Thermoelectric efficiency in graded indium-doped PbTe crystals

Z. Dashevsky, S. Shusterman, M. P. Dariel, and I. Drabkin

Citation: Journal of Applied Physics 92, 1425 (2002); doi: 10.1063/1.1490152

View online: http://dx.doi.org/10.1063/1.1490152
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 JOURNAL OF APPLIED PHYSICS VOLUME 92, NUMBER 3 1 AUGUST 2002

Thermoelectric efficiency in graded indium-doped PbTe crystals

Z. Dashevsky, S. Shusterman, and M. P. Dariela)
Department of Materials Engineering, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel
I. Drabkin
Institute of Chemical Problems for Microelectronics, Moscow 109017, Russia
Received 25 March 2002; accepted for publication 7 May 2002
High efficiency thermoelectric conversion is achieved by using materials with a maximum figure of
merit ZS 2 /k, where S is the Seebeck coefficient, and k, the electrical and thermal
conductivities, respectively. High quality homogeneous thermoelectric materials, based on PbTe
crystals, usually display an elevated value of Z over a narrow temperature range. A maximal value
of figure of merit Z, as a function of electron density, is attained only for one specific location of the
Fermi level, E F , with respect to the conduction band edge, E C . In order to maintain this optimal
Z value, namely, maintain a constant location of the Fermi level, the electron density, which is
determined by the dopant concentration, must increase with increasing temperature. We present a
method for the generation of a dopant indium concentration profile in n-type PbTe crystals that
gives rise to a constant location of the Fermi level, and hence, to an optimal value of Z over a wide
temperature range. The resulting functionally graded material, based on PbTeIn, displays a
practically constant value of the Seebeck coefficient, over the 50 600 C temperature range.
2002 American Institute of Physics. DOI: 10.1063/1.1490152

I. INTRODUCTION orbitals hybridize into an excited sp 2 state. The correspond-

ing s orbital is, therefore, of nonbonding nature and is
It is well established that the efficiency of thermoelectric strongly localized on the impurity atom. As a result, the cor-
semiconductor materials may be improved by generating an responding s level is viewed as the deep-lying one.5 Such a
appropriate graded concentration of the dopant, parallel to level not only releases but also accepts electrons, and it dis-
the temperature gradient that prevails along the sample.1 One plays both donor and acceptor properties, i.e., it is an ampho-
well-known example is that of lead telluride, an n-type ther- teric level. Indium atoms located on substitutional sites dis-
moelectric material for the 100 600 C temperature range, in play in PbTe donor-like properties. The solubility of In in
which a gradient of PbI2 has been set up.2 The preparation of PbTe is of the order of 35 at. %, nevertheless, the electron
a functionally graded material FGM requires determining density reaches a saturation level of n(3 5)1018 cm3
the specific carrier concentration profile that leads to optimal
at T300 K, a level that corresponds to a concentration of
conversion efficiency and is commensurate with the tempera-
only 0.05 at. %. The behavior of indium in IVVI semicon-
ture distribution over the thermoelectric leg.3
ductors has been subject to several investigations.6 8 It was
One common approach that has been used for the prepa-
established that:
ration of such a functionally graded thermoelectric material
i At low temperature the indium energy level E D is
consists of sintering a compacted stack of PbTe powder lay-
close to E C . Its location does not depend on the In concen-
ers, each containing a different concentration of dopant ele-
tration up to N In5 at. %.
ments. The intrinsic disadvantage of this approach is that at
ii Each indium atom that occupies one Pb lattice site
high temperature, after extended duration in service, the ini-
contributes one electron on an impurity level and two al-
tial dopant concentration gradient may decrease on an ac-
lowed states. Thus, the impurity level is half-filled.
count of diffusion-induced homogenization effects and result
iii Indium atoms in interstitial positions are neutral and
in the degradation of the conversion efficiency.
do not contribute to the charge carrier concentration.9
Recently, we have put forward and described a concept
iv At low temperature, the Fermi level E F is deter-
for the preparation of a FG thermoelectric material, based on
mined by the impurity level E D , leading to the so-called
PbTe crystals doped with indium.4 Indium generates in
pinning of the Fermi level.
IVVI compounds a deep-lying impurity level. Deep lying
In the framework of the abovementioned model, the po-
states, in contrast to shallow lying ones, consist of wave
sition of the Fermi level as a function of temperature was
functions that belong to several bands. Their energy levels,
calculated for a given indium concentration. When impurity
consequently, are not connected to any particular band edge,
E C and E V , and may lie within a band as well as within a atoms are introduced, the Fermi level must adjust itself to
band gap. For an indium impurity on a substitutional site, the preserve charge neutrality:
s shell does not participate in bond formation and the In

a
Electronic mail: dariel@bgumail.bgu.ac.il nN D , 1

0021-8979/2002/92(3)/1425/6/$19.00 1425 2002 American Institute of Physics

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 1426 J. Appl. Phys., Vol. 92, No. 3, 1 August 2002 Dashevsky et al.

ii Increasing the In concentration aligned parallel to the

increasing temperature along the thermoelectric leg. This
was done in order to maintain a constant position of the
Fermi level.
iii Setting the lowest dopant concentration region to
coincide with the low temperature edge of the thermoelectric
leg, in order to minimize the adverse effect of a large impu-
rity concentration on the electron mobility.

II. TEMPERATURE PROFILE SIMULATION

FIG. 1. Calculated Fermi level in homogeneous PbTeIn as a function of

Optimization of the indium profile along the thermoelec-
temperature and of the In concentration. tric leg requires determining the temperature profile that is
set up in the semiconductor located between the high tem-
perature T h and the low temperature T c reservoirs. For a
thermoelectric leg of length L that extends from x0 at T h ,
where n is the electron density in the conduction band and to xL at T c , the temperature distribution along a leg can

ND , the number of ionized donors indium. The electron be determined from the heat flux equation under steady state
density is given by: conditions:10
n4 2m de kT/h 2 3/2F 1/2 * ,
where k is the Boltzmann constant, h is the Planck constant,
2 d
dx
a T
dT
dx
I 2
1
T a
I
dS dT
T
dT dx
, 4

m de is the density-of-state-effective mass for electrons in the
conduction band, in PbTe m de (M c ) 2/3 (m l m 2t ) 1/3 M c is
the number of equivalent minima in the conduction band, m l
and m t are the longitudinal and transverse effective mass in
the conduction band; * is the reduced Fermi level equal to
(E F E C )/kT, and F 1/2( * ) is the Fermi integral.
The number of ionized donors N D , is given by7
where a is the cross section of the material and I is the
current. The left-hand side represents heat conduction, the
first term on the right-hand side stands for the Joule heat
generation, the second term for the Thomson effect contribu-
tion. The solution of Eq. 4 is found using the boundary
conditions at the hot and the cold sides of the leg. The heat
flux at the hot side and cold side, taking into account the

2 Peltier effect is given by Eqs. 5 and 6, respectively:

ND N D 1 , 3
E D E F dT
1exp Q h S T h IT h a T h , 5
kT dx x0

where N D is the indium concentration and E D is the In im-

purity level. Figure 1 shows a plot of the calculated values
for different temperatures and different levels of indium im-
Q c S T c IT c a T c
dT
dx
xL
. 6

purity concentration. Note that as the temperature increases, Using Eqs. 4, 5, and 6, the temperature distribution is
the indium concentration has to increase in order for the expressed as

Fermi level to stay close to the impurity level adjacent to the
dT Qh S T h IT h I2 x1
conduction edge E C , at a position which is the most favor- dy
able for achieving the maximal value of figure of merit over dx a T a T a T 0 a t

a wide temperature range. I x dS dT
At high temperature T400 C, the negative influence T dy. 7
of minority carriers holes on the thermoelectric properties a T 0 dT dy
cannot be neglected. Fortunately, electrons from the In level The integration of this expression allows determining the
annihilate the minority carriers and exert a twofold beneficial temperature difference on the thermoelectric leg
effect by:
a Maintaining the high value of the Seebeck coefficient Q h L S T h IT h L
TT h T c
up to 600 C, as a result of the decreasing effect of the mi- k ava k ava

nority charge carriers. L 1 x 1
b Eliminating the appearance in the heat conduction of I 2 dx dy
an additional term due to bipolar diffusion of electron-hole 0 a T 0 T a

pairs. L 1 x dS dT
On the basis of these premises, we have adopted a strat- I dx T dy, 8
egy for designing an indium concentration profile in the 0 a T 0 dT dy
PbTe crystal with the purpose of obtaining optimal effi- where the average thermal conductivity is
ciency. The strategy consisted of:
i Setting up an indium concentration profile in an ini-
tially p-type PbTe crystal by diffusion from a gaseous source.
k a1

1
L
0
L 1
k T
dx. 9
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 J. Appl. Phys., Vol. 92, No. 3, 1 August 2002
FIG. 2. Calculated temperature profile in an n-type PbTe crystal with ex-
tremities fixed at 50 C (T c ) and 500 C (T h ), as a function of the location.
1, 2: two homogeneous PbTe crystals with electron density n 1 51018 and
n 2 81019 cm3 ; 3: graded PbTe crystal with n51018 cm3 at T c and
n81019 cm3 at T h .
An analytical solution for temperature along the thermo-
electric leg T(x) can be determined from Eq. 4, knowing
the temperature dependence of thermal conductivity. As a
first approximation, the temperature distribution T(x) was
calculated from Eq. 4, for I0 and, assuming for the tem-
perature dependence of the thermal conductivity:
1 reflection photographs of an 100 oriented PbTe crystal
k ,
bTc
where b and c are constants
k composition of crystalline PbTe in equilibrium at elevated
b ,
Tk T h k T c
k T h T h k T c T c
c ,
k T h k T c T
and k(T h ) and k(T c ) are the thermal conductivity on the hot
and the cold side of the thermoelectric leg, respectively, and
kk(T c )k(T h ).
The temperature distribution along the leg as a function
of coordinate x, for I0 is given by
1 k Th x/L
T x k T c T T h T h
k Tc
TcTc .
Using this equation for the temperature profile along
thermoelectric leg, the terms in Eq. 7 were calculated tak-
ing into account the known temperature dependence of S, ,
and k in PbTe. Integration of Eq. 7 yields a second approxi-
mation for the temperature distribution along the thermoelec-
tric leg. The results of these calculations for PbTe crystals
with constant electron concentrations n51018 and 8
1019 cm3 and for a graded material n51018 cm3
on the cold side and n81019 cm3 on the hot side are
shown in Fig. 2.
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Dashevsky et al. 1427
III. EXPERIMENT
A. Crystal growth
PbTe crystals were grown by the Czochralski
technique.11 The advantage of the Czochralski technique is
that it also enables the application of high axial temperature
gradients, as compared to crucible confined growth tech-
niques, as well as a better control of the gradient. The option
for an improved control on the axial temperature gradient is
important both for preventing constitutional supercooling ef-
fects and also for the prevention of undesirable crystals de-
fects, e.g., low angle grain boundaries or twins, originating
from too steep temperature gradients. In the crystal growing
process, polycrystalline PbTe is placed in the crucible and
the furnace is heated to above the melting temperature of
PbTe. A 100 oriented seed PbTe crystal was used. To pre-
vent decomposition of the melt during crystal growth, a liq-
uid encapsulation method was employed. The liquid encap-
sulant was a molten boron trioxide (B2 O3 ) layer, about 1 cm
thick. Molten boron trioxide is inert to PbTe at the growth
temperature. The temperature gradient at the crystallization
front and the crystal pull rate were of the order of 2025
K cm1 and 510 mm h1, respectively. In order to enhance
the equalization of the heat flux through the lateral surface of
the crystal, the crucible and the crystal were rotated in oppo-
site directions at an angular rate of 1 s1. The crystal orien-
tation was determined by the Laue diffraction method. Back-
10 clearly revealed the fourfold symmetry and the absence of
any other reflections.
The crystals were grown from a PbTe melt with an ex-
cess Te up to 1 at. %. Deviations from the stoichiometric
11
temperatures induce the formation of lattice defects, vacan-
cies, and possibly interstitials.12 These defects can be
quenched-in by sufficiently rapid cooling, they are electri-
12 cally active and may act as charge carriers that participate in
the electrical conduction process. The atomic imperfections
or lattice point defects associated with excess nonmetal
metal vacancies or nonmetal interstitials form acceptor lev-
els with zero activation energy. When the content of electri-
cally active foreign impurities is low, as compared to the
difference between the concentration of electrically active
excess native defects, the hole carrier concentration can be
expressed as:
14
p2 V Pb 0 I Te ,
where V and I denote the vacancy and interstitial concen-
15
trations, respectively.
The Hall effect is the most commonly used method for
direct measurement of the carrier concentration. At low tem-
perature 80 K, all acceptor impurities are ionized. Under
these circumstances the carrier concentration is equal to the
concentration of the lattice point defects metal vacancies
namely, to the excess Te, of the order of (1 5)
1018 cm3 .
A second group of crystals was grown from a PbTe melt
doped with Na (Pb0.99Na0.01Te). Na is a shallow acceptor in
 1428 J. Appl. Phys., Vol. 92, No. 3, 1 August 2002
FIG. 3. Dependence of the In surface concentration, as determined by EDS,
on the annealing temperature.
PbTe with practically zero ionization energy. The hole con-
centration in these crystals was p71019 cm3 .
B. Doping with In
Doping was done by indium that diffused from a gaseous
source (In4 Te3 ), allowing to maintain a constant level of
surface In concentration during the diffusion anneal. The
concentration profile of the In dopant lies in the 0.1 4 at. %
range and can be varied by changing the diffusion length and
the annealing temperature 600700 C. The concentration
profile of In within the crystal, as will be described in the
following, was assumed to be consistent with the solution of
the diffusion equation for a constant surface source. The sur-
face concentration C S as determined by EDS as a function of
the annealing temperature is shown in Fig. 3.
C. Determination of the In dopant profile in the PbTe
crystal
The determination of dopant concentration variations
and of the location of the p-n junction in the doped crystals is
of utmost importance. The Seebeck coefficient S of electrical
conducting materials is a measure of the carrier concentra-
tion and, hence, of the dopant distribution. We have made
use of a recently developed method for local Seebeck coef-
ficient measurements along the surface of the doped
crystal.13 The determination of the local Seebeck coefficient
is carried out by a simple probe technique. A very thin and
sharp probe, heated to temperature T 1 , is placed in contact at
its tip with the surface of the isothermal sample maintained
at temperature T o . The measuring probe is actually the junc-
tion of a CuCuNi thermocouple. A second, similar thermo-
couple is in good electric and thermal contact with the
sample and its junction is at temperature T o . The voltage
values, V 1 and V 2 , between the CuCu and the CuNiCuNi
wires, respectively, of the two thermocouples are measured
simultaneously. The apparatus that has been constructed al-
lowed a spatial resolution of 10 m. The Seebeck coefficient
variations were measured along a direction normal to the
external free surface on a polished plane of the crystal.
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Dashevsky et al.
FIG. 4. Profile of the Seebeck coefficient in Pb0.99Te1.01 and Na-doped PbTe
crystals after diffusion of indium.
IV. RESULTS AND DISCUSSION
The variation of the Seebeck coefficient S, measured in a
direction parallel to the penetration of In by diffusion in a
p-type PbTe grown from a melt with excess Te crystal is
shown in Fig. 4. The S values for all crystals in which In had
diffused curves 13 drop at the front end of the crystal to a
large negative value reflecting the effect of the large In ad-
dition. The transition from n- to p-type conductivity p-n
junction causes a change of sign of the Seebeck coefficient
and its location can be determined, as described above, by
scanning the local Seebeck coefficient. The presence of In
substituting for Pb on the Pb sublattice overcompensates the
V Pb acceptors and transforms the initial p-type PbTe into
n-type PbTe. Similar measurements were carried out in the
Na-doped p-type PbTe crystals that had no excess Te and
hence no structural vacancies, but due to the presence of Na
on the Pb lattice sites had an initial hole concentration. The
penetration profile of In in this crystal also indicates a cross-
over point of the Seebeck coefficient occurring closer to the
In source, namely at a higher In concentration. These results
can be accounted for by assuming a model that rests on the
following premises:
a Indium atoms in stoichiometric PbTe diffuse essen-
tially by an interstitial mechanism.
b In the PbTe crystal with excess Te, any In interstitial
that encounters a Pb vacancy becomes an active atom,
according to the dissociative mechanism reaction: Ini
V PbInPbe.
c The Seebeck coefficient is sensitive only to active In
atoms located on Pb lattice sites. Each such active In con-
tributes one electron to the conduction band.8
d At In concentrations that exceed the initial V Pb con-
centrations, a kick-out-like mechanism, Ini PbPbPbi
InPb2e, takes place leading to an increased electron con-
centration and to negative values of the Seebeck coefficient.
Interstitial Pb atoms, Pbi are donors and contribute one
electron.12
e The energy barrier for the dissociative mechanism is
significantly lower than for the kickout mechanism. Thus, as
long as V Pb sites are available, the diffusing Ini will prefer-
entially occupy these sites.
The values of S, as one proceeds into the crystal, initially
reflect the number of In atoms located on Pb lattice sites, but
increase algebraically, as one proceeds along the diffusion
 J. Appl. Phys., Vol. 92, No. 3, 1 August 2002
FIG. 5. Diffusivity of In as a function of the reciprocal temperature in
Pb0.99Te1.01 and in Na-doped PbTe crystals.
path, change sign and revert to the positive value, character-
istic of In-free PbTe. We can estimate the In concentration
N In at a location x at which the Seebeck coefficient reverses
its sign from positive sample with V Pb acceptors to nega-
tive sample doped with In. At point x, the contribution of
the electrons due to the presence of In on Pb lattice sites
counterbalances the initial hole concentration, due to the ex-
cess Te, i.e., Pb lattice vacancies, V Pb . Since each In that
jumps into a V Pb contributes three electrons versus the initial
two holes, we can deduce that the In concentration at that
point corresponds to 2/3 of the initial V Pb concentration.
This latter value is known from the prediffusion Hall effect
measurements. Using this value and that of the surface con-
centration, as determined by EDS measurements, the diffu-
sion coefficient of indium in PbTe was approximated by fit-
ting to the appropriate solution of the diffusion equation.
C x,T C s erfc x/2Dt . 16
The value of the diffusion coefficient of indium in
Pb0.99Te1.01 with the relatively high structural vacancy con-
centration at 700 C is high, D4.5109 cm2 /s. Further
measurements performed at different temperatures, allowed
estimating the activation energy E a 1.5 eV Fig. 5. These
results support the initial assumption regarding the interstitial
diffusivity of In in PbTe. A similar analysis was performed
for the Seebeck coefficient profiles in Na-doped PbTe, shown
in Fig. 5. In Na-doped PbTe, there are no structural V Pb , thus
indium can become active only via the kickout mechanism,
but since the overall NaPb is low, the dominant mechanism
is through the reaction Ini PbPbPbi InPb2e. The elec-
tron concentration increases by two electrons for each sub-
stitution of Pb on a lattice site by an interstitial In atom, via
the kickout mechanism. Hence at this point InPb equals 0.5
Na. At the Seebeck coefficient crossover, this electron con-
centration equals the initial hole concentration that is present
on account of the presence of the Na dopant. The diffusivi-
ties of In in Na-doped PbTe are lower by an order of mag-
nitude but associated with the same within experimental er-
ror value of the activation energy as for the PbTe crystals
containing structural vacancies. Since we assumed that in
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Dashevsky et al. 1429
FIG. 6. Thermovoltage as a function of temperature in doped n-type PbTe
crystals.
both PbTe-based crystals, In diffused by an interstitial
mechanism, the overall concentration profiles of In in both
instances should be the same. If the crossover in the Na-
doped PbTe appears to occur at a lower penetration, i.e., a
larger In concentration, it is because the Seebeck coefficient
is sensitive only to active InPb atoms, thus at the crossover in
the Na doped PbTe crystal, a significant Ini is still present.
The apparently lower diffusivities of In in Na-doped PbTe
reflect the effect of the lack of V Pb on the active In con-
centration.
A 4 mm thick slice was cut from the p-type PbTe sample
that had been doped with In that originated from the gaseous
phase. The portion that was cut coincided with the region in
which an In gradient was set up, as determined by the See-
beck coefficient measurements. The two end surfaces of the
graded crystal were polished and positioned between two flat
surfaces. The lower surface was kept at constant 50 C and
the temperature of the upper surface increased to 550 C. The
measured thermovoltage, V of the graded n-doped PbTe In
is shown in Fig. 6. It is noteworthy that the dependence
V(T) is linear within a close approximation. This behavior
of V(T) is very different from that in homogeneous n-type
PbTe doped only by iodine which reaches a saturation level
at elevated temperature Fig. 6. The measured Seebeck co-
efficient SV/T in PbTe doped with In is practically con-
stant (S250 V/K) over a wide temperature range. At
high temperatures, electron-hole pairs can undergo thermal
excitation. Both the electron and the hole components con-
tribute to the Seebeck coefficient. At this temperature
n p
SS n S p
n p n p
b p
S n S p , 17
p p
b nb b
n n
where S n and S p are partial terms for electrons and holes
consequently, n and p are the concentrations of electrons
majority carriers and holes minority carriers, respectively,
b is the ratio of electron and hole mobilities b in PbTe is
close to 1. According to Eq. 17, even the presence of a
small concentration of holes may cause a drastic decrease of
the Seebeck coefficient and, hence, of the conversion effi-
ciency at a high temperature. The practically constant value
 1430 J. Appl. Phys., Vol. 92, No. 3, 1 August 2002
of S up to 600 C that was observed can be attributed to the
negligible influence of the minority carriers. The electrons
present in the In-generated level annihilated the latter.
The near-surface concentration of In, about 3 at. % at
T h , Fig. 3, is well above that needed to ensure a carrier
concentration commensurate with optimal conversion effi-
ciency. This high level of In ensures that a sufficient content
of In will be maintained at the T h side of the thermoelectric
leg in spite of the downward diffusion flux along the tem-
perature gradient, in the course of extended durations of op-
eration of the thermoelectric generator. A significant In con-
centration reaching the T c side of the thermoelectric leg may
affect negatively the mobility of the charge carriers. It is
unlikely, however, that the diffusivities of In at low tempera-
ture will allow any concentration buildup in that region.
V. CONCLUSIONS
i A concept for the preparation of a FG thermoelectric
material based on PbTe crystals doped with In has been put
forward and has been confirmed experimentally.
ii Doping heavily with indium the T h side of the PbTe
crystal allows maintaining an In concentration that ensures
that diffusion effects in the course of extended operation do
not affect adversely the position of the Fermi level and,
thereby, the thermoelectric figure of merit.
iii Indium diffuses from a gaseous source into a p-type
crystal with an excess of Te that generates structural Pb va-
cancies. The influx of In transforms the conductivity from p
to n type.
iv Local Seebeck coefficient measurements along
the crystal allowed determining the diffusion parameters
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Dashevsky et al.
of indium in Pb1x Te1x (E a 1.40.1 eV,D O (92)
102 cm2 /s) and to design In concentration profiles.
v The graded material displays a linear dependence of
the thermovoltage on the temperature difference, suggesting
a practically constant value of the Seebeck coefficient, over a
wide temperature range 50 600 C. This value of the See-
beck coefficient corresponds to an optimal carrier concentra-
tion distribution, generated by the In concentration profile.
vi The results demonstrate the validity of the FGM
approach for preparing thermoelectric materials with im-
proved efficiency for energy conversion.
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13
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XV Internernational Conference on Thermoelectrics, Pasadena, CA, 1996,
p. 412.