Novel, Oxygen-Deficient n ) 3 RP-Member Sr
3
NdFe
3
O
9-δ
and Its Topotactic Derivatives
D. Pelloquin,* J. Hadermann,
†
M. Giot, V. Caignaert, C. Michel, M. Hervieu, and
B. Raveau
Laboratoire CRISMAT-ENSICAEN, UMR6508, 6, Bd du Mare ´ chal Juin,
14050 Caen Cedex, France
Received October 15, 2003. Revised Manuscript Received February 5, 2004
The stabilization of the n ) 3 member of the Ruddlesden-Popper series has been
investigated in the Sr-Nd-Fe-O system. A new series of phases closely derived from RP-
type structures has been synthesized and characterized by X-ray diffraction and electron
microscopy. The control of the oxygen stoichiometry first allowed us to isolate a new highly
oxygen deficient, layered oxide, Sr
3
NdFe
3
O
9-δ
. The structural analysis has revealed that
this oxide crystallizes in an orthorhombic lattice (a
p
2 × a
p
2 × 28 Å), distorted with
regard to the ideal I-type symmetry of the RP-type structures. Interestingly, this oxygen-
deficient n ) 3 RP-member reacts at room temperature with ambient moisture to transform
into a hydrated oxyhydroxide, Sr
3
NdFe
3
O
7.5
(OH)
2
·H
2
O. This second phase can be dehydrated
topotactically in two steps by heating to 400 °C, leading to Sr
3
NdFe
3
O
7.5
(OH)
2
and then Sr
3
-
NdFe
3
O
8.5+δ
, respectively. The reversible character of these hydration/hydrolysis reactions
is also demonstrated.
Introduction
Titanates of the Ruddlesden and Popper series Sr
n+1
-
Ti
n
O
3n+1
1
represent the first members of a huge family
of layered oxides that are closely related to perovskite.
Starting from these compounds, whose structure is built
up from the intergrowth of a single rock salt layer [SrO]
with multiple perovskite layers [SrTiO
3
]
n
, new struc-
tural series were generated by increasing the multiplic-
ity of the rock salt layers, especially introducing Bi, Tl,
Pb, and Hg, or by creating ordered oxygen deficiency
within the multiple perovskite layers. This is exempli-
fied by the numerous high T
c
superconducting cuprates
that were discovered these last 15 years.
2-3
Interest for
the RP structure was also renewed with the discovery
of colossal magnetoresistance in the layered man-
ganites.
4-5
Several bismuth-, thallium-, and lead-based
cobaltites
6-9
and ferrites
10-16
and a chromium-based
oxide, Sr
4
Cr
2.5
O
9
,
17
derived from RP-type structures
were also isolated.
The existence of the three first members of the RP
series Sr
n+1
Fe
n
O
3n+1
,
18-20
all characterized by the pres-
ence of Fe
4+
, makes the system Sr-Fe-O very attrac-
tive for the generation of new RP phases. In such a
system, the introduction of a lanthanide on the Sr sites
or of carbonate groups in the octahedral layers leads to
the formation of Fe
3+
derivatives, as shown by the
existence of RP-type oxides in the system LaSr
3
Fe
3
-
O
10-x
,
21
with x varying from 0 to 1, and oxycarbonates
Sr
4
Fe
3-x
O
10-4x
(CO
3
)
x
.
22
We have investigated the Sr-
Nd-Fe-O system, controlling the oxygen stoichiometry
* Corresponding author. E-mail: denis.pelloquin@ismra.fr.
†
Permanent address: EMAT Laboratory, University of Antwerpen-
RUCA, Groenenborgerlaan 171, 2020 Antwerpen, Belgium.
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BATCH: cm5b07 USER: ckt69 DIV: @xyv04/data1/CLS_pj/GRP_cm/JOB_i10/DIV_cm030351n DATE: March 26, 2004
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