Journal of Magnetism and Magnetic Materials 31-34 (1983) 149-150 149

HIGH CONDUCTIVITY n-TYPE YTTRIUM IRON GARNET

B. A N T O N I N I , A. PAOLETTI, P. P A R O L I , F. S C A R I N C I a n d A. T U C C I A R O N E
Istituto l E S S del CNR, Via Cineto Romano 42, 00156 Rome, Italy

Conductivity of YIG doped with Si, Ge, Sn, Hf and Th, has been measured in the interval 300-600 K. The highest RT value
was 1.14× 10 -3 1"2-Icm-t. Conduction is found to conform to a band model behavior.

A number of studies of the electrical properties of 1.5 2.0 2.5 3.0

n-type yttrium iron garnet (YIG), have been carried out
since the original work of Van Uitert and Swanekamp 5.0
[1]. These studies include measurements of dc conduc-
tivity, Seebeck effect and Hall effect, and have been 60
performed on samples in which x, the Fe 2+ concentra- 4.5
tion, was up to about 0.03 a t o m s / f o r m u l a . The lowest 50 /
measured resistivity was p - - l 0 4 ~ cm at 300 K [2]. /'
4.0 ' /
Conclusions as to the nature of the conduction have
/
often been contradictory, as both a hopping model and 4.0
3.5 i
a band model have been proposed. An insight on the /
conduction mechanism may be obtained by comparing o4,- 3.0 /

the temperature variations of Seebeck coefficient and ,/

resistivity: the former case depends only on the varia- 2.5
tion of n, the concentration of charge carriers, while in &
the latter case, also the mobility enters. HI I
%
In this paper, resistivity and activation energies are co • ]3.0

A'

;).5
,o

2.0

8 YIG:Sn •
,-" / 3
1.5 2.0 2.5 3.0 3.5

E 6 • 107T(K -')
U
Fig. 2. The temperature dependence of p for n-type YIG ob-
tained with different dopants: Hf (left and top scales); Sn, Si,
'0 Ge and Th (right and bottom scales).

measured in a number of n-type Y I G single crystals

1 having different dopants and high F e 2 + concentrations

./ (up to = 0.07 atoms/formula). Furthermore, the tem-

perature variation of the Seebeck coefficient is also
Ref.3 measured.
0~/, e , , The samples were prepared by the flux method using
0 0.02 0.04 0/06 0 a P b O - P b F 2 - B 2 0 a flux. The different dopants were
x (atom/formula) Si 4+ , Ge 4+ , Sn a+ , H f 4+ and Th 4+ . The concentration
Fig. I. Conductivities l / p , at 24°C, of YIG:Si and YIG:Sn of Fe 2+ was evaluated by measuring ul.2, the optical
crystals, for different Fe 2+ concentrations (x). absorption at A = 1.2 #m, and using the calibration of

0304-8853/83/0000-0000/$03.00 © 1983 N o r t h - H o l l a n d
150 B. Antonini et al. / High conductivity n-type YIG
optical absorption with the direct measurement, by
titration with cerium, of Fe 2÷ amounts [3]. The resistiv-
ity measurements, in the range (300-600) K, were made
with a four-point probe method. In fig. 1, the observed
room-temperature conductivities 1/p, are shown for
several YIG : Si and YIG : Sn crystals. Each set of data
exhibits a proportional dependence on Fe 2÷ concentra-
tions (except for a small zero shift). The observed linear-
ity constitutes a strong indication that, in the Fe 2+
concentration range that is being investigated, no appre-
ciable change is occurring in the nature of the conduc-
tion mechanism: all observed changes of 1/p are
accounted for by the sole increase of carrier concentra-
tion.
The temperature dependence of p for the different
dopants is shown in fig. 2: in log p + C, C is an arbi-
trary constant, different for each dopant. One finds
that, in the interval 300-500 K, activation energies U
vary with the different dopants and closely correlate
with site occupancy. In particular, in case of Si and Ge
(d-site dopants), one has U equal to 0.300 and 0.305 eV,
respectively (+0.005 eV); in case of Th (c-site dopant)
U = 0.345 eV; and for Sn and Hf (a-site dopants) U is
0.265 and 0.270 eV, respectively. Furthermore, p, x and
U are related by the general formula p =
( A / x ) explU/kT[, where A = 1.50 × 10 -3 12 cm afu. In
conclusion, the lowest resistivities are associated with
Hf and Sn dopants, because of their lower activation
energies, and, in particular, the lowest we have observed
at 24°C was P~an= (875 + 5) 12cm in a YIG : Sn sample
with x = (0.059 5: 0.001) atoms/formula.
In addition, as shown by fig. 2, Hf has a second
activation energy above 600 K.
Finally, we have investigated the nature of the con-
duction mechanism at room temperature. As mentioned
above, this may be done by comparing the temperature
variations of Seebeck coefficient and resistivity. In par-
ticular, one may compare the temperature derivatives of
log p and of the reduced Seebeck coefficient ¢t': in case
of a band-model mechanism, they should be the same
[1]. Such a study has been previously carried out, on
YIG: Si, in the range 650-1500 K [4] and the results
deafly showed that the activation energy (about 0.3 eV)
reflects mainly the increase of n with temperature (band
model behavior). However, other measurements in a
lower temperature range (250-600 K) [5] gave the same
U as evaluated from the temperature dependence of p,
while the Seebeck coefficient showed only a weak de-
pendence of n on temperature, suggesting conduction to
be by a localized hopping mechanism. The above oppo-
site conclusions for the two successive temperature
ranges seem hardly compatible with each other, particu-
larly since p exhibits the same activation energy (0.3 eV)
in both of them (which rather suggests the same mecha-
nism). Thus we have measured for a YIG : Si sample at
300 K, the temperature derivative of the reduced Seebeck
coefficient a'. We find (within 20% error) d a ' / d T =
- 1.44 × 10 -2. On the other hand, from the resistivity
measurements we obtain: ( d / d T ) log p -- - 1.68 ×
10 -2. We conclude, at variance with ref. [5], that band
model conduction is operative in our crystals, even at
room temperature.
References
[1] See~, for example, R. Metselaar and P.K. Larsen, in: Physics
of Magnetic Garnets, ed. A. Paoletti (North-Holland,
Amsterdam, 1978) p. 417.
[2] R.E. Fontana and D.J. Epstein, Mater. Res. Bull. 6 (1971)
959.
[3] P. Hansen, W. Tolksdorf and J. Schuldt, J. Appl. Phys. 43
(1972) 4370.
[4] P.K. Larsen and R. Metselaar, Phys. Rev. B 14 (t976) 2520.
[5] Ya.M. Ksendzov, A.M. Kotel'nikova and V.V. Makarov,
Sov. Phys. Solid State 15 (1974) 1563.