Physica B 299 (2001) 120}123

Transport mechanisms in La Sr FeO : Evidence for small

    
polaron formation
Woo-Hwan Jung*
Division of Electrical, Electronic and Information Engineering, Howon University, 727, Wolha-Ri, Impi, Kunsan Chon Buk, South Korea
Received 21 July 2000; received in revised form 6 September 2000

Abstract

Transport properties in the ceramic specimen of La Sr FeO (LSF) with orthorhombic structure have been
    
investigated. The electrical resistivity displayed thermally activated temperature dependence above 250 K with an
activation energy of 0.302 eV. The temperature dependence of thermoelectric power and DC resistivity suggests that the
charge carrier responsible for conduction is strongly localized. The experimental results have been interpreted in terms of
a hopping process involving small polaron.  2001 Elsevier Science B.V. All rights reserved.

PACS: 71.38; 72.20.p; 72.20

Keywords: Hopping process; Small polaron; Thermoelectric power

The transport properties of mixed-valence metal- unexpected behavior may give useful clues for the
lic and ferromagnetic perovskite La Sr MO fundamental mechanism of the metal}insulator
\V V 
(M: 3d transition metal) have been paid much at- transition in these perovskite structures.
tention since the discovery of the high-temperature Several groups have studied the La Sr FeO
\V V 
superconductivity in cuprates and giant mag- system and a reasonably clear picture of the con-
netoresistance (GMR) in manganese oxides [1,2]. duction mechanism in these systems has emerged
Replacement of La by Sr in LaMO changes the [5]. One of the origins of the insulating ground

oxidation states of the M ion from 3# to 4#. state of the moderately hole-doped compound is
When M denotes middle elements of Mn, Fe and charge ordering, which shows up most conspicu-
Co, it is expected to show a crossover on the ously around x" in La Sr FeO [4]. In order
 \V V 
metal}insulator transition. It is rather surprising to gain insight into the nature of the transport
that, while La Sr (Mn or Co)O becomes metal- mechanism, we have applied thermoelectric power
\V V 
lic for x'0.2, La Sr FeO does not exhibit on hole-doped LaFeO (La Sr FeO ) over the
\V V       
a metallic phase until x&1 [3,4]. The origin of this wide range of temperatures in addition to the basic
characterization by electrical resistivity measure-
ment. The thermoelectric power is, in contrast to
electrical resistivity, relatively insensitive to the
* Corresponding author. Tel.: #82-63-4507515; fax: #82-
63-4507039.
e!ects of grain boundaries and disorder. We will
E-mail address: phdjung@sunny.howon.ac.kr (W.-H. Jung). show that this material, thermoelectric power

0921-4526/01/$ - see front matter  2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 4 5 2 6 ( 0 0 ) 0 0 5 9 0 - 1
 W.-H. Jung / Physica B 299 (2001) 120}123 121

provides unique insight into the transport In Fig. 1, the temperature dependence of the
mechanism. resistivity in zero "elds and 0.85 T is shown. A pos-
Ceramic sample of La Sr FeO (ab- itive MR e!ect is observed over the wide temper-
    
breviated as LSF) was prepared by solid-state reac- ature range from low temperature to &200 K.
tion. Starting materials La O , SrCO , and Fe O Di!erent theoretical models used for the explana-
    
were mixed in stoichiometric proportions and tion of the DC conductivity data of transition metal
heated in air at 1373 K for 24 h, and 1473 for 24 h, oxides have been reviewed by several workers
and then 1573 K for 24 h with intermediate grind- [6}10]. However, the pair correlation-type model
ing. Powder X-ray di!raction shows clean single- of Mott et al. [6] based on a strong electron}
phase (orthorhombic phase, a"5.502, b"5.512, phonon coupling approximation has been exten-
and c"7.844 As ) patterns. The oxygen sively used for explaining the conductivity data of
stoichiometry was determined by a potentiometric many transition metal oxides. If the charge carriers
titration. The actual composition obtained was responsible for conduction are small polarons, the
La Sr FeO temperature dependence of the DC resistivity due
     
Thermoelectric power measurement was carried to a process of hopping of small polarons predicted
out below 373 K on a sample placed between two theoretically takes the form [6}10]
blocks of oxygen-free high-conductivity copper.

/¹Jexp(E /k ¹), (1)
Both ends of specimen were coated with platinum M
paste and then placed in contact with thin copper where E is the activation energy for small polaron
M
plates. Copper-constantan thermocouples were hopping, and k is Boltzmann's constant. In Fig. 1,
welded to the reverse sides of the copper plates to the straight line on the Arrhenius plot of
/¹!1/¹
measure the temperature and thermoelectric yields E "0.302 eV.
M
power. The MR in the temperature range 80}373 K Measurements of the thermoelectric power as
was investigated in the heating process using the a function of temperature, , between 200 and
four-probe method. The maximum magnetic "eld 350 K are shown in Fig. 2. The thermoelectric
available in the present apparatus is 0.85 T. power of LSF could not be measured at low tem-

Fig. 1. Resistivity (
/T ) of LSF as a function of temperature in zero "eld and in a magnetic "eld of 0.85 T. The solid line represents the
Arrhenius relation between
/T and 1/T.
122 W.-H. Jung / Physica B 299 (2001) 120}123
Fig. 2. Thermopower () as a function of temperature. The straight line represents the linear portions in the Arrhenius plot.
peratures because of high sample impedance. The
thermoelectric power associated with small polar-
on hopping in transition metal oxides is generally
assumed to be dependent on the carrier concentra-
tion and given by one of the temperature-indepen-
dent expressions derived in a high-temperature
limit. The experimental result on the LSF system,
however, showed a broad peak around 250 K, sim-
ilar to that observed in the La Ca MnO sys-
\V V 
tem by Palstra et al. [11], who proposed that the
thermoelectric power, , can be expressed as
"(k /e)(E /k ¹)# , (2)
? 
where E is the activation energy for thermoelectric
?
power and  is the thermoelectric power at asymp-

totically high temperatures } a measure of the en-
tropy of crystalline and magnetic disorder. The
other symbols have their conventional meanings.
!(k /e)ln[2(1!c)/c] where c is the
In Fig. 1, the straight line on the Arrhenius plot of

/T!1/T yields E "0.302 eV, while the linear re-
M
lation of !1/T yields E "0.077 eV.
?
From Fig. 2, we see that the transport gap from
thermoelectric power is much smaller than the
gap derived from resistivity measurements. Ther-
moelectric power measures, in a simpli"ed picture,
!(k /e)ln[(2!c)/c]. If hole con-
the heat current associated with charge motion,
which for usual semiconductors is the activation
energy across the (kinetic) gap. If transport is dom-
inated by one type of carrier, this results in an
equality of the transport and thermoelectric power
gap. In the oxides where the hopping motion of
small polarons dominates electrical transport, E is
?
the potential di!erence between identical lattice
distortions with and without a hole and/or elec-
tron, while E +W #E where W is the hopping
M & ? &
energy of small polaron [6}10,12]. Then a large
di!erence in the magnitudes between E and E is
M ?
a hallmark of the polaronic transport [6].
The extrapolation of  !1/T relation in Fig. 2
yields  "!130
V/K. Heikes's formula [13,14]

and its suggested modi"cations explain well the
high-temperature thermoelectric power. In the
limit of temperature (TPR), the thermoelectric
power for a system of localized carriers with spin is
given by 

relative electron concentration measured as the
number of electrons per available site. The relation
assumes complete correlation so that all double
occupancy is avoided, U<k T where U is on-site
Coulombic repulsion. At the other extreme which
has no correlation and allows double occupancy
(U; T), 

centration is assumed to be the relative Fe> con-
centration,  "!132
V/K for complete correla-

 W.-H. Jung / Physica B 299 (2001) 120}123
tion, nearly equal to the experimental value, and
!150
V/K for no correlation. Then LSF is surely
a strongly correlated system.
Acknowledgements
This work was supported by Korea Research
Foundation Grant (KRF-2000-015-DP0165).
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