Correlation between magnetovolume and giant magnetoresistance effects in doped

La2/3Ca1/3MnO3 perovskites
J. M. De Teresa, J. Blasco, M. R. Ibarra, J. García, C. Marquina, P. Algarabel, and A. del Moral

Citation: Journal of Applied Physics 79, 5175 (1996); doi: 10.1063/1.361544

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 Correlation between magnetovolume and giant magnetoresistance effects
in doped La2/3Ca1/3MnO3 perovskites
J. M. De Teresa, J. Blasco, M. R. Ibarra, J. Garcı́a, C. Marquina, P. Algarabel,
and A. del Moral
Departamento de Fı́sica de la Materia Condensada e Instituto de Ciencia de Materiales de Aragón,
Universidad de Zaragoza-CSIC, 50009-Zaragoza, Spain
La0.62Tb0.05Ca0.33MnO3 and La0.6Y0.07Ca0.33MnO3 have been studied in order to probe into the
mechanisms responsible for the giant magnetoresistance ratios observed in this kind of compound.
The experiments have shown a strong connection between the magnetotransport and
magnetovolume properties. A large volume effect appears above T c which collapses with applied
magnetic field or when the long range magnetic order sets in. Above T c the magnetostriction and
magnetoresistance isotherms are highly correlated. Charge localization with local distortion appears
to be responsible for the transport and volume properties at zero field. Charge mobility and a more
normal volume dependence on temperature are restored by applying high enough magnetic fields.
© 1996 American Institute of Physics. @S0021-8979~96!52208-0#

I. INTRODUCTION dissolved in concentrated nitrid acid resulting in a light so-

lution. Afterwards, citric acid and ethylene glycol were
A lot of experimental and theoretical effort is currently
added in a ratio of 4 g citric acid to 1 ml ethylene glycol and
being devoted to understand the intriguing behavior of
1 g metal nitrates. The solution was heated and the excess
Rx B12x MnO3 ~R5rare earth, B5Ca,Sr,Ba,Pb! and related
nitrid acid and water were boiled off giving a brown
compounds.1–10 The main interest of some of these com-
~yellow–brown in the yttrium-doped compound! gel. The gel
pounds is the exhibition of giant magnetoresistance ~GMR!
was heated to give a black–brown ~brown in the yttrium-
ratios across a wide range of temperatures. The understand-
doped compound! powder. This precursor was calcined at
ing of the relevant mechanisms which produce the GMR in
1173 K overnight. The remaining black powder was cold
these perovskitelike materials is of great importance due to
pressed to 4 kbar and sintered at 1273 K for 3 h with inter-
the vast technological applications of GMR devices.
mediate grindings. Finally the pellet was sintered at 1573 K
Recent works on Pr1/2Sr1/2MnO3 ~Refs. 5 and 11! have
for 8 h resulting in a hard black ceramic material. The
given evidence for charge ordering accompanied by a first-
samples were analyzed by means of x-ray powder diffraction
order change of the lattice parameters which strongly in-
resulting in a single phase with a perovskitelike structure.
creases the resistivity. In this article we study the volume
A superconducting coil was used to produce steady mag-
change of doped La2/3Ca1/3MnO3 across the temperature
netic fields up to 12 T. Both resistance ~MR! and thermal
range where GMR ratios are observed. In these compounds
expansion ~MS! were simultaneously measured in two differ-
the resistance shows a maximum at around T c , when the
ent pieces of the same sample in order to correlate both prop-
ferromagnetic long-range order sets in, marking the cross-
erties. Resistance ~MR! was measured with the standard four
over from a nonmetallic state to a metallic one. The highest
points technique; the contacts were done with silver paste on
GMR ratios appear around T c . The presence of lattice dis-
bar-shaped samples. The magnetic field was applied parallel
tortions above T c was assumed to be a signal of charge
to the current. Linear thermal expansion (DL/L) was mea-
localization.12 Consequently resistance and volume effects
sured using the strain–gauge technique. The volume thermal
would be highly correlated in this region. Simultaneous mea-
expansion (DV/V) was calculated as three times the linear
surements of resistance and linear thermal expansion have
thermal expansion. For the MS results the strain parallel ~li!
been carried out to check this possibility. The effect of ap-
and perpendicular ~l'! to the applied field was measured.
plying a magnetic field on the transport and volume proper-
Volume magnetostriction ~VMS! and anisotropic magneto-
ties has also been measured through magnetoresistance ~MR!
striction ~AMS! are straightforwardly calculated as
and magnetostriction ~MS! experiments up to 12 T. The col-
v5li12l' and lt 5li2l' , respectively.
lapse of the charge-ordering state under applied magnetic
Magnetization and initial magnetic susceptibility ~xac!
field in Pr1/2Sr1/2MnO3 has recently been reported5 and con-
under applied fields up to 5 T were carried out with a quan-
sequently the GMR ratios in doped La2/3Ca1/3MnO3 can be
tum interference device magnetometer ~SQUID!.
connected with the collapse of the localized-charge state un-
der applied magnetic field.
III. RESULTS AND DISCUSSION
Magnetization measurements ~not presented here! gave
II. EXPERIMENT
ferromagnetic order at T c '220 K for the terbium-doped
The samples were prepared using a gel precursor in or- compound and T c '160 K for the yttrium-doped compound.
der to obtain well-mixed reagents. Stochiometric amounts of These temperatures coincide with the maxima of the resis-
La2O3 , Tb4O7 ~Y2O3 in the yttrium-doped compound!, tance at zero field shown in Fig. 1. Consequently the onset of
CaCO3, and MnCO3 with nominal purities .99.9%, were ferromagnetism makes the samples leave the nonmetallic

J. Appl. Phys. 79 (8), 15 April 1996 0021-8979/96/79(8)/5175/3/$10.00 © 1996 American Institute of Physics 5175
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 FIG. 1. Resistance vs temperature at 0, 1, and 12 T and MR~%! at 12 T of
~a! La0.62Tb0.05Ca0.33MnO3 and ~b! La0.6Y0.07Ca0.33MnO3 .
state and enter the metalliclike state. This transition has re-
cently been considered to be a first-order insulator–metal
transition.9 It has been proposed9 that an abrupt increase in b
~the matrix element which describes the electron hopping
ratio between Mn sites! at T c is a possible mechanism for the
crossover from one state to the other.
The effect of applying a magnetic field is twofold ~see
Fig. 1!. First the transition is shifted to higher temperatures
and second the resistance values are strongly diminished in
all temperatures. It brings about large MR values at 12 T
~MR~%!5100$[ r (0)2 r (H)/ r (H)%! which are shown in
Fig. 1. At around T c , MR~%! reaches values of '700 for the
terbium-doped compound and '3800 for the yttrium-doped
compound. A strong connection between T c values and MR
ratios has been observed in other work:4,9,10 for lower T c
values, larger MR ratios are obtained.
The connection between resistance and volume effects is
of great interest because it can give a new insight into the
problem. In Fig. 2 we show the volume thermal expansion
versus temperature under different magnetic fields. The in-
sets show the differences obtained between the curves under
zero and applied magnetic field. The volume thermal expan-
sion curve under 12 T ~this field has almost supressed the
nonmetallic state! is similar to the usual anharmonic lattice
contribution. Under zero field ~simultaneously with the
strong resistance effect! an extra contribution appears. At
;T c a strong lattice contraction ~'0.8%! accompanies the
crossover from the nonmetallic to the metallic behavior. This
rather steep change of the lattice parameters at T c can be
5176 J. Appl. Phys., Vol. 79, No. 8, 15 April 1996
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195.19.233.81 On: Thu, 14 Nov 2013 10:21:02
FIG. 2. Volume thermal expansion vs temperature at 0, 1, 5, and 12 T of ~a!
La0.62Tb0.05Ca0.33MnO3 and ~b! La0.6Y0.07Ca0.33MnO3 . The insets show the
difference of the relative volume DV/V~0 T!2DV/V~1 T! and DV/V~0 T!
2DV/V~12 T! obtained from these measurements.
related to the abrupt change of b claimed by Hwang et al.9
The extra contribution to the volume thermal expansion
above T c can be due to the progressive charge localization
with decreasing temperature of the e g Mn electrons13 until T c
is reached. This localization can cause a local distortion of
the lattice. At T c the insulator–metal transition accompanied
by volume change would delocalize the e g electrons and the
metallic behavior would take place.
In Fig. 3 we show the isotherms of MR and VMS at
different temperatures for the Tb-doped compound. Although
GMR exists below and above T c , the resistance isotherms
have different shape in both regions. Below T c @see inset of
Fig. 3~a!# the curvature is always positive and a rapid change
of resistance takes place at low fields. Above T c the curva-
ture changes from negative to positive at a field (H c ) which
moves upwards with increasing temperatures. Below H c the
resistance is rather flat, evolving rapidly above H c towards a
tendency to saturation. The VMS ~v! and AMS ~lt ! versus
temperature at the maximum field ~12 T! are shown in Fig. 4.
The AMS is the typical of a ferromagnet: zero above T c and
small below T c . The VMS is intriguing: zero below T c and
very large above T c . This unusual volume effect has its
De Teresa et al.

FIG. 3. ~a! Resistance vs applied magnetic field at temperatures .T c . The
inset shows the results at temperatures below T c . ~b! Volume MS as a
function of applied magnetic field at temperatures above T c .
maximum value at T c and rapidly vanishes when the
insulator–metal transition takes place. In Fig. 3~b! the shape
of the VMS isotherms above T c can be seen. The VMS iso-
therms are extremely similar to the MR isotherms. It seems
evident that above T c the transport and volume properties are
intimately related with each other. It appears that both, the
charge localization and the local distortion which take place
at zero field, are released by applying a magnetic field, caus-
ing large MR and VMS effects. These effects are also visible
J. Appl. Phys., Vol. 79, No. 8, 15 April 1996
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195.19.233.81 On: Thu, 14 Nov 2013 10:21:02
FIG. 4. Volume ~v! and anisotropic ~lt ! MS at 12 T vs temperature.
in the pure La2/3Ca1/3MnO3 compound and will be published
elsewhere.
In summary, MR and MS measurements have revealed a
tight relationship between the transport and volume proper-
ties of doped La2/3Ca1/3MnO3 above T c suggesting a charge
localization which causes a volume effect. These phenomena
disappear at T c , when the long range magnetic order sets in,
where a large volume contraction takes place ~0.8%!, or by
applying high enough magnetic fields, bringing about GMR
ratios and large VMS values above T c .
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De Teresa et al. 5177