol1] e

Basic Solution A LCD 2.42  109 69.3 0.9943 5.70  108 79.1 0.9638
MCD 1.28  109 67.5 0.9992 2.50  107 83.9 0.9683
HCD 1.14  109 66.5 0.9937 2.53  107 83.6 0.9676
Basic Solution B LCD 3.11  1010 64.3 0.9986 4.86  108 77.8 0.9581
MCD 8.07  1011 59.6 0.9996 2.69  108 77.8 0.9587
HCD 5.52  1011 58.1 0.9991 2.18  108 79.6 0.9650
Commercial Solution LCD 3.34  1010 64.4 0.9978 3.50  109 71.8 0.9413
MCD 3.11  1010 64.4 0.9999 1.62  108 76.2 0.9664
HCD 2.85  1010 64.1 0.9997 3.22  108 78.5 0.9660
SPS þ PEG LCD 2.87  1010 64.2 0.9843 3.73  1010 65.3 0.9812
MCD 9.47  1011 60.3 0.9963 5.85  1010 66.0 0.9417
HCD 4.26  1011 57.7 0.9968 6.19  109 73.6 0.9542
136 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138

Fig. 7. Parabolic growth constants of (a) Cu3Sn (ε) and (b) Cu6Sn5 (h) of selected electroplating chemistries at a MCD as a function of inverse temperature. The slope determines the
phase activation energy (Q/R) and lnðk0p Þ the pre-exponential factor.

SPS þ PEG MCD samples and will be analysed using the physico-
chemical approach. This behaviour is associated with small dense
voids that form at the Cu/Cu3Sn interface. The impact of a high
density of voids at the Cu/Cu3Sn interface is assumed to have a
diffusion barrier effect on diffusing Cu. As Cu3Sn and Cu6Sn5 form
so do interfacial voids, at a critical point (observed typically after
24 h) the diffusion of Cu atoms across the Cu/Cu3Sn is inhibited (see
having a narrow homogeneity range, determining an accurate
compositional range of these compounds is difficult. To overcome
these issues, Wagner's concept of an integrated interdiffusion co-
efficient D~ b is introduced. This is effectively the compositional
int
average of a phase represented as,
b2

Fig. 9) due to the void diffusion barrier. ZNB

~b ¼
D ~ dNB
D (6)
To analyse this case more quantitatively the physicochemical int
approach will be utilised [29]. A more detail and worked explana- NB
b1

tion of this method can be read from Ref. [23]. To use this approach,
the molar fluxes need to be determined from the phase growth data
presented in the activation energy section. As the phases that form
within the CueSn system are regarded as line compounds or as
Where integrating over a sufficiently small and unknown compo-
b b
sition range NB1 (left hand side) and NB2 (right hand side) of the b
homogeneous phase of the interdiffusion coefficient D ~ , the average
integrated interdiffusion coefficient of the phase can be deter-
mined. As the integrated interdiffusion coefficient term of a stoi-
chiometric composition is to be determined, compositional
gradients and molar volumes can be assumed to be constant. As the
solubility of the end components at the temperature presented in
this work are low, the integrated interdiffusion coefficient can be
approximated as follows,

h
~ ε ¼ 3 ðDx Þ þ 3 Vm Dx Dx
ε 2 ε ε
D int h (7)
16 2t 22 Vm 2t

Fig. 8. FIB image of a SPS þ PEG sample thermally annealed at 423 K (150
C) for 4 h.
Large grain sizes are viewable in Cu and Sn, small grains can be seen in Cu3Sn and no Fig. 9. Illustration of CueSn system after 24 h of isothermal annealing. Voids located at
distinguishable grains in Cu6Sn5. Pt is used to stabilise the Sn layer during FIB cross- the Cu/Cu3Sn interface form a diffusion barrier inhibiting the diffusion of Cu atoms
sectioning. from Cu towards Sn.
 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138 137

From the physicochemical approach there are multiple reaction

changes occurring where we assume that reactions at the interfaces
are, (i) unchanged and (ii) not rate limiting. The reactions are split
into two phases, phase I and phase II. Phase I is the initial CueSn
system state with interfacial reactions occurring before voiding
affected the Cu/Cu3Sn interface (see Fig. 1). Phase II is where voids
form a diffusion barrier for Cu at the Cu/Cu3Sn interface, illustrated
h
in Fig. 9. Dxε0 and Dx0 are the initial thickness formed during phase I
of Cu3Sn and Cu6Sn5 respectively. All thicknesses are given as a
function of the square root of time. This all results in the following
thickness relationships,
Phase I:
 
20 8 20 8
Dxε ¼ Vmε 4q þ pþ q r s (13)
9 3 9 3
 
11 11 11 11 11
Dxh ¼ Vmh rþ rþ s p q (14)
6 9 3 9 3
Phase II:
 
8 20 8
Fig. 10. IMC phase thickness as a function of thermal annealing HCD commercial so- Dxε  Dxε0 ¼ Vmε q r s (15)
lution sample. Measured data plotted with the physicochemical approach simulated 3 9 3
results. Figure is divided into two phases, (I) pre- and (II) post- Cu/Cu3Sn interfacial
void barrier formation.  
11 11 11 11
Dxh  Dxh0 ¼ Vmh rþ rþ s q (16)
6 9 3 3

h In phase II as the Cu source is removed, (3q) of Cu is unable to

h 2 h
~ h ¼ 30 ðDx Þ þ 3 Vm Dx Dx
ε
D (8) react with ðqÞ of diffusing Sn to form Cu3Sn. Additionally as Cu is
int
121 2t ε
22 Vm 2t unable to diffuse across the Cu/Cu3Sn interface the reaction where
The thicknesses used to determine the integrated interdiffusion (p) of diffusing Cu reacts with ð11=9pÞ of Cu6Sn5 to form Cu3Sn does
coefficients were calculated from the activation energy data, this not occur. The Cu3Sn phase will grow with ð8=3qÞ moles but is at
results in D~ ε ¼ 1:02  1018 ½m2 s1  and the same time consumed by Cu6Sn5 by ð20=9rÞ and ð8=3sÞ moles.
h int
~
Dint ¼ 1:51  10 18 2 1
½m s  for Cu3Sn and Cu6Sn5 respectively. The consumption of Cu3Sn outstrips its formation resulting in a
Solving for the flux parameters p, q, s & r requires Boltzmann's decrease in the Cu3Sn thickness. The difference with the Cu6Sn5
solution to Fick's laws, in combination with the ratio of diffusivities. phase is that there will be no consumption of ð11=9pÞ moles thus
The flux parameters can be determined by solving the following reducing the overall consumption of the Cu6Sn5 phase. The overall
equations (9e12) simultaneously, result is a faster growth rate of the Cu6Sn5 phase.
The results of the simulated IMC thickness growth seen in Fig. 10
ε   show that Cu/Cu3Sn void formation hinders the diffusion of Cu
~ ε ¼ Vm N ε q þ N ε p Dxε
D (9)
int
2t Cu Sn resulting in a reduction in the Cu3Sn phase and a promoted Cu6Sn5
phase growth. This assessment is in agreement with the observed
h   data where after 24 h of isothermal annealing Cu3Sn decreases in
~ h ¼ Vm N h s þ N h r Dxh
D (10) thickness and the rate of Cu6Sn5 growth increases. It is clear from
int Cu Sn
2t
Fig. 10 that the simulated thickness of the Cu6Sn5 phase has been
 underestimated. This underestimation is from the calculation of the
D*Cu  p activation energy from the diffusion couple tests. As discussed in
 ¼ (11)
D*Sn  q the previous section, the parabolic growth constants for the tem-
ε
perature of 373 K (100
C) is higher than expected resulting in an
 overall lower phase growth activation energy. This underestima-
D*Cu  r
 ¼ (12) tion resulted in a slower simulated growth of the Cu6Sn5 phase than
D*Sn  s expected. With this exception, the results from the simulated data
h
accurately represent the effects of voids on IMC growth kinetics.
Results for the flux parameters are,
h i
p ¼ 3:262  104 mol m2 t 2
1
6. Conclusions

h i Voids formed in the CueSn system are shown to be a function of

q ¼ 0:109  104 mol m2 t 2
1
electroplating parameters. Both the electroplating chemistry
composition and the current density effect the voiding character-
h i istics of an interface. The average void size and density have been
r ¼ 0:391  104 mol m2 t 2
1
reported. Observation of the average void density included the
rapid formation of voids followed by saturation where after the
h i initial formation, there was little to no change in the density. The
s ¼ 1:118  104 mol m2 t 2
1
average void size appeared to grow linearly with time at varying
growth rates. CueSn IMC growth rates observed in this work
138 G. Ross et al. / Journal of Alloys and Compounds 677 (2016) 127e138
appeared to be dependent on interfacial voids. The impact that
voids had on the IMC growth kinetics varied depending on the
voiding behaviour of the interface. The physicochemical approach
was used to analytically assess the process occurring at the phase
interfaces, in order to understand the effects of voids on the reac-
tive diffusion processes. The most common effect that interfacial
voiding had was the reduction of the Cu3Sn phase and the favoured
growth of Cu6Sn5. As an interface evolved, voids that formed at the
Cu/Cu3Sn interface effectively disrupted the Cu diffusion path
which created the situation where the Cu6Sn5 phase consumed the
Cu3Sn phase.
Acknowledgements
The authors would like to thank EU Eniac, Finnish Funding
Agency for Technology and Innovation, Okmetic and Murata Elec-
tronics Oy for their financial support for the Lab4MEMS II project.
€ntyoja for the
An additional acknowledgement goes to Nikolai Ma
sample preparation and imaging.
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