Low temperature thermoelectric properties of n-type CoSb 3

P. R. Realyvazquez-Guevara1, F. J. Rivera-Gomez1, A. Faudoa-Arzate1, M. E.

Botello-Zubiate1, C. R. Santillan-Rodrguez1, J. A. Matutes-Aquino1
1

Centro de Investigacin en Materiales Avanzados, S.C., Chihuahua, Chih.,

Mxico.
Polycrystalline skutterudite (CoSb 3) was prepared using a sequence of
processes including arc-melting, melt spinning, grounding, cold pressing and
annealing. At cryogenic temperatures, the I-V curves showed a non-linear and
hysteretic behavior. This non-linear behavior was originated from a fielddependent ionization mechanism, which becomes important at low
temperatures. The hysteresis was attributed to the drastic decrease of heat
capacity which produces Joule heating at cryogenic temperatures. Seebeck
coefficient, electrical and thermal conductivities were measured from 4 to 393
K. The effect of extrinsic carriers from non-stoichiometric variation was
analyzed. An estimate value of 0.5 eV for the bandgap energy, Eg, was
determined from Seebeck coefficient measurements. The maximum calculated
value ZT = 0.015 occurred at the maximum measured temperature of 400 K.
From heat capacity measurements, a Debye temperature of 295 K was
calculated. The presence of localized low-lying optical phonon modes of the
unfilled CoSb3 framework were observed.
Keywords: Thermoelectrics; skutterudites; low temperature; thermoelectric
properties.

1. Introduction
Thermoelectric (TE) materials provide a solution for power generation and is
considered as an attractive option for waste heat recovery systems [1]. The
main obstacle to widespread use of TEs in diverse industries is the low
efficiency of TE materials for converting thermal energy into electric energy [2].
TE conversion efficiency is mainly determined by the dimensionless
thermoelectric figure of merit, ZT, defined as ZT = S2T/(e+L), where S is the
Seebeck coefficient, T is the absolute temperature, is the electrical resistivity,
e and L are the electronic and lattice thermal conductivities respectively. Thus,
the higher the ZT, the greater the TE performance. S, and e are interrelated,
making one parameter difficult to optimize without adversely affecting the
others. Therefore, high ZT values arise from the beneficial combination of high
power factor, S2, and low thermal conductivity, ( e+L) [3]. Enhancing the
power factor can be obtained by many methods, such as band engineering and
electronic state distortion to enhance the Seebeck coefficients [4, 5]. Low
thermal conductivity can be obtained by either filling the voids of the crystal
structure in TE materials with cage-like structures or by nanopatterning and
nanostructuring [6, 7].

Skutterudites, one of the most promising materials for thermoelectric

applications, are good examples of the phonon-glass-electron-crystal concept
proposed by Slack [8] and, therefore, they are regarded as potential candidates
for next-generation thermoelectric materials for electrical power generation
using either solar energy or waste heat [9]. The general formula of skutterudite
compound is AB3, here A is a group VIIIB transition metal such as Co, Ir or Rh
and B is a pnictogen atom such as, P or Sb. The unit cell of these compounds

are of the space group Im 3

and consist of 32 atoms, where six out of the

eight simple cubic metal sublattices are filled with a near square planar ring
formed by four pnictogen atoms (Sb4).
Skutterudites are intermetallic compounds with a non-congruent melting point.
Melt spinning method had been explored as an alternative processing method.
The advantage of applying rapid solidification techniques to materials such as
skutterudites lies in the quenching-in of the peritectic microstructure with small
grain size (dependent on the wheel velocity). This results in a very short lengthscale for reactant diffusion resulting in faster solid state conversion of the
desired phase [10].

In this work, the properties of CoSb 3 at sufficiently low temperatures are

measured so as to avoid the cumbersome contributions of the anharmonic
effects and the interference from high-energy optical modes, making easier the
results interpretation. The presence of field-dependent ionization mechanism
was observed. Details of the influence of Sb deficiency on the measured
properties were investigated. Energy bandgap was calculated from Seebeck
coefficient measurements. Finally a study of the temperature-dependent lattice
dynamics of the compound was present.

2. Materials and methods

Polycrystalline skutterudite (CoSb 3) was prepared using a sequence of
processes including arc-melting, melt spinning, grounding, cold pressing and
annealing. To avoid oxidation, each individual process was carried out under
protective Ar atmosphere. Co pieces with a purity of 99.5% (Alfa Aesar) and Sb
shoot with a purity of 99.9999% (Alfa Aesar) were used as raw materials.
Volatilization of Sb during the fabrication of CoSb 3 was compensated by adding
10 wt% excess of stoichiometric amount of Sb. As a first step, an arc melting
furnace was used to obtain an ingot. Afterwards, the button was re-melted
under vacuum in an induction furnace. To obtain the ribbons, the melt was
ejected onto the copper wheel of a melt-spinning system, rotating with a
tangential velocity of 30 m/s. The resulting products were a mix of finely
divided ribbon flakes and wider ribbon sections. The ribbons were grounded
using an agate mortar and the resulting powder was loaded into a die cavity of
8 mm 8 mm. Then, the powder was cold pressed under a uniaxial pressure of
2

5 MPa during 1.5 min. Finally, the resulting green body was annealed at 650 C
during 2 hr. The heating and cooling rates were of 10 C/min.
Phase composition was determined by powder X-ray diffraction (XRD)
(PANalytical: XPert PRO. Cu K). Rietveld refinement of the XRD diffraction
pattern was carried out using the Fullprof program [11].
The morphology of the ribbons and of the annealed sample were analyzed by
scanning electron microscopy (SEM) (JEOL-JSM 5800). Chemical composition
and sample homogeneity were checked by Energy-Dispersive X-Ray (EDX)
microanalysis attached to the SEM. The actual composition was determined by
averaging distinct spots on the surface of each sample and by normalizing the
resulting chemical formula to a cobalt atom.
I-V curves of the annealed prism-shaped sample (8 x 8 x 2 mm 3) were
measured by the AC four-probe method between 2 and 300 K. The sample was
soldered to the puck of the AC Transport Option of a Physical Property
Measurement System (PPMS, Quantum Design) using four silver wires and
Pb/Sn braze.
Seebeck coefficient, electrical resistivity and thermal conductivity were
measured between 3 and 400 K several times on the as-obtained sintered
sample and after cutting the sample to confirm the previous results. A 4-point
method in thermal transport option (TTO) of a Physical Property Measurement
System (PPMS, Quantum Design) was used to measure the thermoelectric
properties. The PPMS sample puck provides both thermal and electrical
contacts to the sample.
The low-temperature heat capacity was measured on a 23.6 (+/0.02) mg
sample from 5 to 50 K in a Physical Property Measurement System (PPMS,
Quantum Design). The sample was fixed to the platform by a small amount of
thermal conductive grease. The heat capacity contributions of the puck and of
the layer of grease were measured in an addendum run prior the sample
measurement and subtracted from the data to obtain the heat capacity of the
sample.

3. Results and discussion

3.1 Structural characterization
The X-ray diffraction pattern of some hand-grounded ribbons as prepared by
melt spinning, with a complex phase composition, is shown in Fig. 1a. The Sb,
CoSb, CoSb2 and CoSb3 phases were detected, with Sb as the main phase.
Fig. 1b shows the result of the Rietveld refinement performed through FullProf
program to the X-ray diffraction pattern of the annealed bulk sample. A single
phase sample with a lattice parameter equals to 9.0302 was determined.

Fig 1. (a) XRD pattern of the ribbons obtained by melt spinning, (b) plot of the
observed intensity, the calculated intensity and the intensity difference for the
Rietveld refinement of the annealed bulk sample.
3.2 Microstructure
The melt-spun ribbon have two distinct surfaces: one that directly touches the
copper wheel (contact surface) and another which does not contact the copper
wheel (free surface). These two sides differ in their microstructure. The
microstructure on the contact surface exhibit two different zones, one of them
with rounded grains located into a depression with size distribution between
0.5 and 1.25 m, and other zone with a mix of rounded, square and irregular
grain shapes, with a boarder size distribution, from 0.1 to 1 m, as observed in
SEM-BEI image in Fig. 2a. The free surface exhibit rounded grains with welldefined grain boundaries, as shown in SEM-BEI images in Fig. 2b, with a grain
4

size distribution between 0.85 and 1.5 m. These differences in the

microstructures of both surfaces were to be expected, since the contacting
ribbon surface has a higher cooling rate.
The annealing process resulted in a broadening of the grain size distribution
from 0.1-2 m in the as-spun ribbons, to 0.6-50 m in the as annealed bulk
sample, as shown in Fig. 2c and 2d.

BEI

4,000X

5m

(a)

SEI

4,000X

5m

5,000X

3m

(b)

500X
(c)

BEI

40m

SEI
(d)

Fig 2. (a) Backscattered electron image (BEI) of the contact surface of the
ribbon and (b) BEI of the free surface of the ribbon, (c) SEI of the annealed
bulk material at 500X and (d) 5,000X.

The atomic composition as determined by EDX was found by averaging 10

separate elemental analyses performed at randomly selected zones of the
sample. The stoichiometry of Co was normalized to 1 since it is the least likely
element to be lost by vaporization during processing. The stoichiometric ratio
of the Sb was derived from this normalized value. The nominal composition of
the sample determined by this process was CoSb2.81, which indicates a Sb
deficiency. This deviation from the stoichiometric relation is a very common
issue encountered during the fabrication of CoSb 3 [12]. The Sb-deficiency
provides extrinsic carrier that have impact on the band gap, and hence on
electronic transport properties.
5

3.3 I-V Curves

Figure 3a shows the current-voltage (I-V) characteristics from 2 to 300 K. The IV curve measured at 2 K shows a non-linear and hysteretic behavior. I-V
measurements taken at closer temperature intervals, between 2 to 40 K, are
shown in Fig. 3b. Above T = 30 K, the I-V curves are linear i.e. they show an
ohmic-like behavior. As the temperature decreases below T = 30 K a non-linear
and hysteretic behavior appears. This behavior becomes more significant as
the temperature decreases.

Fig 3. (a) Current-voltage (I-V) characteristics between 2 and 300 K, at T < 50

K a non-linear and hysteretic behavior appears. (b) A closer temperature
6

interval, from 2 and 40 K, showed that the non-linear and hysteretic behavior
appears at T < 30 K.

At cryogenic temperatures, electrons are generally trapped in localized states,

and they do not have enough energy to get out of their localized states.
Although the temperature reduction causes a suppression of the thermal
excitation mechanism which promote electrons from the valence band into the
conduction band, the field-dependent ionization mechanism, which is usually
too weak at 300 K to be observed, become important at lower temperatures
[13]. Generally speaking, the application of strong electric fields enhance
emission of carriers due to Poole-Frenkel effect, phonon-assisted tunneling and
direct tunneling. The experimental investigations of carrier emission applying
low-electric fields, below 1 kV/cm, which is our case, has been attributed to the
Poole-Frenkel effect, which is caused by the lowering of the Coulomb barrier
[14].
As shown in figure 3b, as temperature decreases and a non-linear behavior
appears, there is a critical electric field beyond which the electric current
increases more rapidly than in the linear regime. The voltage at which the
electric conduction increases more rapidly is known as breakdown voltage and
the magnitude of the breakdown voltage in which field-dependent ionization
mechanism appears increase as temperature decreases. The effects discussed
above disappears at T > 30 K, where thermal energy starts to promote carriers
from the valence band into the conduction band (ohmic-like behavior).
Finally, it should be mentioned that for sufficiently large currents, self-heating
of the sample can occur at cryogenic temperatures [13]. This self-heating
results from the fact that the specific heat decreases drastically at cryogenic
temperatures. As a result, the lattice temperature may become much higher
than the ambient temperature due to Joule heating. This gives rise to the
hysteretic behavior of the I-V curves.
3.3 Thermoelectric properties
Figure 4 shows the electric resistivity (a), Seebeck coefficient (b), total thermal
conductivity (c) and lattice thermal conductivity (c) of the polycrystalline CoSb 3
sample, which are the physical magnitudes determining its thermoelectric
behavior.

Fig 4. (a) Electric resistivity, (b) Seebeck coefficient, (c) thermal conductivity
and, (d) lattice thermal conductivity for the CoSb 3 annealead sample.

Fig. 4a shows the decrease of electrical resistivity of CoSb 3 with increasing

temperature, which is the typical behavior of an intrinsic semiconductor. A
resistivity value of 1.1 mm was observed in the sample at 300 K which is
similar to the value reported by other authors [15]. The room temperature
resistivity values reported for CoSb3 differ by three orders of magnitude [16].
This difference is due to variations of non-stoichiometry and defect structures.
Sb-deficient samples tend to present higher electrical resistivity, due to band
structure changes caused by point defects [17].
Variations of non-stoichiometry of CoSb3 leads to either n-type or p-type
conductivity, depending on whether the samples were synthetized under Sbrich or Sb-deficient conditions. Sb-enriched samples have p-type conduction
and Sb-deficient samples will lead to an excess of electrons in the conduction
band, showing an n-type behavior [18]. Although Sb-vacancy has been
tentatively considered to be an important native point defect, densityfunctional theory calculations performed by Park et. al. [19] determined that in
8

Sb-deficient samples, interstitial Co ( Co i ) is the most stable isolated native

point defect. According to Park et. al,

Co i

is an acceptor-like defect, with a

very low formation energy value of 0.5 eV. This low formation energy value can
yield a high concentration of

Co i

and because of this the formation of

Co i -

pair was proposed, which is a stable defect at low temperature. Unlike the
isolated

Coi , the

Coi -pair is a donor-like defect

The temperature-dependent Seebeck coefficient, S, showed in Fig. 4b, has

negative values in the measuring temperature interval, typical of an n-type
behavior. As previously stated, the analyzed sample is Sb-deficient, therefore
providing extrinsic carriers, i.e.: extra electrons. The absolute values of S
increase up to around 364 K, reaching a maximum of 412 VK-1, and then
gradually starts to decrease with increasing temperature. This maximum
absolute value is larger than the values previously reported by various authors;
however, this value is in good agreement with the value of -400 VK-1 at 380 K
reported by W.S. Liu et at [20]. As It can be observed, the absolute value of the
Seebeck coefficient starts to decrease at the highest measuring temperature,
which is consistent with the observation made by other authors in n-type CoSb 3
[17]. The slope change is caused by the change from weak extrinsic
conductivity, originated by the Sb-deficiency, to intrinsic conductivity.
The analytical expression,

E g=2 e|S|max T max , developed by Goldsmind and

Sharp relates the bandgap, Eg, with the absolute maximum value of the total
Seebeck coefficient,

|S|max , and with the temperature,

T max , at which this

absolute maximum value occurs. Then, from the measured absolute maximum
value of the Seebeck coefficient, a calculated value

E g=0.48 eV

was

obtained, which is comparable with the values reported by W.S. Liu et. al. [17].
Experimental observations made by W.S. Liu et. al. led to the conclusion that ntype CoSb3 has a larger energy bandgap than p-type CoSb 3.
Fig. 4c shows the temperature dependence of the thermal conductivity of
CoSb3. Interestingly, our sample presents a thermal conductivity value of 3.2
WK-1m-1 at 300 K, which is lower than typical values of CoSb 3 prepared by
traditional methods (7.0 WK-1m-1) [21], and this fact is an incentive to improve
the figure of merit ZT. Thermal conductivity presents a maximum value of 8.24
WK-1m-1 at 50 K. For temperatures lower than 50 K, thermal conductivity
decreases due to the decreasing of specific heat when the temperature
decreases, as proposed in the Debye phonon model. For temperatures higher
than 50 K thermal conductivity decreases due to thermally activated phononphonon Umklapp scattering process.

Fig. 4d shows the lattice thermal conductivity estimated using the relation

= e + L , where the electronic contribution,

Wiedemann-Franz law,

e =L0 T , where

L0

e , is given by the

is the Lorenz number (2.45 x

10-8 WK-2). Comparing Fig. 4d with Fig. 4c, it can be seen that the lattice
thermal conductivity, L , is the dominant contribution to the total thermal
conductivity because of the relatively high values of electrical resistivity , i.e.,

L .
Fig. 5 shows the temperature dependence of the calculated thermoelectric
figure of merit, ZT, from the measured values of S, and . The maximum
value

ZT =0.015

occurs at the maximum measuring temperature T= 400 K,

which is in good agreement with other authors [18].

Fig 5. Figure of merit as function of temperature for the CoSb3 annealead

sample.

3.3 Specific heat

By measuring the specific heat at sufficiently low temperatures the
cumbersome contributions of the anharmonic effects and the interference from
high-energy
optical
modes
can
be
avoided,
facilitating the interpretation of measurements [22]. Fig. 6 shows the
experimental

C p /T

vs. T2 values from T=5 to 50 K, together with its non-

linear fitting using the theoretical formula

10

f ( x )= + x + A 2E 1 x(3 /2)

E1 / x

E2 / x

e
2
(3 /2)
+
B

E2
/ x
2
/ x
2
(e
1)
(e
1)
e

E1

E2

containing terms with Debye and Einstein models contributions, where

x=T 2

, and are the electronic and lattice contributions to the specific heat
respectively,

E 1

modes, and

and
and

E 2
B

are the Einstein temperatures of the localized

are the spectral

weights. Table 1 shows the

obtained fitted values with the Debye model only (i), the Debye model plus one
Einstein mode (ii) and the Debye model plus two Einstein modes (iii). As it can
be
seen
from
Table
1,
the
goodness of fit improves with the inclusion of Debye model plus two Einstein
modes,
with
a
Chi squared value
calculated
4

from

= 0.0002. A Debye temperature D=

the
2

D=(12 N A k B / 5 )

fitted

value

of

and

using

295 K was
the

formula

Fig 6. Cp/T vs T2 plot obtained from the nonlinear least square fitting of specific
heat experimental data () to a model containing the Debye model plus two
Einstein modes. From the fitting the relative contributions to the electronic
11

specific heat (), Debye term () and the two Einstein modes (E1 and E2) were
obtained.

Fitted
Paramet
er
(J/molK2)
(J/molK4)
A (J/molK)
E1 (K)
B (J/molK)
E2 (K)
2

0.0808

Debye model +
one Einstein mode
(ii)
0.0207

Debye model+
two Einstein
modes (iii)
0.0099

2.6272 x 10-4

1.3135 x 10-4

7.4966 x 10-5

20.7778

5.3883

107.54
-

68.21
32.4088

0.1974

0.0041

145.73
0.0002

Debye model (i)

Table 1. Physical parameters for three different models: the Debye model only
(i), the Debye model plus one Einstein mode (ii) and the Debye model plus two
Einstein modes (iii). The parameters were obtained by nonlinear least square
fit of specific heat data.

As CoSb3 is an unfilled skutterudite, a zero Sommerfeld coefficient () must be

expected at low temperatures, due to the fact that there are no free electrons
[23]; however, a value of 9.9 mJ/mol-K2 was obtained because of the nonstoichiometry of the sample that provides extra free electrons. Also, rattling
modes at low temperature are unexpected, however the data showed localized
oscillations mainly from low-lying optical phonon modes involving collective
motions of the 4-membered Sb rings present in the CoSb 3 framework [23, 24].
4. Conclusions
It was showed that the combined arc-melting, melt-spinning, milling, cold
pressing and annealing processes are a viable route to obtain thermoelectric
skutterudite. A non-linear and hysteretic behavior was observed in the I-V
curves at low temperature. The non-ohmic behavior was originated from fielddependent ionization, which become important at low temperature. The
hysteresis and the variable electrical resistivity for T < 30 K were attributed to
the drastic decrease of heat capacity which produces Joule heating at cryogenic
temperatures. The electrical resistivity, Seebeck coefficient and thermal
conductivity were measured and the value of figure of merit was calculated.
Influence of Sb deficiency was present. The sample had an n-type electrical
behavior, reaching an absolute maximum Seebeck coefficient at 364 K and
12

then a change in the trend was observed, due to the change from extrinsic to
intrinsic conduction. The energy bandgap, influenced by the Sb-deficiency, was
calculated to be 0.48 eV. The maximum figure of merit reached was of 0.015 at
the maximum measured temperature of 400 K. Future word aims to enhance
the figure of merit though several methods, including additional doping and
nanostructuration. From specific heat data, a Debye temperature,

D=

295

K, was calculated and the presence of localized low-lying phonon modes, with
Einstein temperatures of E1 = 68.21 and E2 = 145.73 K were identify.

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