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Compositional change during Sputtering of (Ti,Zr)NiSn and NbNiSn Thin

Films on Different Substrates for Thermoelectric Applications

Conference Paper · February 2013

DOI: 10.13140/2.1.4780.2880

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Proceedings of the 2012 Powder Metallurgy World Congress & Exhibition PM 2012 Yokohama, ed. Hideshi Miura, Akira
Kawasaki, ISBN 978-4-9900214-9-8, 2013-02, Copyright © Japan Society of Powder and Powder Metallurgy (JSPM)

16E - S1- 13 (6 pages)

Compositional change during Sputtering of (Ti,Zr)NiSn and NbNiSn

Thin Films on Different Substrates for Thermoelectric Applications
1 2 2
Wilfried Wunderlich , Ami Koori , and Yoshito Matsumura
1 Tokai University, Fac. Eng. Mat. Sci. Dep., Kitakaname 4-1-1, 259-1292 Hiratsuka, Japan
2 Tokai University, Fac. Eng. Energy Dep., Kitakaname 4-1-1, 259-1292 Hiratsuka, Japan

Email: wi-wunder@rocketmail.com

Abstract.
Thermoelectric material with Half-Heusler phase such as TiNiSn has been reported as a possible with figure-of-merit larger
than ZT>1. We produced several specimens by arc-melting with different compositions in order to produce targets for
magnetron sputtering. Thin films were sputtered with this technique on different substrates, including Ni, Cu, Ti metals and Si
wafers and their Seebeck coefficient was measured. The SEM-EDX observations confirmed their homogenous element
distribution. All thin films show good electric conductivity and reasonable Seebeck coefficient, which has the high values for
(TiZr)NiSn and NbNiSn thin films deposited on Cu.

Introduction
Intermetallic phases composed of (TiZr)NiSn crystallize in half-Heusler (HH) structure and are considered as successful
thermoelectric (TE) materials [1-8]. The Seebeck coefficient is maximal for a Titan to Zirconium ratio of around 2:1 [2], where Ti
and Zr commonly share one of the three available crystallographic sites. Thin film devices integrated into Si technology are
expected to be of large interest for practical applications in order to build small devices.
The conventional design for thermoelectric devices has a Π-shape consisting of bulk materials, where one leg is n-type, the
other p-type semiconductors. However, thin films of thermoelectric material have several advantages. They utilize the
confinement of electrons in the interface or allow straining the thin film by epitaxial growth [8]. In one geometric realization the
interface between different materials lies parallel to the heat gradient, and this idea has even been brought to an extreme by
placing a sandwich structure with an interface on the hot and cold end of a thermoelectric device [4,8-10]. This geometry allows
an easy and cheap way to utilize interfaces effects in thermoelectric and, hence, it is used in the experiments presented in this
paper. After explaining the experimental details and microstructure observations, this paper describes the characterization of
thermoelectric performance of thin films by applying a large temperature gradient [2,11,12] and compares their properties to
such of bulk samples. This paper extends our first paper [4] on Magnetron sputtering experiments of (Ti,Zr)NiSn on different
substrates. This time we focus on the composition change of target and thin film composition and the increase of the Seebeck
voltage on different substrates.

Experiment
The experimental procedure is described in Fig. 1. At first bulk specimens were produced by weighing fine powders with high
purity of Ti, Zr, Ni, Nb or Sn (Fine chemicals, Japan). Pellets were cold pressed with 50 MPa and a diameter of 15 mm and an

Fig.1 Experimental procedure for producing the specimens for the target Fig.2 Picture of the (Ti,Zr)NiSn target with
(upper part) and the thin film sputtering (below). attached 10 specimens.
Fig.3 SEM micrograph of an arc-metlted (Ti,Zr)NiSn specimen Fig.4 SEM micrograph of the NbNiSn target after 5h
used as target. sputtering.

average weight of 5 g. The arc melting was achieved by using pressed powder pellets, details are described elsewhere [2,3].
After arc-melting for at least two times the resolved half-spherical specimens were sliced and attached by silver paste with the
large area upwards unto onto a brass discs, 60 mm in diameter. The disc was before covered completely by a 1 mm Ti sheet.
As shown in Fig. 2 about ten specimens were arranged in a circle, where the highest sputter ratio was found in previous
experiments. Care was taken that all specimens have roughly the same height, because experience showed that edges which
are higher are preferentially sputtered. According to the SEM-EDX measurements of composition of the produced thin films the
target was modified. As seen in Fig. 2 we have replaced three specimens by square shaped pure Ti sheets. In the beginning of
this research we used oil for lubricating the cold pressing of the powder, but this yields to pores in specimens as seen in the
upper left and middle left specimens in Fig. 2. After knowing this, it was avoided.
The arc-melted specimens were still inhomogeneous. As confirmed by SEM-EDX the NiSn rich phase appears dark (Fig. 3),
the TiSn or NbSn rich phases appear light-grey and in rare cases not mixed Ti or Nb are observed as dark spots [3,7]. When
comparing the specimens of the target before and after sputtering (Fig. 3 and 4), it can be noticed that after sputtering the
surface become rough. SEM-EDX measurements confirmed that the remaining parts are enriched in Ni or Sn. The conclusion
as discussed in a later section is that strong bonding of Ni3Sn2 yields to a poor sputter rate compared to the other elements. We
often replaced targets, so we have no long-term experience for one target. When assuming that all material sputtered away from
the target reaches the substrate, then this effect should vanish for continuous processing.
The use of home-made sputter targets is concluded to be a very efficient and economic method. The composition of the
target can be easily changed by replacing specimens with those of other composition. While in the case of bulk specimens usual
two weeks annealing time at 700 oC were reported [7] in order to achieve homogeneity, the thin films in our experiments always
have homogeneous element distribution, as described later.
The substrate consists of pieces of Si wafer (5” n-type, Sumco, Finebrand, Japan) with polished (111) or (100) surfaces and
pieces of Ni, Cu and Ti pure metals (High purity Chemicals, Japan) or their alloys. The pieces were mounted to the substrate
holder by conducting tapes. The sputter conditions were 50 W plasma power, distance 60 mm, substrate temperature 180 oC,
and sputter time 60 min. Before each sputter experiment the target was pre-sputtered for ten minutes to remove surface
contamination. The specimen characterization was performed by Hitachi SEM operated at 20 kV, equipped with EDX (Noran).
Seebeck voltage was measured by attached Ni wires in air under a high temperature gradient up to ∆T = 650 K as described
previously [2,11,12], which results in comparable Seebeck coefficients that the usual measurements under small temperature
gradients. By closing the electric circuit between hot and cold end the short-circuit current can be measured [2,11,12].

Results and discussion

The Seebeck measurement on a (Ti,Zr)NiSn thin film on pure Cu as substrate is shown in Fig. 5. The inset shows the
geometry of measurement, the thin film was attached to two Ni-wires, which had a temperature difference ∆T as shown on the
horizontal axis in Fig. 5. The (Ti,Zr)NiSn thin films show their maximum Seebeck voltage at ∆T =600 K, while NbNiSn thin films
show a more linear behaviour up to a temperature gradient of ∆T= 650 K (Fig. 6). In the case of NbNiSn the bulk specimens
showed a poor Seebeck voltage of less than 10mV, while surprisingly the thin film deposited on Cu shows higher values of 50
mV (Fig. 6).
The behaviour of the Seebeck voltage measurements of bulk (Ti,Zr)NiSn specimens have been reported in previous papers
[2-4]. Five different series as indicated by the numbers in Fig.7 a and c were measured. The arrows in Fig. 7a indicate the
 Fig.6 Seebeck Voltage as a function of temperature
Fig.5 Seebeck Voltage as a function of temperature
difference for NbNiSn thin film deposited on a pure Cu
difference for the (Ti,Zr)NiSn thin film deposited on a pure Cu
substarte in the same geometry as shown in the inset of Fig.5.
measured in the geometry shown in the inset.

deviation of the desired composition by weighing the powder from the actual one measured by SEM-EDX. The accuracy of
SEM-EDX measurement of chemical composition by the Cliff-Lorimer method is less than 1 %. We assume that the specimen
was homogenous within the 200x200 µm2 measurement area. So from these two arguments we can conclude that the deviation
was caused by the arc-melting process. Sn has the lowest melting point compared to the other elements, and hence has the

Fig.7 Composition and colour scheme of (a,b) Seebeck voltage at ∆T =500 K and (c,d) short-circuit current of (a,c) bulk
specimens, (b,d) sputtered (Ti,Zr)NiSn thin films. The arrows indicate the deviation of the desired composition from the actual
one.
Table 1 Seebeck coefficient, maximum Seebeck voltage U, and maximum short circuit current I at a temperature difference of
∆T =500 K for (TiZr)NiSn and NbNiSn thin films deposited on several substrate materials as mentioned.

(Ti.Zr)NiSn thin film NbNiSn thin film

Seebeck Max U Max I Seebeck Max U Max I
coefficient at ∆T =500K coefficient at ∆T =500K
[mV/K] [mV] [µA] [mV/K] [mV] [µA]
Al-alloy -0.05 -35 -3 0.05 35 3
Cu-alloy -0.06 -50 -300 0.06 50 300
Glass -0.02 -5 -1 0.02 5 1
Fe-alloy -0.02 -10 -5 0.02 10 5
Ni -0.02 -25 -10 0.02 25 10
Si (100) -0.02 -25 -10 0.02 25 10
Si (111) -0.05 -50 -200 0.05 50 200
Ti-alloy -0.02 -4 -20 0.02 4 20

vapour pressure. The arrows indicate that the composition has shifted and remained a lack of Sn. So, we still failed to reach the
exact composition for the Half-Heusler phase marked by the black triangle in Fig. 7, but nevertheless the Seebeck voltage is the
highest for specimens near this composition. In the case of the thin film magnetron sputtering using a target composed of such
specimens, a similar shift of the composition is observed as indicated by the arrows in Fig. 7 b. In this case the directions of the
arrows are slightly different. We find a lack in Ni and Sn, because they obviously are sputtered as Ni3Sn2 nano molecules,
because of their strong mutual interatomic bond as explained by the high melting point of Ni3Sn2 at around 1250 oC. Sputter
ratios for each element depend on applied voltage, the plasma conditions like sputter gas, gas pressure, but in the case of
ternary or quaternary compounds there are no literature data available.
We have performed five sputter experiments for (Ti,Zr)NiSn with different compositions as marked with the numbers 6 to 10
in Fig. 7. We could not reach exactly the Half-Heusler composition, but it is obvious from Fig. 7 that the compositions of
specimen #10 corresponds to that of bulk specimen #5 and reaches large values for both, Seebeck voltage and short-circuit
current. Sputter experiments of NbNiSn show similar results. Nb behaves similar to Ti and the specimens also have a deficit in
Sn and Ni due to the above mentioned low sputter rate of Ni3Sn2.
Table 1 summarizes the result for the three sputter experiments of thin films which had a composition close to the half-
Heusler phase. The main result is that the type of substrate has a large influence on the Seebeck voltage and short circuit
current compared to the chemical compositions of the thin films. The Seebeck coefficient was determined from the average
slope of Seebeck voltage against temperature difference. Particularly (Ti,Zr)NiSn specimens showed non-linear behaviour with
a maximum Seebeck voltage often below ∆T=600K. That is the reason why Table 1 shows all three electric transport properties
separately. Large values for Seebeck voltage were achieved for metallic substrates with high electric conductivity, which were
Cu and Al. In summary we have tested twelve different substrates, that were Al-2.7%Mg-6.67at%Si alloy, pure Cu, Cu 9 at%Al
alloy, and Cu-3.7at%Zn-3.1at%Si-0.64at%Sn, which is the Japanese 10 yen coin, glass, pure Ni, Fe-0.4at%C, SUS304
stainless steel, n-doped Si with (100) or (111) surface, pure Ti, and a Ti-6%Si alloy. There is no significant difference between
each kind of alloy with the same base element, except for Si wafers, where the (111) surface showed larger values of Seebeck
voltage than the (100) surface. The results suggest that a large number of carriers provided by the substrate is responsible for
large Seebeck voltage of the composite. In case of insulating substrates or those with small carrier concentrations the thin film
show smaller Seebeck values. The conclusion is that a larger carrier concentration of the substrate is beneficial for the Seebeck
voltage of the thin film. Further research is required to check whether electron confinement at the interface plays a role as well.
The NbNiSn thin films could confirm these results, but with opposite sign of Seebeck voltage. While in the case of
(Ti,Zr)NiSn bulk specimens showed a maximum Seebeck voltage of -80 mV and short circuit current of -400µA [2], the
deposited thin films show slightly smaller values. In the case of NbNiSn the bulk specimens showed smaller values (-10 mV and
-5µA), but the thin film values are larger and consistent with the (Ti,Zr)NiSn values.
Microstructural characterization is shown in Fig. 8 to 10. The element distribution for the deposited (Ti,Zr)NiSn thin film are
very homogeneous as can be seem from the SEM-EDX chemical maps (Fig. 8). The surface roughness is very smooth, except
for the two specimens with large Sn –content numbered as 8 and 9 in Fig. 7. EDX confirmed that metallic excess Sn was
deposited on top of the thin films. Fig. 9 confirmed that layers with different composition can be grown subsequently. The cross
section shows columnar growth confirming the Thornton model for thin film growth. The thin film has strong bonding to the
substrate, no matter which shape it has. When removing the masking tape, the thin film breaks at this line; this is an evidence
Fig.8 SEM-Chemical mapping of the (Ti,Zr)NiSn thin film deposited on Si Fig.9 SEM micrograph showing the cross section
(111) wafer conforming its homogeneity. of four deposited layers with compositions as
mentioned.

Fig.10 SEM characterization of (a,b) NbNiSn (c) (Ti,Zr)NiSn thin films on structured Cu-3.7%Zn-3.1%Si-0.64%Sn substrate
(10 yen coin). In (a) the thin film covers the entire substrate, while in (b,c) the border, the upper part is the substrate, the lower
part the thin film.

for strong bonding to the substrate. In rare cases deposition of Sn-rich particles are observed at the edges of metallic specimens.
Fig. 10 shows the deposition of both (Ti,Zr)NiSn and NbNiSn thin films on the structured surface of a Japanese 10-yen coin.
When covering the substrate completely, there are no defects and the film thickness remains always constant, hence always
copying the structure of the substrate on its top surface (Fig. 10a). This is also observed on unpolished metallic surfaces, the
thin film surface reproduces a scratched surface of the substrate. On the other hand there are cases where the stiffness of the
masking tape prevents covering of the substrate structure. Then the thin film follows the tape structure and gets thicker at such
corners, as seen on left and right side of Figs. 10 b and c. While the bonding of (Ti,Zr)NiSn thin film is perfect even on flat glass
surfaces, the NbNiSn thin film repels, peels off or rolls, when the surface is too flat. Also substrate bending in concave shape
can be a reason for peeling off the NbNiSn film, when additional factors come together, like scratches or force from removing
the masking tape. This can be seen in the upper part of Fig. 10c.
Thin film deposition of intermetallic phases for thermoelectric applications is a pressing hot subject, because it allows
creating and designing many new devices. This paper could give some hints for understanding the mechanism, why some
interface enhances the Seebeck voltage of half-Heusler thin films, but further research is necessary.

Conclusions
The following results are obtained
(1) The described method using arc-melted specimens as a target for magnetron sputtering is an efficient method to test the
thin film growth of various intermetallic alloys. The composition of the arc-melted specimens for the target shifted from the
weigh-in ratio towards Ti, Zr and Ni-rich composition due to the large vapor pressure of Sn. The composition of the thin film
shifted from the target composition towards (Ti,Zr) due to the poor sputter rate of the strongly bonded Ni3Sn2 phase.
(2) The (Ti,Zr)NiSn thin films showed the same Seebeck voltage, Seebeck coefficient and short circuit current as in the case
of bulk materials when deposited on Cu, Cu-Al, Cu-Zn alloys or Si(111) wafers. For other substrate materials smaller values are
observed. The main result of this research is that influence on the Seebeck voltage from the substrate is much stronger than the
 variation with chemical composition of the thin film. The explanation is the increase in charge carrier concentration at the Fermi
level by the substrate or possible electron confinement at the interface.
(3) The Seebeck voltage and coefficient for NbNiSn, which was rather low in the case of bulk materials, is almost similar than
that of (Ti,Zr)NiSn thin film but with opposite sign; it is a n-type, when deposited on Cu, Cu-alloys or Si(111) wafers.
(4) The bonding of the (Ti,Zr)NiSn thin films onto all substrates are very good regardless structured substrates or types of
substrates. In the case of NbNiSn it is fairly good. Both thin films grow without defects very densely and homogeneous.

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