Materials Letters 58 (2004) 3876 – 3878

www.elsevier.com/locate/matlet

Joining of Mo to CoSb3 by spark plasma sintering by

inserting a Ti interlayer
Junfeng Fan, Lidong Chen*, Shengqiang Bai, Xun Shi
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences,
1295 Dingxi Road, Shanghai 200050, China

Received 23 April 2004; accepted 23 July 2004

Available online 7 September 2004

Abstract

CoSb3-based skutterudite compounds are promising candidates as advanced thermoelectric (TE) materials used in TE power generation.
The electrode fabrication is one of the key techniques in constructing TE elements for the practical application. In the present study, sintering
of CoSb3 powder and joining of CoSb3 to molybdenum electrode have been simultaneously performed by spark plasma sintering (SPS)
technique. The insertion of Ti interlayer between Mo and CoSb3 is effective to join CoSb3 to Mo by forming an intermediate layer of TiSb at
the Ti–CoSb3 boundary and a composition–gradient alloy layer at the Ti–Mo boundary. Potential voltage measurement results indicated that
CoSb3/Ti/Mo joint interface has a low electrical resistance. The CoSb3/Ti/Mo joints also have a moderately high shearing strength and high
thermal duration stability.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Thermoelectric; Electrode fabrication; Adhesion; Sintering

1. Introduction order to obtain a high efficiency of energy conversion, the

Thermoelectric (TE) material can convert heat energy
directly to electric power by the Seebeck effect. The
thermoelectric power generation has increasingly attracted
worldwide attention for the applications as special power
supplies or in the recovery of exhaust heat energy or the
solar heat energy, because it is characterized by high
reliability and friendliness to the environment [1,2]. Doped
and filled CoSb3-based skutterudite compounds are newly
developed advanced TE materials for the applications in
power generation, because they possess moderately high
thermoelectric performance in the intermediate temperature
region (600–900 K) [3–6].
Electrode fabrication is one of the key techniques in
constructing TE elements for the practical applications. In
* Corresponding author. Tel.: +86 21 52412520; fax: +86 21
52413122.
E-mail address: cld@mail.sic.ac.cn (L. Chen).
0167-577X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2004.07.041
electrodes need to have high electrical conductivity and
thermal conductivity. It is also important to reduce both the
electrical resistance and thermal resistance of the interface
between TE material and metallic electrode. High thermal
duration stability and low thermal stress in the interface are
also important for the long-term use in power generation. In
the past three decades, as the typical applications, TE
devices using PbTe and/or SiGe-based alloys have been
successfully developed and used in various space programs
[7,8]. Fe and Ni are the commonly known electrode
materials for PbTe elements, and carbon or tungsten is
applicable for fabricating SiGe elements [1,9,10]. Recently,
some studies have been reported on the fabrication of TE
unicouple elements using doped and/or filled CoSb3-based
skutterudite materials [7,11,12]. However, there are few
reports on the details of the joining process, and the thermal
and electrical characters of the joints of electrode and
CoSb3-based thermoelectric materials, though these factors
have a strong influence on the conversion performance,
operating reliability and operating life of TE elements.
 J. Fan et al. / Materials Letters 58 (2004) 3876–3878 3877

Although, for the practical applications, the doped CoSb3 CoSb3 powder compact and joining of CoSb3 to metal is
and CoSb3-based filled skutterudites should be the candi- simultaneously performed in one SPS process.
date materials rather than the undoped CoSb3 binary The microstructures of the CoSb3/Ti/Mo joints are
skutterudites, it is essential and beneficial for achieving examined by scanning electron microscopy (SEM) and
both scientific and technological comprehension to inves- electron probe micro-analysis (EPMA). The electrical
tigate the joining process and interface characters by using contact in the interface is evaluated by measuring the
CoSb3 binary skutterudite. In the present study, joining of potential profile of the joints by a four-probe method.
CoSb3 to molybdenum electrode has been carried out by The bonding strength is measured by a shear test. The
spark plasma sintering (SPS) technique by inserting a using environment of thermoelectric modules in power
titanium interlayer. The microstructures of the interface, generation is usually inert atmosphere in an encapsulated
the electrical and mechanical properties and thermal stability state or vacuum such as for space application [1,7,12]. In
of the joints are studied. order to evaluate the thermal duration stability of the
joints in the using environment, the CoSb3/Ti/Mo samples
are exposed at 773 K for 1000 h in vacuum. The
2. Experimental procedure microstructure analysis and potential profile measure-
ments are also carried out for the samples after heat
Fe and Ni are not suitable for CoSb3 elements due to exposure.
their large thermal expansion coefficients (a Ni=13.310 6
K 1, a Fe=11.810 6 K 1) as compared to CoSb3 (a CoSb3=
6.410 6 K 1), though they have high electrical conduc- 3. Results and discussion
tivities and thermal conductivities. The high chemical
activity of Fe and Ni to CoSb3 also restricts their application CoSb3 is sintered and joined with Mo plate simulta-
in CoSb3 elements, because Ni and Fe can partially neously by inserting a thin Ti interlayer. The relative density
substitute Co site at high temperatures and therefore give of the obtained CoSb3 body is about 98%. In all cases of
influence on the thermoelectric transport properties of shearing strength test, fracture occurs along the Ti–CoSb3
CoSb3 or CoSb3-based filled skutterudites [3,6]. Titanium interface indicating the bonding strength of Ti/Mo is higher
has a close thermal expansion coefficient with CoSb3 but its than that of CoSb3/Ti. The average shearing strength is 58
thermal conductivity and electrical conductivity are too MPa while that of the CoSb3 bulk material is measured at
small for the electrode material. Molybdenum has a high about 80 MPa.
electrical conductivity (1.9107 S m 1) and a high thermal There are no cracks found around the overall interfaces
conductivity (142 W m 1 K 1) and its thermal expansion of CoSb3/Ti/Mo joint. The thickness of Ti interlayer is
coefficient (6.6210 6 K 1) is close to that of CoSb3. In the about 200 Am. Between Ti and Mo, there is an intermediate
present experiment, metallic molybdenum is chosen as the region with a thickness of about 50 Am in which the
electrode material.
CoSb3 ingots are obtained by melting the constituent
elements in vacuum-encapsulated quartz tube at 1333 K
followed by annealing at 873 K for 150 h. The resulting
ingots are ground into powder for use in the next sintering
and joining process. The spark plasma sintering (SPS)
technique (Sumitomo Coal Mining, SPS 2040) is applied to
join CoSb3 and Mo plate. A disk-shaped Mo plate (purity:
99.9%) in thickness of 2 mm and diameter of 10 mm is used
as the electrode. However, Mo was not able to join directly
to CoSb3 below the decomposing temperature of CoSb3
(T de=1147 K) [13]. Ti is used as the inter-layer inserted
between Mo and CoSb3.
The joining process includes two steps. Firstly, a disk-
shaped Ti/Mo multi-layer plate is fabricated by sintering Ti
powder (purity: 99%) compact on a Mo plate through SPS
process at 1253 K within a graphite die of 10 mm inner
diameter under a pressure of 40 MPa in a vacuum. The Ti
side of the obtained Ti/Mo plate is polished and ultrasoni-
cally cleaned in ethanol for use in the next process. As the
second step, CoSb3 powder is placed on the Ti side of Ti/Mo
plate mounted in a carbon die, and then sintered at 853 K Fig. 1. The SEM micrograph and EPMA composition profiles of joint
under pressure of 40 MPa in vacuum. The sintering of interfaces of CoSb3/Ti.
3878 J. Fan et al. / Materials Letters 58 (2004) 3876–3878
Fig. 2. Potential voltage profiles in the CoSb3/Ti/Mo joints.
contents of Mo and Ti changed gradually in a reverse
manner. It is known that Mo and Ti can form solid solution
in a wide composition range [14]. This intermediate layer
between Ti and Mo is composed of Mo–Ti solid solution
with graded Mo and Ti contents formed by the inter-
diffusion between Ti and Mo. This Ti/Mo graded layer may
contribute to the tight bonding between Ti and Mo as
indicated by the shear test result. Fig. 1 shows the
microstructures and the EPMA composition profiles near
the CoSb3/Ti interface. There are two inter-layers, bAQ and
bBQ. The bAQ area is about 5 Am in thickness and bBQ about
1–2 Am. By the EPMA analysis, area bAQ is composed of
Ti and Sb in a molar ratio of about 1:1. So the area bAQ is
considered to be corresponding to the binary compound of
TiSb. This binary compound layer may be formed by the
inter-diffusion process between Sb and Ti during SPS
process. The composition of the narrow area bBQ is difficult
to be examined by EPMA analysis; however, it may be the
ternary compound of Ti–Sb–Co because the EPMA
analysis showed the existence of these three elements. Ti
is not detected within the CoSb3 area, indicating that the
diffusion of Ti is bblockedQ by the intermediate layers bAQ
and bBQ.
Fig. 2 shows the potential profile near the joint interface
of CoSb3/Ti/Mo. No abrupt change in voltage was found
around the interface, which indicated that the intermediate
layers formed around the interfaces did not bring any
electrically resistive layers and the interfacial resistance in
the present CoSb3/Ti/Mo system is minimized.
In order to investigate the thermal duration stability of
the CoSb3/Ti/Mo joints, a long-term exposure test was
carried out for SPS-joined samples. The thickness of the
intermediate layer and composition profile did not change
and the molar ratio of Ti/Sb in the TiSb region was kept
unchanged after exposure at 773 K for 1000 h compared
with the as-sintered sample. Furthermore, the potential
profile showed no changes compared with the as-joined
samples. No abrupt change in voltage was found around
the interface. These results indicated that heat exposure at
the present condition did not bring any changes in the
interface microstructures and electrical contact of the
joints. The CoSb3/Ti/Mo joints have excellent thermal
duration stability.
4. Summary
Metallic Mo has been successfully joined to CoSb3
thermoelectric material by inserting a thin Ti layer by SPS
process. Ti–Mo solid solution layer with graded composi-
tion was formed at the Ti/Mo interface, while TiSb binary
compound layer was examined in the CoSb3/Ti interface.
The joint interface showed a good electrical contact and a
moderately high shearing strength that is about 58 MPa. The
long-term heat-exposure test showed the good thermal
stability of the CoSb3/Ti/Mo joints.
Acknowledgements
This work was partially supported by National Natural
Science Foundation of China under grant nos. 50325208
and 50310353 and National High Technology Research and
Development Program of China (863 program) under grant
no. 2001AA323070.
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