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0
H
ext
D M
A
M
B
M
B
, 2
n
v
is the density of magnetic ions on one sublattice, g
J
is the
Lande
0
/3k
B
. For ferro-
magnetic materials, sublattices A and B are equivalent and
the ordering temperature is T
M
F
(1)C. Standard thermo-
dynamic considerations show that the magnetic contribution
to the specic heat c
m
is given by
c
m
H
ext
, Tc
m
0,T
T
2
T
2
0
H
ext
0
MdH
ext
T
,
3
where can be taken as either the mass or molar density.
9
Figure 2 shows the numerically calculated values of c
m
as a
function of temperature and applied eld for the antiferro-
magnetic material EuMo
6
S
8
with the Eu ions in the 2 va-
lence state and the parameters: J3.5, g
J
2.0, n
v
3.64
10
27
m
3
and the ordering temperature T
M
A
arbitrarily
xed to be 1.5 K. Above the ordering temperature, the mag-
nitude of the Schottky anomaly increases and then saturates
even up to very high magnetic elds.
Figure 3 shows the superconducting and magnetic contri-
bution for (Sn
0.50
Eu
0.50
)Mo
6
S
8
as a function of both tem-
perature and eld, together with the calculated magnetic con-
tribution solid lines. The zero-eld contribution c(0,T) was
obtained by extrapolating by eye the specic heat from the
critical temperature (T
c
) down to T0 K and then sub-
tracted from the total specic heat. This extrapolation only
affects the values of B
c2
and obtained at the highest eld
measured. At all lower elds, the extrapolation is constrained
in the region of the jump by measurements of the normal-
state properties measured in higher elds cf. Fig. 4. The
calculated values were obtained using the free ion values of
J and g
J
i.e., 3.5 and 2, respectively, a value of n
v
within
3% of the nominal composition consistent with x-ray data
showing almost single-phase material, and a value of T
M
A
0.350.5 K. This value for the ordering temperature is
consistent with the range 0.20.6 K for EuMo
6
S
8
cited in the
literature.
10
The agreement between calculations and experi-
ment above 10 K conrms that the Eu
2
ions are essen-
tially free ions. Figure 4 shows the specic heat after the
magnetic contribution has been subtracted for the
(Sn
0.65
Eu
0.35
)Mo
6
S
8
and (Sn
0.50
Eu
0.50
)Mo
6
S
8
samples. Both
samples show a eld-independent specic heat above
10 K, characteristic of nonmagnetic superconductors in-
cluding SnMo
6
S
8
.
11
The size of the specic-heat jump (c)
FIG. 2. c
m
as a function of temperature and applied eld, cal-
culated for antiferromagnetic EuMo
6
S
8
with T
M
A
1.5 K, J3.5,
g
J
2.0, and n
v
3.6410
27
m
3
.
FIG. 3. cc(0,T) as a function of temperature and applied eld
for (Sn
0.50
Eu
0.50
)Mo
6
S
8
; symbols are the experimental data and
solid lines are the calculated values.
NIGEL R. LEIGH AND DAMIAN P. HAMPSHIRE PHYSICAL REVIEW B 68, 174508 2003
174508-2
can be equated to the upper critical eld (B
c2
) and the
Ginzburg-Landau parameter using
12
c
T
c
dB
c2
dT
2
1.16
0
2
2
T1
. 4
Using the data in Fig. 4, the specic-heat jump at each eld
is analyzed using a standard procedure that considers an ide-
alized sharp jump that conserves entropy and from which c
and B
c2
are then obtained.
11
The temperature dependence of
is then determined using Eq. 4 and the results are pre-
sented in Fig. 5 including data obtained on SnMo
6
S
8
). The
average values of (T) and the normal-state resistivity in-
crease systematically as the doping level is increased consis-
tent with an expected increase in the conduction electron
scattering rate. The marked improvement in analysis,
achieved by accurate subtraction of the magnetic back-
ground, shows that increases as T decreases for both mag-
netic samples, which is similar to metallic superconductors.
13
The data also conrm the very high technologically impor-
tant values of dB
c2
/dT for these Eu-doped compounds
(6.1 TK
1
for x0.35 and 5.5 TK
1
for x0.50) that
are both larger than the undoped sample (3.9 TK
1
).
The calculations of c
m
are computationally demanding,
particularly if the free parameters J, g
J
, n
v
, and T
M
are
completely unknown. For antiferromagnetic materials, si-
multaneous transcendental equations must be solved numeri-
cally at an accuracy sufcient to nd the integrals and double
derivatives in Eq. 3. We have compared the behavior of the
Schottky anomalies predicted from the numerical solutions
with the heat capacity that follows from a simple approxi-
mate form for the magnetization M given by
MM
s
tanh
CH
ext
M
s
T
M
s
tanh
g
J
J1
B
0
H
ext
3k
B
T
,
5
where J now represents the degeneracy of the ground state,
M
s
the saturation magnetization where M
s
n
cell
g
J
B
J and
n
cell
is the number of magnetic ions per unit cell, and is
the Curie-Weiss constant where T
M
F
in the ferromagnetic
case and CT
M
A
in the antiferromagnetic case. Above
T
M
the results from both the approximate form and those
calculated using the full functional form for M Fig. 2 have
the same general features. At low elds, the magnitude of the
peak of the anomaly either increases or decreases with in-
creasing eld for the antiferromagnetic or ferromagnetic
case, respectively. Hence there is a signicant difference
from the standard analysis of Schottky anomalies that does
not consider interacting ions, since this work provides a
simple direct interpretation of the increase/decrease in the
magnitude of the peak in the anomaly just above the ordering
temperature. This intrinsic behavior for the Schottky
anomaly above the ordering temperature is not found from
simple partition function calculations that consider noninter-
acting ions. In high elds, a saturation in the peak value of
the Schottky anomaly is found. From Eq. 5 analytic forms
for the eld-temperature dependence i.e.,
0
H
ext
peak
vs T
peak
)
and for the saturation value (c
m
sat
) of the peak can be calcu-
lated of the form
0
H
ext
peak
6.54
g
J
J1
T
peak
, 6
c
m
sat
1.12
n
cell
RJ
J1
, 7
where R is the molar gas constant. The prefactors, 6.54 and
1.12, were chosen to ensure that Eqs. 6 and 7 are consis-
tent with the rigorous calculation for Eu
2
and should only
be considered approximate across the rare-earth series. The
equations can be used to calculate the Curie temperature and
Curie constant of single-phase materials or the quantity of
FIG. 4. (cc
m
)/T as a function of temperature and applied eld
for (Sn
0.50
Eu
0.50
)Mo
6
S
8
. Inset: (cc
m
)/T as a function of tempera-
ture and applied eld for (Sn
0.65
Eu
0.35
)Mo
6
S
8
; the applied elds in
the inset and the inset axes and are the same as in the main gure.
FIG. 5. as a function of temperature for (Sn
1x
Eu
x
)Mo
6
S
8
with x0.00, 0.35, and 0.50.
DERIVING THE GINZBURG-LANDAU PARAMETER FROM . . . PHYSICAL REVIEW B 68, 174508 2003
174508-3
second-phase materials of known magnetic properties with-
out advanced computation. We have successfully used this
approach to model the specic heat above 3 K of a
(Pb,Gd)Mo
6
S
8
superconductor (T
M
A
1 K) with
6% Gd
2
S
3
magnetic second phase (T
M
A
5.5 K).
11
We have analyzed the Schottky anomalies in the literature
for the 1-2-3 high-temperature superconductors
YbBa
2
Cu
3
O
7
, ErBa
2
Cu
3
O
7
, and DyBa
2
Cu
3
O
7
Ref. 14 us-
ing Eqs. 6 and 7, and derived the values of g
J
(J1) and
J shown in Table I. The values of g
J
(J1) are in reasonable
agreement with free ion values. The magnitude of the peak
value of the heat capacity at the Schottky anomaly for these
materials increases with increasing eld above the ordering
temperature indicating antiferromagnetic ordering at low
temperatures. The calculated values of J are all close to 0.5,
indicative of the ground state of the rare-earth ions in these
compounds being a doublet state. These observations are
consistent with neutron-diffraction measurements on
ErBa
2
Cu
3
O
7
that show a two-dimensional antiferromagnetic
doublet ground state.
14
IV. CONCLUSION
We conclude that the ground-state properties of a mag-
netic system can be deduced from specic-heat data using
the two approximate equations provided Eqs. 6 and 7
and that the increasing or decreasing magnitude of the
Schottky anomaly above the ordering temperature used to
indicate antiferromagnetic or ferromagnetic ordering, respec-
tively. Hence the magnetic contribution can be calculated for
both single and multiphase compounds, which is necessary
for accurately determining B
c2
and in strongly magnetic
superconductors.
1
V. L. Ginzburg, J. Exptl. Theoret. Phys. U.S.S.R. 31, 202 1956
Sov. Phys. JETP 4, 153 1957.
2
S. S. Saxena, P. Agarwal, K. Ahilan, F. M. Grosche, R. K. W.
Haselwimmer, M. J. Steiner, E. Pugh, I. R. Walker, S. R. Julian,
P. Monthoux, G. G. Lonzarich, A. Huxley, I. Sheikin, D. Braith-
waite, and J. Flopuquet, Nature London 406, 587 2000.
3
T. R. Kirkpatrick, D. Belitz, T. Vojta, and R. Narayanan, Phys.
Rev. Lett. 87, 127003 2001.
4
S. Keys and D. P. Hampshire, in Handbook of Superconducting
Materials, edited by D. Cardwell and D. Ginley IOP Publish-
ing, Bristol, 2003, Vol. II, p. 1297.
5
H. Eisaki, H. Takagi, R. J. Cava, B. Batlogg, J. J. Krajewski, W.
F. Peck, K. Mizuhashi, J. O. Lee, and S. Uchida, Phys. Rev. B
50, 647 1994.
6
D. N. Zheng, H. D. Ramsbottom, and D. P. Hampshire, Phys.
Rev. B 52, 12 931 1995.
7
V. L. Ginzburg and L. D. Landau, Zh. Eksp. Teor. Fiz. 20, 1064
1957 A.C.S.I.L. Translation No. 1247.
8
N. R. Leigh, I. J. Daniel, D. N. Zheng, and D. P. Hampshire,
IEEE Trans. Appl. Supercond. 167, 175 2000.
9
H. Mitamura, T. Sakakibara, G. Kido, and T. Goto, J. Phys. Soc.
Jpn. 64, 3459 1995.
10
O. Pena and M. Sergent, Prog. Solid State Chem. 19, 165 1989.
11
N. R. Leigh, Ph.D. thesis, Durham University, 2001.
12
K. Maki, Phys. Rev. 139, A702 1965.
13
M. Decroux, P. Selvam, J. Cors, B. Seeber, O. Fischer, R. Chev-
rel, P. Rabiller, and M. Sergent, IEEE Trans. Appl. Supercond. 3,
1502 1993.
14
H. P. van der Meulen, J. J. M. Franse, Z. Tarnawski, K. Kad-
owaki, J. C. P. Klasse, and A. A. Menovsky, Physica C 152, 65
1988.
TABLE I. Values of c
m
sat
and (
0
H
ext
)/T
peak
determined from the specic-heat data of Meulen et al.
Ref. 14 for 1-2-3 high-temperature superconductors. Values of J and g
J
(J1) are estimated from these
results using Eqs. 6 and 7. Shown in square brackets are the theoretical values of J and g
J
(J1) for the
free ions.
Material
c
m
peak
(J K
1
mole
1
) J
(
0
H
ext
)/T
peak
(T K
1
) g
J
(J1)
ErBa
2
Cu
3
O
7
3.5 0.6 7.5 0.6 10.9 10.2
YbBa
2
Cu
3
O
7
3.5 0.6 3.5 1.0 6.5 5.1
DyBa
2
Cu
3
O
7
2.5 0.4 7.5 0.4 16.4 11.3
NIGEL R. LEIGH AND DAMIAN P. HAMPSHIRE PHYSICAL REVIEW B 68, 174508 2003
174508-4