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Are Intermetallics in Solder Joints Really Brittle?

Chin C. Lee, Pin J. Wang, and Jong S. Kim


Electrical Engineering and Computer Science
Materials and Manufacturing Technology
University of California
Irvine, CA 92697-2660
cclee@uci.edu
In this paper, we collect and review the physical
properties of the important intermetallics in solders joints,
Cu6Sn5, Cu3Sn, Ni3Sn4, and AuSn4 These properties are
compared with that of reference materials Cu and Sn3.5Ag to
see where these intermetallics stand in terms of brittleness.
Better understanding of these properties help uncover the
fundamental reason of why a solder joint breaks. Four fracture
categories in flip chip solder joints are reviewed and discussed
to find out whether the interfacial fracture is related to the
IMC brittleness.

Abstract
In nearly all soldering processes, it is the intermetallic
(IMC) layer that bonds the solder to the base metal. Thus, the
IMC layer is necessary for any successful soldering operation
used in the electronic industry. That is, a solder joint always
has at least one IMC layer. While the IMC layer is needed, it
is not static. It grows in subsequent reflows and during aging
with time. Its growth without control could have adverse
effect on the reliability. This is particularly true for flip-chip
solder joints. The IMC, while necessary, seems to have also
brought some problems. Thus, many packaging and solder
experts believe that "the intermetallics are brittle and they can
often embrittle the solder joints". On the other hand, not one
really presents quantitative analysis to illustrate that the IMC
is indeed brittle. No one really interprets what it means by
"brittle." In this paper, we collect and review the physical
properties of four commonly seen intermetallics: Cu6Sn5,
Cu3Sn, Ni3Sn4, and AuSn4. These properties are compared
with that of reference materials Cu and Sn3.5Ag solder.
Based on the measured properties available, we analyze and
evaluate whether these IMCs are indeed brittle. Based on the
fracture of flip chip solder joints reported by others, we assess
whether the fracture is caused by the "brittle" nature of the
intermetallic as many believe or by something else.

2. Properties of Intermetallics
Table I exhibits the important properties of four
commonly seen intermetallics in flip chip solder joints that we
were able to collect: Cu6Sn5, Cu3Sn, Ni3Sn4, and AuSn4. Cu
and Sn3.5Ag solder are also included as references. As can be
seen, the table is far from complete. The compound that lacks
the most measured properties is AuSn4. This is surprising
because "Au or AuSn4 embritlement" is a well documented
phenomenon [24-26] and yet so little was known about this

1. Introduction
In all soldering processes used in the industry, the
fundamental principle of solder being able to bond to the base
metal is the formation of intermetallic (IMC) layer. The most
widely used soldering process is to bond Sn-based solders to
copper (Cu). In this popular process, tin (Sn) atoms form
Cu6Sn5 intermetallic with bare Cu. This IMC layer links the
Sn-based solder to the Cu. For bonding to Cu plated with Ni,
Ni3Sn4 is formed. For nearly all soldering processes reported
by electronic industries, the IMC layer is necessary for any
successful soldering operation. That is, a solder joint always
has at least one IMC layer.
While the IMC layer is necessary, it is not static. It grows
in subsequent reflows and during aging with time. Its growth
without control could have adverse effect on the reliability of
the solder joints. This is particularly true for flip-chip solder
joints [1-26]. As a result of various reliability issues related to
IMCs and IMC growth, IMC seems to have brought more
problems than solution. Thus, we often heard comments like
"brittle intermetallics" [19-23] and "Au or AuSn4
embrittlement" [24-26]. We probably have heard similar
statement for probably more than 3 decades. And yet, not one
really presents quantitative analysis and argument to illustrate
that the IMC is indeed brittle. No one really interprets what it
means by "brittle".

1-4244-0985-3/07/$25.00 02007 IEEE

compound.
The young's modulus of Cu, Cu3Sn, Cu6Sn5 and Sn3.5Ag
are: 130, 108, 86, 53 GPa, respectively. This gives the
commonly seen structure Cu/Cu3Sn/Cu6Sn5/Sn3.5Ag a
continuing decrease in stiffness and thus a decrease in elastic
mismatch. The modulus of Ni3Sn4 is 133 GPa which is much
higher than that of Sn3.5Ag solder. Thus, the Ni3Sn4/solder
interface has very high elastic mismatch. The Vickers
hardness of Cu6Sn5, Cu3Sn, and Ni3Sn4 are 378, 343, and 365
kg/mm2. These values are extremely high comparing to 30 for
Cu and 100 for Ni, both in kg/mm2 (Vickers) [37]. The
hardness of these three compounds is in the range of high
strength steel. In comparison, Cu is very soft. This might have
made many solder and packaging engineers to believe that the
IMC is brittle. However, many of them probably were not
aware that these three IMCs were so hard before they thought
that IMCs were brittle. On the other hand, hard materials do
not have to be brittle. The tool steel is extremely hard but it is
not brittle at all. In fact the tool steel is very tough.
We were not able to find tensile strength data of the
intermetallics. Without knowing the tensile strength, the
strength of these intermetallics under tension cannot be
evaluated. Keep in mind that "hardness" is measured under

compression.
So far, we still could not find a scientific and quantitative

definition of "brittle" or "brittleness." "Brittleness" appears to


be a subjective impression rather than a quantitative
evaluation. We could not find any established method that
measures "brittleness." If brittleness cannot be measured, how
can anyone make a comment of "intermetallics are brittle."?

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Table I - Key properties of Cu, Sn3.5Ag solder and four commonly seen intermetallics in flip chip solder joints.

96.5Sn3.5Ag 1271
221

Cu6Sn5 1281

Cu3Sn 1281

415

676

Ni3Sn4 1281
796

7.4

8.28

8.90

8.65

0.78

0.341

0.704

0.196

5.88xl 05

0.812xl 05

0.57xl 05

1.12xl 05

0.35xl 05

Thermal Expansion
CoeffJ (/0C)

16.42x1 0-6

22.2x1 0-6 [35]

16.3x1 0-6

19.OxlO-6

13.7xl 0-6

Yield Strength (psi)

10,000

3,600

19.3x1 0-6
[29]

Ultimate Tensile
Strength (psi)
Fracture Toughness

32,000

5,000-7,000
2.80 [30]

5.72[30]

4.22[30]

2.50[30]

Young's modulus (GPa)

129.8 [32]

52.73

85.56 [33]

108.3

133.3

71 [30]

Poisson's ratio

0.339

0.36

0.309

0.299

0.330

0.31 [33]

Hardness** (Vickers)

37 (Brinell)

14.8 (Brinell)

378 [34]

343 [34]

365 [34]

59.2 [30]

Properties

Copper 1271

Melting Point (C)

1,083
8.94
3.862

Density (g/cc)
Thermal Conductivity
(watt/cm-K)
Electrical Conductivity

(/Qcm)

(MPa/m112)

AuSn4
252

**Note: For conversion between Brinell hardness and Vickers hardness, see [36]
3. Are Intermetallics in solder joints really brittle?
In situations like this, we check the dictionary to find the
meaning of "brittle' that is understood by ordinary people.
The dictionary defines "brittle" as "easily broken." [38].
Condition under which an object is "easily broken" is not
specified. Thus, the condition should be that of which an
object is used or being used. So, the complete question to ask
should read "Are intermetallics in solder joints easily
broken?" The answer can be either "yes" or "no" depending
your impression of "how easy is easily." With the "easily"
understood by ordinary people, we would tend to believe that
the answer is no. That is, intermetallics in solder joints are not
easily broken. If the IMC were easily broken or brittle, all the
electronic products with solder joints would have reliability
issues.
Among the measurable properties, the one most closely
related to "brittleness" is probably fracture toughness.
Fracture toughness is measured during hardness test using
indentation. The hardness (Vickers) is defined as the load on
the indenter divided by the surface area of the indentation
observed, expressed in Kg/mm2. If cracking shows up from
the corners of the indentation, fracture toughness can be
determined. It is given by [39],
Fracture toughness =
0.016 (modulus/hardness)1/2 [load/(crack length)3/21

Here, the crack length is measured from the crack tip to the
center of the indentation. If cracking is not observed on the
indentation with the load applied, fracture toughness cannot
be determined. The fracture toughness of the four IMCs
shown in Table is 2 to 3 times of typical glass. Recent nanoindentation study on Cu6Sn5 and CuNiSn compounds does not
show cracking on the indentation marks [40].

We do not believe that fracture toughness data in Table I


can be applied to IMCs in solder joints without considering
the setting difference of the IMC in solder joint versus the
IMC in indentation test. In the indentation test, the IMC is
subjected to localized compression load produced by a
diamond tip. This condition does not exist for IMCs in solder
joints. The materials adjacent to IMC layer in solder joints are
solder, Cu, or Ni. Under compression, these materials are very
soft comparing to the IMC. The IMC layer is also quite thin
with large aspect ratio. Under compression, we do not believe
that the IMC will fracture.
If fracture within an IMC layer occurs, it most likely

happens under tension rather than under compression. Since


tensile strength of IMCs is still not available, there is not
sufficient scientific data to support the statement of "IMC is
easily broken under tension." Thus, there is no sufficient
scientific information to support the comment of "IMCs are
brittle."

4. The fracture of flip chip solder joints


Flip chip solder joints may fracture during various
reliability tests such as isothermal aging, thermal cycling,
thermal shock, mechanical loading, bending test, impact test,
and drop test. Fracture surfaces or interfaces vary and often
depend on test methods. They can be roughly divided into
four categories below:
1. Within solder,
2. Solder/IMC interface,
3. Within IMC region,
4. IMC/copper interface,
It seems that the key parameter that dictates the fracture
mechanism or fracture interface is the strain rate. For low

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2007 Electronic Components and Technology Conference

strain rate such as in isothermal aging, thermal cycling, and


slow mechanical loading, fracture tends to occur inside the
solder due to fatigue. In this case, the solder has enough time
to go through the complete plastic stain variation cycle and
becomes fatigued after certain number of testing cycles. For
high strain rate such as in the case of impact test, drop test,
rapid bending test, and thermal shock test, the strain rate is so
high that the solder material does not have time to incur
plastic deformation before the momentum transmits through
the entire solder joint structure. The momentum experienced
by the solder joint is proportional to the strain rate. Fracture
will occur along the weakest interface of the solder joint
structure. At high strain rates, the solder material, with no
time to deform in-elastically, appears stronger in terms of
tensile strength. This is referred to as strain-rate hardening.
Thus, at high strain rates, the chance of fracture inside the
solder material decreases.

Fig. 3-Crack propagates through the (Cu, Ni)6Sn5 IMC after


the drop test according to the JESD22-B1 11 standard [17]

Fig. 4-Voids form between Cu3Sn and Cu substrate after


7600-hour high temperature storage at 175 C [42]
Fig. 1- Cracks are inside the solder after thermal cycling
at 0C-1000C [2]

Fig. 2-Crack propagates along the interface of the bulk


solder/IMC layer after shear cycling test. The frequency of
the tests is 0.43 Hz. The shear displacement amplitudes are
set to values between 0.18 and 0.28 mm [41]

Among the four fracture categories, three are related to


intermetallic region (Figs. 2, 3, and 4). For fracture within
IMC region, it is usually caused by having more than one IMC
in the region. Fracture tends to go through the boundary
between two different IMCs [8]. Fracture seldom cuts cross a
single IMC phase. Table II exhibits the crystal structure and
lattice constants of Cu, Sn, and the four intermetallics
reviewed. For interfaces along Sn/IMC, IMCI/IMC2, and
IMC/Cu in a solder joint structure, the crystal structure and
lattice constants of materials in both sides of the interface are
very different. Thus, it is not realistic to expect that these
interfacial boundaries would always give a strong bond. When
fracture occurs along one of these interfaces, we really do not
see how this is related to the "brittle nature of IMCs." Two
materials put together do not always produce a strong bond on
the interface if they cannot share electrons effectively. Planar
boundary is easier to break comparing to a weaving boundary
because the materials in both sides of a planar boundary do
not have gripping or locking mechanism to increase the
strength. Fracture along interfacial boundaries can be
accelerated by interfacial stresses produced by difference in
physical properties such as thermal expansion coefficients and
mass density.

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Table II - Crystal structures and lattice constants of Cu, Sn and four intermetallics
Crystal structure
Face-centered cubic [43-44]
oc phase: Face-centered cubic [45-46]
D phase: Body-centered tetragonal [47-49]
Ni3Sn4 Monoclinic [50]
Cu6Sn5 Monoclinic [51]
Cu3Sn Hexagonal [50]
AuSn4 Orthorhombic [52]

Lattice constant
a =3.61509 A [43-44]
oc phase: a= 6.4912 A [45-46]
D phase: a = 5.8314 A, c = 3.1815 A [47-49]
a=12.472A, b=4.069 A, c=5.293 A, f=101051'[50]
a=11.022A, b= 7.282A, c= 9.827A, f=98.84[51]
a=2.753 A, c=4.385 A [50]
a = 6.45 A, b = 6.49 A, c = 11.60 A [52]

Cu
Sn

8.

5. Summary
We collected and reviewed the properties of Cu6Sn5,
Cu3Sn, Ni3Sn4, AuSn4, Cu and Sn3.5Ag to first understand
whether IMCs are brittle as many believe. Our conclusion
seems to indicate otherwise. There is no sufficient scientific
data to support the statement of "IMCs are brittle." Fracture
along interfaces such as solder/IMC, IMCG/IMC2, and
IMC/Cu is not related to whether the IMC is brittle or not.
Rather, this interfacial fracture is caused by insufficient bond
strength along the boundary. To blame brittle fracture in flip
chip solder joints to IMCs being brittle probably needs
reconsideration and further assessment.

9.

10.

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