Journal of Alloys and Compounds 460 (2008) 478484

Study on the properties of Sn9ZnxCr lead-free solder

Xi Chen , Anmin Hu, Ming Li, Dali Mao
Key Laboratory for High Temperature Materials & Tests of the Ministry of Education, School of Materials Science and Engineering,
Shanghai Jiao Tong University 200030, PR China
Received 28 February 2007; received in revised form 16 May 2007; accepted 23 May 2007
Available online 29 May 2007

Abstract
The influences of different Cr content to lead (Sn)Zn solder were investigated. Sn9ZnxCr shows finer and more uniform microstructure
than Sn9Zn. Thermal gravimetric analysis (TGA) and Auger electron spectroscopy (AES) results show that adding Cr significantly improves
the oxidation resistance of Sn9Zn solder, and reduces the thickness of oxidation film of Sn9ZnxCr solder. When Cr content is 0.1%, the
Sn9Zn0.1Cr solder have the best oxidation resistance. In addition, the effect of Cr addition on the wettability, melting point and mechanical
properties of Sn9Zn solder was discussed.
2007 Elsevier B.V. All rights reserved.
Keywords: Oxidation; Microstructure; Mechanical properties

1. Introduction
Leadtin (SnPb) solders are being widely employed in the
microelectronics industry due to their superior wetting properties, moderate melting temperatures and low-cost. However,
it has been pointed out that lead is harmful to human health
because it pollutes groundwater and causes lead poisoning [14].
Due to environmental and health concerns, efforts in replacing
conventional SnPb eutectic solder with lead-free alternatives
have begun [27]. Considering performance, reliability, cost
and resource, the SnAg and SnZn alloys have received the
most attentions. Compared with SnAg solder, SnZn solder
has many advantages, such as low melting point (198 C), adequate mechanical strength, low-cost and abundant supply, so it
has a bright development prospect and a great market potential
[813]; but because the Zn element is quite active, SnZn solder
is easy oxidation, poor wetting, and dross formation [1416]. It
is no doubt that the key issue is improving the oxidation resistance of SnZn solder. Recent researches [17] have shown that
oxidation is the major factor in poor wetting during soldering
to electrodes. In wave soldering process, oxidation will cause
excessive dross formation, it does not only waste solder, but also
causes solderability problem, which worsens reliability of solder

Corresponding author. Tel.: +8621 62933344; fax: +8621 62932522.

E-mail address: limpidsky@sjtu.edu.cn (X. Chen).

0925-8388/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2007.05.087

point. There is of importance to improve oxidation resistance of

SnZn solder.
Generally, there are two ways to partially improve wetting
ability of SnZn solder. One is to develop a new kind of flux
which is fit for lead-free soldering and the other is to improve
oxidation resistance by alloying. In this paper, we focus on the
second one. Some researches [18] have shown that P and La
can improve oxidation resistance of SnZn solder, and K. L.
Lin [19,20] has reported the effect of alloying addition of Al
and Ga to SnZn solder on oxidation resistance. Ag addition
has been reported to improve the wettability and oxidation resistance of the Sn9Zn solder alloy by Takemoto et al. [21] because
it decreases the anodic dissolution of Zn when the solder alloy
contacts with the Cu substrate. C. Y. Chou et al. [22] have disclosed that the addition of Cu in the Sn9Zn solder can decrease
the Zn activity and reduce the Zn segregation effect. Yu et al.
[23] have shown that Indium addition can decrease the melting
point of the SnZnIn solder alloys and enhances the wettability
between SnZnIn solder alloys and Cu substrates. But research
about oxidation resistance of SnZn solder is extremely limited.
According to former research about the effect of different alloying elements, such as La, Cr, Ti, Al, on SnZn based solder, we
suppose that Cr is the best choice that improves the oxidation
resistant of SnZn base solder [24]. In this work, we studied the
effects of different Cr content on the microstructure, oxidation
resistance, wetting properties and tensile properties of SnZn
based lead-free solder.

X. Chen et al. / Journal of Alloys and Compounds 460 (2008) 478484

479

Table 1
Chemical compositions of alloys used in this study (wt%)
Alloy

Zn

Cr

Sn

Sn9Zn
Sn9Zn0.05Cr
Sn9Zn0.1Cr
Sn9Zn0.3Cr

8.78
8.72
7.93
8.34

0
0.042
0.13
0.24

Bal.
Bal.
Bal.
Bal.
Fig. 1. Schematic illustration of sample for tensile test.

2. Experiment
Sn9ZnxCr alloys with x = 0, 0.05, 0.1, and 0.3, respectively,
were prepared from the pure metals (>99.99 wt%). The alloys
were melted within quartz tubes under nitrogen atmosphere, by
homogenizing and repeatedly shaking at 800 C over 8 h. During
this process, KCl/LiCl eutectic mixture served as a barrier layer
for oxidation. The compositions of alloys were investigated by
inductively-coupled plasma emission spectrometer (ICP-AES).
The chemical compositions of the alloys used in this study are
listed in Table 1.
Oxidation resistance of the alloys was investigated by thermal
gravimetric analysis (TGA), and brightness of surface compared
with each other after being oxidized at 250 C for different time.
Composition of the surface layers of different alloys were investigated by Auger electron spectroscopy (AES) after oxidation
at 250 C. Alloy microstructures were investigated using scanning electron microscopy (SEM). The spreading experiment was
carried out according to Chinas National Standard GB1136489 [25], the solder spheres were placed on Cu substrates and
the solderCu couples were heated at 250 C for 90 s. The
spreading areas were calculated by software, and the results are
average values from three measurements. The solidus and liquidus temperatures of the alloys were investigated by differential
scanning calorimetry (DSC). The tensile experiment was carried out according to Chinas National Standard GB/228-2002
[26]. Alloys with varying degrees of Cr content were machined

Fig. 2. TGA results of Sn9ZnxCr alloys (x = 0, 0.05, 0.1, 0.3).

into tensile specimens (Fig. 1). The entire experimental process,

including data acquisition and calculation, was controlled by
computer.
3. Results
3.1. TGA analysis
For understanding of the relationship between oxidation
resistance and Cr content, TGA is used and the results are

Table 2
Brightness distinction of alloys with different Cr content after heating at 250 C
Alloy

Heating time
Before

Sn9Zn

0.05

Sn9ZnCr

Cr content (wt%)

0.1

0.3

1h

2h

3h

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X. Chen et al. / Journal of Alloys and Compounds 460 (2008) 478484

Fig. 3. AES results of (a) Sn9Zn, (b) Sn9Zn0.05Cr, (c) Sn9Zn0.1Cr, and (d) Sn9Zn0.3Cr alloys.

demonstrated in Fig. 2. Oxidation resistance of Sn9ZnxCr

is obviously better than Sn9Zn. Furthermore, Sn9Zn0.1Cr
solder has the best oxidation resistance, while Sn9Zn0.3Cr
has the worst. The ability of different Cr content to improve
oxidation resistance decreased in the order of 0.1, 0.05, and
0.3%.
To qualitatively comparing oxidation resistance of alloys with
different Cr content, they were heated at 250 C for different
time. The results were listed in Table 2. It seems that 0.05% Cr
addition can keep the surface of Sn9Zn alloys bright, and 0.1%
Cr addition has a better effect. When Cr content is above 0.1%,
the brightness distinction is obscure.

3.3. Microstructure
Fig. 5 shows the SEM photographs of all specimens. Sn9Zn
alloy exhibits coarse dendrite structure and large and long rod or
needle-like Zn-rich precipitates [27]. While the microstructure
of Sn9ZnxCr alloys, which is dispersed rod or needle-like or
particle ZnCrrich phase in the -Sn matrix, is much finer and

3.2. AES analysis

Fig. 3 shows AES result. It indicates that Zn segregates in the
surface of all specimens, while Cr segregates in the subsurface
layer, and leads to thinner oxidation film.
Difference of the thickness of oxidation film (Fig. 4) implies
distinction in oxidation resistance among alloys, contained different contents of Cr. There are two key phenomena, one is that
oxidation film of Sn9ZnxCr alloy is much thinner than Sn9Zn
alloy, and the other one is that the thickness of oxidation film is
related with Cr content. It demonstrates that Sn9Zn0.1Cr has
the thinnest oxidation film; meanwhile Sn9Zn0.3Cr has the
thickest.

Fig. 4. Comparison of thickness of oxidation film among Sn9ZnxCr alloys

(x = 0, 0.05, 0.1, 0.3).

X. Chen et al. / Journal of Alloys and Compounds 460 (2008) 478484

481

Fig. 5. Microstructure of (a) Sn9Zn, (b) Sn9Zn0.05Cr, (c) Sn9Zn0.1Cr, and (d) Sn9Zn0.3Cr alloys.

more uniform, and there is little difference in the microstructure

of different Cr content.
3.4. Inuence on wettability
In general, there are two reasons explaining the poor wetting
of Sn9Zn: one is ZnO at the interface of solder and substrate
[14], the other one is the increase of surface tension caused by
Zn [15]. We suppose that ZnO is the major reason. As indicated,
Cr addition can improve oxidation resistance of Sn9Zn solTable 3
DSC results of Sn9ZnxCr alloys (x = 0, 0.05, 0.1, 0.3)

Fig. 6. Comparison of spreading area.

Alloy

Solidus ( C)

Liquidus ( C)

Melting range ( C)

Sn9Zn
Sn9Zn0.05Cr
Sn9Zn0.1Cr
Sn9Zn0.3Cr

198.18
198.10
198.26
198.04

202.69
202.70
202.75
202.54

4.51
4.60
4.49
4.50

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X. Chen et al. / Journal of Alloys and Compounds 460 (2008) 478484

der, and then we wonder how it affects wettability of Sn9Zn

solders. Spreading areas were calculated and compared it with
the eutectic Sn37Pb (made by Yunnan Tin Company Limited, Gejiu, P. R. C.) and Sn3.5Ag0.75Cu (made by Senju
Metal Industry Co., Ltd., Tokyo, Japan) solder, as presented in
Fig. 6.
On the whole, although wettability of Sn9ZnxCr alloy
is poorer than Sm-37Pb and Sn3.5Ag0.75Cu, Cr addition
can slightly improve wettability of Sn9Zn alloy. In accord
with TGA results, Sn9Zn0.1Cr has the best wettability, while
Sn9Zn0.3Cr has the worst.
3.5. Inuence on thermal properties
Fig. 7. Influence of Cr content on tensile strength and elongation of Sn9Zn
alloy.

Sn9ZnxCr alloys were investigated by DSC, and compared

with eutectic Sn9Zn alloy. Table 3 shows the results. Although

Fig. 8. Subsurface layer of (a) Sn9Zn0.05Cr, (b) Sn9Zn0.1Cr, (c) and (d) Sn9Zn0.3Cr alloys.

X. Chen et al. / Journal of Alloys and Compounds 460 (2008) 478484

refining microstructure, Cr has little influence on the thermal

properties of Sn9ZnxCr alloys. This phenomenon can also be
seen in SEM micrographs (Fig. 5); because of small quantities,
Cr does not cause great changes in the thermal properties of
Sn9ZnxCr alloy.
3.6. Inuence on tensile properties
Fig. 7 shows the stress-strain curves of Sn9Zn alloy with
different Cr content. The addition of Cr can significantly
improve the plasticity of Sn9Zn alloy. The plasticity of different Sn9ZnxCr alloys decreases in the order of Sn9Zn0.1Cr,
Sn9Zn0.05Cr, and Sn9Zn0.3Cr. We suppose that addition
of Cr destroys the coarse and brittle Zn-rich phase, and forms
much finer microstructure, as shown in Fig. 5. But excessive
Cr is detrimental to the plasticity of Sn9Zn alloy because the
Cr-rich phase is somewhat brittle.
4. Discussion
From the above research, the oxidation film and surface of
Sn9ZnxCr series alloy is much thinner and brighter than
Sn9Zn alloy (Figs. 2 and 3); it indicates that segregation of
Cr in the subsurface layer of Sn9ZnxCr solder can prevent
further oxidation. The influence of complicated oxide on the
diffusion rate of reactant ion can be explained by the Hauffe
atomic rule [28] as the oxidation resistance of steel. Presumably, a complicated oxide has contained ZnO and chromium
oxide but still retains the crystal structure of ZnO. It has been
proved that alloying addition of Cr can be oxidized to Cr3+ ions
which can improve the oxidation resistance of steel. On the other
hand, ZnO is typical n-semiconductor. In the Sn9ZnxCr solder, some Cr3+ ions replace Zn2+ ions in ZnO crystal lattice, and
then the reduction of interstitial Zn2+ ions leads to decrease the
rate of diffusion. It is known that, for n-semiconductor, formation
of oxidation film is controlled by diffusion of interstitial ion. As
the concentration of interstitial Zn2+ ions decreases, oxidation
would be suppressed.
While when Cr content is up to 0.3%, the oxidation resistance
of Sn9Zn solder becomes worse (Fig. 2), K. L. Lin [19,20] also
found that the addition of Al can increase the oxidation resistance
of SnZn solder, but they also found excess Al (0.001%) deteriorates wettability of the solder [29], but they did not explain the
reason. To clarify matters, the micrograph of subsurface layer
of all specimens is shown in Fig. 8. When Cr content is 0.05%,
there is no precipitated phase appeared in the subsurface layer, as
Cr content is up to 0.1%, there is few SnZnCr precipitated phase,
while the precipitated SnZnCr becomes more distinct as Cr content up to 0.3%. It is obviously that, Cr addition can increase the
oxidation resistance only when Cr is as solid solution state, however, when the Cr content is upon to 0.10.3%, some proportion
of Cr addition precipitates as a SnZnCr phase, the precipitation is not only harmful to continuity of the solder, but also
leads to chromium-poor zone around it in the subsurface layer,
these may be why the Sn9Zn0.3Cr solder has lower oxidation
resistance.

483

5. Conclusion
The addition of Cr makes Sn9ZnxCr alloy form finer
microstructure than Sn9Zn alloy. Segregation of Cr in the subsurface layer of Sn9ZnxCr alloy can prevent further oxidation.
Sn9Zn0.1Cr alloy has the best oxidation resistance, while
Sn9Zn0.3Cr has the worst. We suppose that chromium-poor
zone and bad continuity of the solder, which caused by some
proportion of Cr addition precipitates as a third phase SnZnCr,
leads to lower oxidation resistance of Sn9Zn0.3Cr alloy. Small
addition of Cr has little influence on the wettability and thermal
properties of Sn9Zn alloy. Sn9ZnxCr alloy exhibits better
plasticity than Sn9Zn alloy.
Acknowledgments
This work is sponsored by Shanghai nano technology promotion center (Contact No. 05nm05043) and Shanghai pujiang
program (Contact No.05PJ14065). We thank the Instrumental
Analysis Center of Shanghai Jiaotong University, for the use of
the AES, SEM and ICP equipment.
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