Journal of Alloys and Compounds 528 (2012) 135–140

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Journal of Alloys and Compounds

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Comparative study on structure and magnetic properties of polycrystalline

Prx Y1−x Ba2 Cu3 O7−ı prepared in oxygen and argon atmosphere
C. Stari a,b , L. Cichetto Jr. b , C.H.M.A. Peres b , V.A.G. Rivera c , S. Sergeenkov b,∗ , C.A. Cardoso b , E. Marega c ,
F.M. Araújo-Moreira b
a
Instituto de Física, Facultad de Ingeniería, UdelaR, Julio Herrera y Reissig 565, C.C. 30, 11000 Montevideo, Uruguay
b
Materials and Devices Group, Department of Physics, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil
c
Instituto de Física de São Carlos, USP, 13560-970 São Carlos, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: We report a systematic study on the influence of the synthesis routes on the structural and magnetic prop-
Received 15 February 2012 erties of polycrystalline Prx Y1−x Ba2 Cu3 O7−ı . We have prepared high-quality samples of this material by
Accepted 10 March 2012 following a sol–gel method based on heat treatment in both inert argon and oxygen atmospheres in order
Available online 17 March 2012
to compare their effect on the formation of the superconducting phase using X-ray powder diffraction.
Magnetic measurements (DC and AC susceptibility) clearly demonstrate that, for the same concentration
Keywords:
of Pr, the superconducting transition temperature markedly increases in all samples prepared in argon
Polycrystalline Prx Y1−x Ba2 Cu3 O7−ı
atmosphere, including pure Pr-123.
Sol–gel method
Argon gas atmosphere © 2012 Elsevier B.V. All rights reserved.
Structure
Magnetic susceptibility
Critical temperature

1. Introduction further corroborated the results of Fehrenbacher and Rice [11].

Despite many attempts (both theoretical and experimental) in
recent years to prove (or disprove) the existence of superconduc-
tivity in PrBa2 Cu3 O7−ı (Pr-123) samples, this issue still remains
highly polemical (for numerous discussions on different aspects
of this fascinating subject, see, e.g., [1–10] and further references
therein). Since the discovery of high temperature superconduc-
tivity in YBa2 Cu3 O7−ı (Y-123), there has been a great interest in
substituting different elements on different sites of Y-123. In partic-
ular, one would expect that, due to a decrease in the concentration
of mobile holes, the critical temperature (TC ) in Prx Y1−x Ba2 Cu3 O7−ı
must be notably depressed. Indeed, according to the theoretical
predictions of Fehrenbacher and Rice [11], the absence of super-
conductivity in Pr-123 is due to the existence of a local Pr (4f)–O
(2p) hybridized state which binds holes to the Pr site. They also
showed that the strength of this hybridization depends on the
Pr–O distance. The experimentally observed dependence of TC on
the mean rare-earth ionic radius in many mixed cuprate mate-
rials [12] supports this idea. Later on, Liechtenstein and Mazin
[13] using the so-called local spin density approximation (LSDA)
∗ Corresponding author. Tel.: +55 16 3351 9638; fax: +55 16 3361 4835.
E-mail addresses: sergei@df.ufscar.br, sergei@fisica.ufpb.br (S. Sergeenkov),
faraujo@df.ufscar.br (F.M. Araújo-Moreira).
At the same time, it was argued that a change in Pr–O distance
might cause a change of Pr valence (and several measurements
[14,15] seem to confirm such a change). Even though some X-ray
spectroscopy and photoemission measurements [16,17] suggest
that Pr occurs only in the trivalent state in these materials, oth-
ers [18–20] strongly suggest a possibility of variable Pr valence. In
the last two decades, superconductivity in Pr-123 samples has been
reported by some authors where the method of syntheses appears
to be responsible for the formation of the stable superconducting
phase [21–23]. Recently, based on the density functional the-
ory and using the full-potential linearized augmented-plane-wave
method, the electronic structure of Pr-123 has been carefully re-
examined by Ghanbarian and Mohammadizadeh [24]. As a result,
they found that there is a more stable solution (missed by Liech-
tenstein and Mazin [13]) which favors intrinsic superconductivity
of pure Pr-123 samples. Their findings can also explain the loss
of superconductivity observed in 17 O NMR spectroscopy study of
the conventional non-superconducting Pr-123 samples [25]. They
argue that this phenomenon is caused by the forced transition of
holes from O2(2p␴ ) orbitals to O2(2p␲ ) orbitals. Inspired by these
latest theoretical findings, in this paper we present a systematic
study on how the internal atmosphere during the synthesis process
influences the formation of the pure phase (using X-ray diffrac-
tion (XRD) technique) and modifies the superconductor transition
(using AC/DC susceptibility measurements) in the polycrystalline

0925-8388/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2012.03.048
136 C. Stari et al. / Journal of Alloys and Compounds 528 (2012) 135–140

Table 1
Atmospheric conditions used for samples preparation along with the values of the critical temperature (TC ) and lattice parameters (a, b, c) deduced, respectively, via AC/DC
magnetic measurements and Rietveld analysis.

Sample-gas Calcination/sintering Orthorhombic symmetry c ± 0.04 (Å) TC (K) from AC /DC
(a − b)/(a + b) × 10−4

Pr01-O2 Oxygen/oxygen 59 11.67 79/78

Pr01-Ar Argon/argon 57 11.68 87/86
Pr02-O2 Oxygen/oxygen 57 11.68 61/63
Pr02-Ar Argon/argon 80 11.68 83/82
Pr03-O2 Oxygen/oxygen 79 11.68 60/59
Pr03-Ar Argon/argon 81 11.68 86/85
Pr04-O2 Oxygen/oxygen 83 11.70 43/43
Pr04-Ar Argon/argon 84 11.69 61/60
Pr06-Ar Argon/argon 85 11.70 88/87
Pr08-Ar Argon/argon 78 11.69 88/87
Pr09-Ar Argon/argon 61 11.74 87/86
Pr10-Ar Argon/argon 51 11.71 90/90

samples of Prx Y1−x Ba2 Cu3 O7−ı . Our results clearly demonstrate
that, for the same concentration of Pr, the superconducting tran-
sition temperature markedly increases in the samples prepared
in argon (rather than oxygen) atmosphere, including pure Pr-123
samples.
2. Samples characterization and magnetic measurements
High quality Prx Y1−x Ba2 Cu3 O7−ı bulk polycrystalline samples
have been prepared by following a chemical route based on the
polymeric precursor method (PECHINI) [26]. This method allows
the attainment of more homogeneous samples (in comparison
with other methods [27]) through a more effective elimination
of secondary phases. During the heat treatment process, differ-
ent atmospheres (oxygen and argon) were used (see Table 1). In
order to compare the influence of the atmosphere on the forma-
tion of the superconducting phase, this procedure was done during
both the calcination of the powder and the sintering of the pressed
pellets. All samples were annealed in oxygen at 450 ◦ C for 5 days.
The phase purity and the structural characteristics of our samples
were confirmed by both scanning electron microscopy (SEM) and
X-ray diffraction. In this last case, we have also performed the stan-
dard Rietveld analysis. Crystalline phases were confirmed through
a Rigaku instrument with a Si 111 monochrometer with a wave-
length of 1.5418 Å (Cu K␣). The analysis of the XRD data (Fig. 1)
shows that no secondary phases are present in our samples and that
the peaks correspond to the orthorhombic structure with Y-123
stoichiometric phase. To define the critical temperature (TC ) of our
samples, we measured the DC and AC magnetic susceptibility. DC
measurements were performed using a Quantum Design-MPMS-5
SQUID magnetometer working in the temperature range from 2 to
400 K and the field range from 0 to 200 Oe. AC measurements were
performed by using a high-sensitivity homemade susceptometer
(operating in the screening method and the reflection configura-
tion [28–30]) with the amplitude of 0.1 Oe and the frequency of
35 kHz.

Fig. 1. XRD patterns: (a) for Prx Y1−x Ba2 Cu3 O7− ı samples with x = 0.1, 0.4 and 1.0 prepared in oxygen atmosphere, and (b) for Pr-123 sample prepared in oxygen (top) and
argon (bottom) atmospheres.
 C. Stari et al. / Journal of Alloys and Compounds 528 (2012) 135–140 137

Fig. 2. SEM images of Prx Y1−x Ba2 Cu3 O7−ı samples with different Pr content prepared under different atmospheric conditions: (a) Pr01-O, (b) Pr01-Ar, (c) Pr03-O, (d) Pr03-Ar,
(e) Pr08-Ar, and (f) Pr10-Ar.

3. Results and discussion
From the analysis of the X-ray powder diffraction data we con-
clude that all samples have orthorhombic symmetry (see Table 1).
Notice that a rather small orthorhombicity (a − b)/(a + b) ≤ 10−3 in
these samples is inconsistent with the cooperative Jahn–Teller sce-
nario [31]. Therefore, the values obtained here are quite similar
to those reported by Peng et al. [1]. Since argon prevents the for-
mation of super-oxides of the Pr6 O11 type, such a behavior can be
directly linked to the atmospheric treatment. In this context, sam-
ples with Pr fraction higher than 0.4 prepared in argon atmosphere
during the synthesis (principally during calcinations) show better
quality with no secondary phases (see Fig. 1(b)). Calcinations under
argon flux are found to prevent the formation of BaCuO2 and BaPrO3
phases (in addition to the above mentioned super-oxides) and show
no transition of orthorhombic to tetragonal structure. Fig. 2 shows
SEM images of grain-boundary morphology for Prx Y1−x Ba2 Cu3 O7−ı
samples with different concentration of Pr prepared in oxygen and
argon atmosphere (for example, Pr01–O stands for the sample with
x = 0.1 treated in oxygen, etc.). As is clearly seen from these images,
the samples prepared in argon atmosphere have an average grain
size two times larger (around 10 ␮m) than the samples treated in
oxygen.
According to Table 1, the lattice parameter c remains essen-
tially unchanged upon doping. Furthermore, the unit cell volume
remains quasi constant with increasing of Pr as well. In other
138 C. Stari et al. / Journal of Alloys and Compounds 528 (2012) 135–140

words, we did not observe any transition in crystal symmetry

Fig. 3. The temperature dependence of AC susceptibility for Prx Y1−x Ba2 Cu3 O7−ı
sample with x = 0.1 prepared in oxygen (O2 ) and argon (Ar) gas atmospheres.
from orthorhombic to tetragonal phase for any value of Pr con-
centration. Contrary to the common believe that substitution of Pr
for Y in Prx Y1−x Ba2 Cu3 O7−ı leads to depression of the supercon-
ducting transition temperature TC , we observe the manifestation
of stable bulk superconductivity for samples with x ≥ 0.5 (from
our measurements of DC and AC magnetic susceptibility, see
Figs. 3–5). A typical temperature dependence of AC susceptibil-
ity for Prx Y1−x Ba2 Cu3 O7−ı sample with x = 0.1 prepared under
different gas atmospheres is shown in Fig. 3 along with the esti-
mated critical temperatures. Recall [22,30] that AC technique is
based on detecting very low fraction of superconducting grains
present in the polycrystalline sample through applying (normally
to the sample’s surface) the AC magnetic field hAC (t) = h0 cos(ωt)
with h0 = 100 mOe and ω = 32 kHz. In contrast, DC measurements
for systems with strong paramagnetic background (like studied
here Pr doped Y-123) are more challenging and require a rather
careful analysis. More precisely, the above-mentioned background
should be subtracted from the raw DC data (following the conven-
tional procedure [32]) before making any conclusions regarding
the presence (or absence) of true intrinsic superconductivity in
the analyzed samples. Notice that manifestation of this param-
agnetic signal in DC susceptibility (or magnetization) often masks

(a) Pr0.1Y0.9 Ba2Cu3O7-δ (b) Pr0.2Y0.8Ba2Cu3O7- δ

0.0 0.0

O2
-0.5
-0.1
χDC (arb. units)

χDC (arb. units)

Ar

-1.0 O2
-0.2

Ar

-1.5
-0.3
30 45 60 75 90 0 30 60 90
T(K) T(K)

(c) Pr0.3Y0.7 Ba 2Cu3O7-δ

(d) Pr0.4Y0.6Ba2Cu3O7-δ
0.00 0.0
χDC (arb. units)

χDC (arb. units)

-0.05 -0.2

-0.10 O2 -0.4 O2

Ar Ar

-0.15 -0.6
30 45 60 75 90 15 30 45 60 75 90
T(K) T(K)

Fig. 4. The temperature dependence of DC susceptibility for Prx Y1−x Ba2 Cu3 O7−ı bulk samples with x = 0.1 (a), 0.2 (b), 0.3 (c) and 0.4 (d) prepared in oxygen (O2 ) and argon
(Ar) gas atmospheres.
 C. Stari et al. / Journal of Alloys and Compounds 528 (2012) 135–140 139

(a) Pr0.6Y0.4Ba2Cu3O7-δ (b) Pr0.8Y0.2Ba2Cu3O7-δ

0.0 0.0

-0.2
χDC(arb. units)

χDC(arb. units)
-0.1

-0.4

Ar -0.2 Ar
-0.6

-0.8 -0.3
15 30 45 60 75 90 15 30 45 60 75 90
T(K) T(K)

(d) Pr1Ba2Cu3O7-δ
(c) Pr0.9Y0.1Ba2Cu3O7-δ
0.0 0.0

-0.1

-0.1
χDC(arb. units)
χDC(arb. units)

-0.2 Ar

Ar
-0.2
-0.3

-0.3 -0.4
15 30 45 60 75 90 20 40 60 80 100
T(K) T(K)

Fig. 5. The temperature dependence of DC susceptibility for Prx Y1−x Ba2 Cu3 O7−ı bulk samples with x = 0.6 (a), 0.8 (b), 0.9 (c) and 1.0 (d) prepared under argon flux treatment.

the superconducting behavior (seen via AC or transport measure-
ments) for heavily doped samples (with x > 0.6), The temperature
dependence of DC magnetic susceptibility, depicted by Figs. 4 and 5,
was determined via field-cooled experiments in applied mag-
netic field HDC = 200 Oe after subtraction of the paramagnetic
background.
The deduced from our AC and DC measurements values of
TC are shown in Table 1. As we can see, for the same Pr con-
centration, TC increases for all the samples prepared in argon
atmosphere (as compared with the samples prepared under oxy-
gen treatment), including Pr-123 system. The latter is clearly seen
in Fig. 5(d) which shows DC magnetic susceptibility measurements
for Prx Y1−x Ba2 Cu3 O7−ı samples with x = 1.0.
At the same time, according to Fig. 4(a)–(d), lightly doped sam-
ples (with 0.1 ≤ x ≤ 0.4) prepared in oxygen atmosphere exhibit
a decrease of TC with an increase of Pr concentration. These
results are in agreement with the findings based on the resistivity
measurements [33] which allows us to conclude that Pr substi-
tution (at least up to x = 0.4) into Y chain sites of YBCO leads to
quite a noticeable decrease of the bulk critical temperature TC
(due to an expected weakening of the interlayer mediated super-
conducting properties of the doped samples) without inducing an
orthorhombic–tetragonal phase transition (Cf. Table 1).
4. Conclusion
In summary, a comparative study of structural and magnetic
properties of high quality Prx Y1−x Ba2 Cu3 O7−ı polycrystalline sam-
ples prepared under different atmospheric conditions has been
presented. In particular, we found that contrary to the conven-
tional procedure based on oxygen treatment, the samples treated
under argon flux showed an increase of the critical temperature for
0 ≤ x ≤ 1. This is because argon effectively prevents the formation of
Pr6 O11 super-oxides. These results, in combination with previous
140 C. Stari et al. / Journal of Alloys and Compounds 528 (2012) 135–140
reports on Pr-123 samples, unambiguously prove the presence of
superconductivity in all members of the YPr-123 family, including
pure Pr-123.
Acknowledgments
We thank Marcel Ausloos for useful discussions. The authors
gratefully acknowledge Brazilian agencies FAPESP, CNPq and CAPES
for financial support. Cecilia Stari thanks CAPES (IEL Nacional-
Brazil) for the fellowship.
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