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J Supercond Nov Magn (2015) 28:459467

DOI 10.1007/s10948-014-2725-7

ORIGINAL PAPER

Synthesis, Structure, and Properties of the Superconductor


Ba1x Kz Bi1y Pby O3
Hao Zhang Xiaohuan Lin Yuntian Zheng
Shuang-er Li Guobao Li Fuhui Liao Jianhua Lin

Received: 7 June 2014 / Accepted: 18 August 2014 / Published online: 3 September 2014
Springer Science+Business Media New York 2014

Abstract The series of BaBi1y Pby O3 (0 y 1) has


been synthesized by high-temperature solid-state reaction.
X-ray and selected area electron diffraction data indicate
that BaBi1y Pby O3 (0 y 0.88) crystallizes in space
group P1 and BaBi1y Pby O3 (0.93 y 1) crystallizes in
space group Imma. The samples with the nominal formula
BaBi1y Pby O3 (y = 0.70, 0.80, 0.90) shows superconductivity with transition temperature (Tc ) around 11 K. When
BaBi1y Pby O3 (0 y 0.80) was treated with KOH and
KF at 450 C, the corresponding samples with the nominal formula Ba1x Kz Bi1y Pby O3 (0 y 0.80) were
obtained, which shows superconductivity withTc changing
from 30 to 11 K.

Ba and K) and the B site (such as Bi) in BKBO can be


changed by other elements to form a serials of superconductors, e. g., Sr1x Kx BiO3 (x = 0.450.60, Tc . 12 K) [2],
Sr1x Rbx BiO3 (x . 0.50, Tc . 13 K) [2], BaBi1x Pbx O3
(x = 0.050.30, Tc . 13 K) [3], BaPb1x Sbx O3 (x . 0.25,
Tc . 3.5 K) [4], (K0.87 Bi0.13 )BiO3 (Tc . 3.5 K) [5],
Ba0.9 K0.1 Pb0.75 Bi0.25 O3 (Tc . 3.5 K). [6] Most of them
are single-site (A or B)-doped BaBiO3 . Double-site (both
A and B) doping BaBiO3 -based superconductors are rare.
Here, our tries to synthesize Ba1x Kx Bi1y Pby O3 are presented. Some new superconductors with Tc around 20 K
were found.

Keywords Superconductivity Perovskite BaBiO3


Tructure Opotactic reaction

2 Experiment

1 Introduction
Ba1x Kx BiO3 (BKBO) is a very interesting superconductor
with transition temperature (Tc ) about 30 K because it has
three-dimensional ABO3 perovskite structure and no transition metal elements. [1] The atoms at the A site (such as
H. Zhang X. Lin G. Li () F. Liao J. Lin ()
Beijing National Laboratory for Molecular Sciences,
State Key Laboratory of Rare Earth Materials Chemistry
and Applications, College of Chemistry and Molecular
Engineering, Peking University Beijing 100871,
Peoples Republic of China
e-mail: liguobao@pku.edu.cn
e-mail: jhlin@pku.edu.cn
Y. Zheng S. Li
Beijing National Day School, Beijing 100039,
Peoples Republic of China

The samples with the nominal formula BaBi1y


Pby O3 (y = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9,
and 1.0, noted as BBP1, BBP2, ..., BBP11) were synthesized by solid-state reactions at the temperature between
800 and 900 C using BaCO3 (A.R.), Bi2 O3 (A.R.), and
PbO2 (A.R.) as raw materials in a process similar to synthesize BaBi1x Tax O3 (0 . x . 0.5) reported previously.
[7] The obtained BBP1 to BBP11 were mixed with KOH
and KF with a ratio of BaBi1y Pby O3 :KOH:KF = 1:4:2
by weight. The mixtures were then treated at 450 C for 4 h
and cooled to room temperature at 60 C/h. The cooled
mixtures were washed with water and dried at 80 C. The
corresponding samples were noted as BBP1K, BBP2K, ...,
BBP11K, respectively.
Powder X-ray diffraction (PXRD) data of the samples
were first collected for checking the phases of the samples
on a Rigaku D/Max-2000 diffractometer using a rotating
anode (CuK, 40 kV and 100 mA), a graphite monochrometer and a scintillation detector. After that, the PXRD data

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samples were obtained also from JEM2100F with an accelerating voltage of 200 KV. Magnetic susceptibility was
measured in the temperature range between 5 and 50 K
by SQUID magnetometer (Quantum Design MPMS) in an
applied magnetic field of 100 Oe. Resistance of selected
sample was measured between 2 and 50 K by physical
property measurement system (PPMS).

3 Results and Discussion


3.1 Crystal Structure and Superconductivity
of BaBi1y Pby O3 (0.0 y 1.0)
Fig. 1 X-ray diffraction patterns of BaBi1yPbyO3 (y = 0, 0.1, ...,
1.0, noted as BBP1, BBP2, ..., BBP11, respectively)

of the samples for Rietveld refinement using GSAS [8, 9]


were collected on a PANalytical Empyrean diffractometer
The existence of Ba,
with CuK1 radiation (1.540598 A).
K, Bi, Pb, and F in the obtained samples were checked
by EDS performed on high-resolution electron microscropy
JEM2100F. The selected area electron diffraction of the

The X-ray diffraction patterns of the samples BBP1 to


BBP11 are similar to each other as shown in Fig. 1, indicating that they may have the similar structure. In our
previous work [7], many efforts have been performed to
confirm that BaBiO3 crystallizes in space group P1 at room
b = 6.186 (1) A,

temperature with a = 6.141(1) A,


= 59.90 (1) , = 59.98 (1) ,
c = 6.144 (1) A,
= 59.87 (1) . The similarity of the X-ray diffraction
patterns of BaBi1y Pby O3 (0.0 . y 1.0) induces that all

Fig. 2 SAED patterns along different directions (ae) and the Rietveld plot of X-ray diffraction data (f) of BBP11

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Table 1 Rietveld refinement details for BBP11 and BBP10


BBP11
Phase Aa
Lattice parameter

b = 8.5110 (3) A,

a = 6.0285 (3) A,

c = 6.06523 (3) A

b = 8.5293 (3) A,

a = 6.0417 (3) A,

c = 6.06867 (3) A

Space Group
Ba1
Ba2
Pb/Bib
Pb/Bib
O1
O2
O3
O4
O5
O6
R factorc

Imma
0.0000, 0.2500, 0.5028 (3)

Imma
0.0000, 0.2500, 0.5017 (3)

0.0000, 0.0000, 0.0000

0.0000, 0.0000, 0.0000

0.0000, 0.2500, 0.0532 (3)


0.2500, 0.0293 (3), 0.2500

0.0000, 0.2500, 0.0546 (3)


0.2500, 0.0499 (3), 0.2500

Rwp = 0.092, Rp = 0.057

Rwp = 0.087, Rp = 0.056

BBP10
Phase B
b = 6.0526 (3) A

a = 6.0367 (3) A,
= 59.76 (2)
c = 6.0560 (3) A,
= 60.16 (2) , = 60.13 (2)
P1
0.2503 (3), 0.2479 (3), 0.2670 (3)
0.7496 (3), 0.7458 (3), 0.7682 (3)
0.0000, 0.0000, 0.0000
0.4995 (3), 0.5018 (3), 0.4986 (3)
0.3505 (3), 0.1532 (3), 0.6732 (3)
0.8041 (3), 0.7332 (3), 0.2402 (3)
0.7675 (3), 0.2560 (3), 0.2326 (3)
0.2522 (3), 0.8125 (3), 0.6864 (3)
0.1922 (3), 0.7578 (3), 0.2513 (3)
0.6807 (3), 0.2545 (3), 0.7639 (3)

a The

ratio of phase A:phase B is 0.81:1.00


ratio of Pb/Bi in phases A and B is about 0.925 and 0.880, respectively
c Rn1 , Rn1 are the R factors of the whole patterns and the peaks only, respectively
wp
p
b The

of them may crystallize in space group P1. However, the


space groups reported for BaBi1y Pby O3 (0.0 y 1.0)[10,
1215] are different from P1 except BaBiO3 . Therefore,
careful checking was performed and the results were presented below.
BaPbO3 (BBP11) has been reported to crystallize at room temperature in several different space

groups: Pnma (a 6.023, b 8.504, c 6.062 A)


[18, 19],
[2022], and
Imma (a 6.030, b 8.509, c 6.069 A)
90.0. ) [16,
I2/m (a 6.023, b 8.504, c 6.062 A,
17]. The previous discussion on the structure of BaPbO3
is mainly based on the X-ray and neutron diffraction. As
Fig. 3 The Rietveld plot of
X-ray diffraction data of
BBP-10 with two phases

proved, the selected area electron diffraction (SAED) is


very useful to help the determination of the structure of
a compound [7, 23, 24], which will show the diffraction
conditions to help the choice of the corresponding space
groups. Then the SAED patterns of BBP11 were obtained
and shown in Fig. 2. The following diffraction conditions
can be obtained: hkl, h+k+l=2n; hk0, h= 2n and k= 2n

with a 6.023, b 8.504, c 6.062 A,
90.0. . These diffraction conditions correspond to
the space group Imma and its subgroups: Im2b, I112/b,

I11b with a 6.023, b 8.504, c 6.062 A,
90.0 , and do not agree with the space group Pnma
and I2/m (a 6.023,
(a 6.023, b 8.504, c 6.062 A)

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Fig. 4 SAED patterns along different direction indexes in orthorhombic (a1, a2, a3, a4, and a5) and triclinic (b1, b2, b3, b4, and b5) lattice, and
the Rietveld plot of X-ray diffraction data (c) for BBP9

90.0 ). Therefore, our data


b 8.504, c 6.062 A,
confirm that the space group Imma can be used to describe
the structure of BaPbO3 at room temperature (usually, we
like to use the highest possible space group to describe
the structure of a compound). The powder X-ray diffraction data obtained by us can be fitted well with this space
group as shown in Fig. 2f. The refinement details are
listed in Table 1.
As reported, BBP10 with the nominal formula
BaPb0.90 Bi
0.10 O3 may be tetragonal [10] (I4/mcm,
a= b 2ap , c 2ap ; ap , the lattice parameter a of
the simple
cubic perovskite),

orthorhombic [11] (Imma,


a 2 ap , b 2ap , c 2 ap ), or biphasic (tetragonal
plus orthorhombic) [25]. Our results show that BBP10 is
biphasic, orthorhombic plus triclinic. The powder X-ray
diffraction patterns of BBP10 can be fitted well with the
two phases as shown in Fig. 3. The details of the refinement
are listed in Table 1.

Similarly,
BBP9 may also be tetragonal [10] (I4/mcm,

a=b 2ap ,c 2ap ), orthorhombic [11] (Imma, a 2p ,


b 2ap , c 2ap ), or biphasic (tetragonal plus orthorhom-

Fig. 5 The volume of unit cell of the phases in the samples

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bic)[25]. The diffraction conditions for I4/mcm and Imma


are hkl: h+k+l= 2n; 0kl: k, l= 2n and hkl: h+k+l= 2n;
and hk0: h, k= 2n, respectively. The SAED patterns of
BBP9 are shown in Fig. 4a. It is found that if the patterns

are indexed with a 6.05, b 8.61, c 6.05 A,

90 , 90 , 90 , the diffraction conditions hkl:


h+k+l= 2n can be agreed, but the conditions 0kl: k, l= 2n
and hk0: h, k= 2n are not agreed. Therefore, the space
groups I4/mcm and Imma should not be used to describe
the structure of BBP9. As the X-ray diffraction patterns of
BBP9 is very similar to that for BBP1(that is BaBiO3 ), the
structure model of BaBiO3 was used to describe BBP9. It
is found that the SAED patterns of BBP9 can be indexed
b 6.04,
well with the space group P1 with a 6.06 A,

c 6.06 A, 60.19 , 59.83 , 60.09 as


shown in Fig. 4b. The powder X-ray diffraction patterns for
BBP9 can be fitted well with the space group P1 as shown
in Fig. 4c.
As for BBP8 to BBP2, similar cases are found as that
for BBP9. The powder X-ray diffraction patterns for BBP8
to BBP2 can be fitted well with the structural model for

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BaBiO3 . The volumes of the unit cell for BBP1 to BBP11


are shown in Fig. 5. It is found that the volume of the unit
cell decreases linearly with the increase of the amount of Pb
in the samples.
The magnetic susceptibilities of the samples BBP1 to
BBP11 were measured. Only the samples BBP8, BBP9, and
BBP10 show superconductivity with Tc around 11 K. Their
temperature-dependent magnetic susceptibilities are shown
in Fig. 6. In addition, the resistance of BBP9 was measured
from 2 to 20 K, which confirms that the BBP9 is a superconductor with Tc around 11 K. This agrees well with the
previous reports by other researchers. The shielding volume
fractions of the three samples are also shown in Fig. 6. The
superconductive volume fraction (shielding volume fraction) measured from the present samples is very small even
the X-ray diffraction data show that BBP8 and BBP9 are
single phase without observable impurities. Of course, the
superconductive volume fraction for the two-phase sample
BBP10 is less than BBP8 and BBP9. The reason for this
phenomenon is complex and not clear. One may argue that
during the measurement, only the surface of a supercon-

Fig. 6 The temperature-dependent magnetic susceptibilities and shielding volume fraction of BBP8 (a), BBP9 (b), BBP10 (c), and the temperature
dependent resistance of BBP9 (d)

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Fig. 7 The Rietveld plot of X-ray diffraction data (a), the temperature-dependent magnetic susceptibilities (b), the EDS of two kinds of particles
(c, d) of BBP1K

ductor has a contribution, the core can be omitted. Then the


shielding volume fraction should be less than 1. One may
also argue that the superconductive phase is beyond the normal phase (maybe we can call them as the diffraction phase,
which means that these phases can be distinguished by Xray, neutron, and electron diffraction patterns), the present
diffraction method could not distinguish the superconductive phase from the nonsuperconductive phases. Then, it is
easy to understand that the shielding volume fraction for the
single phase BBP8 and BBP9 is far less than 1, and is different from each other. At this case, the shielding volume
fractions for other samples are not shown.
3.2 Crystal Structure and Superconductivity
of Ba1x Kz Bi1y Pby O3 (0.0 y 1.0)
It is found that there are four kinds of case for the samples BBP1K to BBP11K: (1) three phases appear in BBP1K,
(2) two phases appear in BBP2K to BBP6K, (3) one
phase appears in BBP7K to BBP9K, and (4) BBP10K and
BBP11K do not show superconductivity. Then, no details
on BBP10K and BBP11K are mentioned below. Superconductivity is found for the samples BBP1K to BBP9K, the
details for these samples are shown below.

3.2.1 BBP1K
The Rietveld refinement of the X-ray diffraction data of
BBP1K indicates that there are three phases in BBP1K
as shown in Fig. 7a. They all crystallize in space group

P1 with pseudo-cubic lattice parameter a about 4.348 A


(phase B), and 4.289 A
(phase
(noted as phase A), 4.341 A
C), respectively. The ratio of phase A:phase B:phase C
is 3.9(3):7.4(3):1.0 suggested by the Rietveld refinement.
BBP1K shows superconductivity with Tc around 30 K as
shown in Fig. 7b. According to the work published by Pet
et al. [26], the superconductivity shown by BBP1K may be
induced by phase C, whose pseudo-cubic lattice parameter a is among the range showing 30 K superconductivity
for Ba1x Kx BiO3 . The amount of K in the sample BBP1K
has been carefully analyzed by EDS method performed on
high-resolution electron microscropy JEM2100F after considering that BBP1K has at least three phases. Most of the
particles analyzed show no the signal for K as shown in
Fig. 7c, only about 10 % of the particles analyzed show
the signal for K as shown in Fig. 7d (Cu and C are due
to micro grid to containing the sample, Fe and Cr, are
due to sample holder). According to this, it may be suggeted that there are no K in phase A and phase B, and

J Supercond Nov Magn (2015) 28:459467

the K mainly apprears in phase C. The lattice shrinkage of


the phases A and B from the precursor BaBiO3 is therefore attibuted to the deficiency of Ba in the A site of
ABO3 perovskite.

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these samples exhibiting superconductivity with Tc decreasing from 25 K for BBP2k to 15 K for BBP6K, which is
shown in Fig. 8.
3.2.3 BBP7K to BBP9K

3.2.2 BBP2K to BBP6K


It is found that there are two phases in BBP2K to BBP6K
as indicated by the Rietveld refinement as shown in Fig. 8a.
The two phases all crystallize in space group P1. The corresponding lattice parameters decrease comparing to their
precursor. No K is found by checking about twenty particles of each BBP2K to BBP6K by EDS method as shown in
Fig. 8b for BBP3K. Magnetic measurements show that all of

The Rietveld refinement of the X-ray diffraction for BBP7K


to BBP9K shows that there is one phase in them as shown
in Fig. 9. It is found also by EDS that there is no K
in these samples. Magnetic measurements show that they
show superconductivity with Tc about 11 K. In order to
measure the resistance of BBP7K between 2 and 20 K,
the sample BBP7K was pressed into pellet and heating at
500 C for 4 h, and noted as BBP7K-500, which was also

Fig. 8 The Rietveld plot of X-ray diffraction data (a) of BBP3K, the EDS of BBP3K (b), the temperature dependent magnetic susceptibilities of
BBP2K (c), BBP3K (d), BBP4k with zero-field cooling and 100 Oe field cooling (e), BBP5K (f), BBP6k (g)

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Fig. 9 The Rietveld plot of X-ray diffraction data (a) of BBP7K, the EDS of BBP7K (b), the temperature-dependent magnetic susceptibilities of
BBP7K (c), BBP7K-500 (treated again at 500 C for 4 h) (d), BBP8k (f), BBP9K (g), and the temperature dependent resistance of BBP7k-500 (e)

Fig. 10 The volume of unit cell (a) of the phases in the samples and transition temperature Tc (b) found in the samples

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confirmed by magnetic measurement to show superconductivity as shown in Fig. 9d. The temperature-dependence
resistant of BBP7K-500 confirmed that BBP7K-500 was
superconductor with Tc at 11 K.

4 Summary
The series of BaBi1y Pby O3 (0 . y . 1) has
been synthesized by solid-state reaction. X-ray and
selected area electron diffraction data confirm that
BaBi1y Pby O3 (0 . y . 0.88) crystallizes in space
group P1 and BaBi1y Pby O3 (0.93 . y . 1) crystallizes in space group Imma. The samples with the nominal formula BaBi1y Pby O3 (y = 0.70, 0.80, 0.90) shows
superconductivity with transition temperature (Tc ) around
11 K. When BaBi1y Pby O3 (0 . y . 0.80) was treated
with KOH and KF at 450 C, the corresponding samples with the nominal formula Ba1x Kz Bi1y Pby O3 were
obtained. The corresponding reaction is found to be topotactic because the topological structure of BaBi1y Pby O3 and
Ba1x Kz Bi1y Pby O3 is the same.
The sample Ba1x Kz BiO3 (BBP1K) consists of three
phases, which may all crystallize in space group P1. Two
of them do not contain K, and the third phase contains K which may be contributor of the superconductivity
with Tc around 30 K found in this sample. The samples Ba1x Kz Bi1y Pby O3 (y = 0.1, 0.2, 0.3, 0.4, and 0.5,
noted as BBP2K, BBP3k, BBP4K, BBP5K, and BBP6K,
respectively) consist of two-phase crystallizing in space
group P1. The EDS data show that there is no K in the
samples, which mean that the samples can be noted as
Ba1x Bi1y Pby O3. The decrease of the volume of unit cell
shown in Fig. 10 agrees well with this suggestion. Superconductivity with Tc around 20 K is found for these samples, which means that new superconductors may appear,
because as we know, there is no report on such materials. More work is needed to confirm this observation. The
samples Ba1x Kz Bi1y Pby O3 (y = 0.6, 0.7, and 0.8, noted
as BBP7K, BBP8k, and BBP9K, respectively) consist of
one-phase crystallizing in space group P1. No K is found
in these samples by EDS data. Superconductivity with Tc
about 11 K was confirmed for BBP7K.
Acknowledgments This work is supported by the National Key
Basic Research Project of China (2010 CB833103) and the National
Natural Science Foundation of China (Grant 21271014).

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