Solid State Sciences 4 (2002) 14131418

www.elsevier.com/locate/ssscie
Structural and transport properties of a new class of oxide ion conductors:
Nd
4
[Ga
2(1 x)
M
2x
O
7 +x

1x
]O
2
(M=Ti, Ge)
Olivier Joubert, Arnaud Magrez, Anthony Chesnaud, Maria Teresa Caldes,
Venkataraman Jayaraman, Yves Piffard

, Luc Brohan
Institut des matriaux Jean Rouxel, UMR CNRS-Universit de Nantes n
o
6502, 2, rue de la Houssinire, BP 32229, 44322 Nantes cedex 03, France
Received 15 July 2002; accepted 24 September 2002
Dedicated to Professor Neil Bartlett on the occasion of his 70th birthday
Abstract
The Nd
4
[Ga
2(1 x)
M
2x
O
7 +x

1x
]O
2
(M = Ti, Ge) compounds have been prepared by solid state reaction. Nd
4
(Ga
2
O
7
)O
2
and
Nd
4
(Ti
2
O
8
)O
2
both exhibit a cuspidine-like structure and they form a complete solid solution. Upon substituting Ge for Ga, the cuspidine
structure is maintained up to x = 0.3. Although both Ti and Ge substitutions for Ga induce a concomitant lling of oxygen vacancies,
opposite effects are observed on the oxide ion conductivity: Ti plays a detrimental role whereas the Ge improves the conductivity. A possible
interpretation is that additional oxygen atoms are trapped in the coordination polyhedron of Ti
4+
whereas they are forced to increase the
coordination number of Ga
3+
when Ge
4+
is introduced in the structure. The highest conductivity at 800

C, 0.5 10
3
S/cm, is
obtained for Nd
4
[Ga
1.8
Ge
0.2
O
7.1

0.9
]O
2
.
2002 ditions scientiques et mdicales Elsevier SAS. All rights reserved.
Keywords: Cuspidine-like phases; Oxide ion electrolytes
1. Introduction
Over the last three decades, extensive efforts have been
made worldwide to identify oxide ion electrolytes for SOFC
that could be used at moderate temperatures
(700

C). However this remains a challenge and the most

widely used oxide ion conductors are still acceptor-doped
ZrO
2
compounds, although their high operational tempera-
ture (800

C) is a major drawback.
As part of these efforts to nd suitable alternate struc-
tures which would exhibit high oxide ion conductivity, we
have recently focused on cuspidine-type compounds. Min-
erals of the cuspidine group can be described by the for-
mula M

4
(Si
2
O
7
)(O,OH,F)
2
, where M

stands for cations

in octahedral (or roughly octahedral) coordination [1]. The
structure of the prototype cuspidine compound, Ca
4
(Si
2
O
7
)-
(OH,F)
2
[2], (space group (SG) P2
1
/a with a = 10.906
, b = 10.521 , c = 7.518 and = 109.3

) can
be described as built up from ribbons of edge sharing
*
Corresponding author.
E-mail address: piffard@cnrs-imn.fr (Y. Piffard).
Ca(O,OH,F)
6
octahedra running parallel to the c axis, and
Si
2
O
7
groups (Fig. 1). Such ribbons are interconnected
Fig. 1. [100] view of the cuspidine structure (Ca
4
Si
2
O
7
(OH,F)
2
).
1293-2558/02/$ see front matter 2002 ditions scientiques et mdicales Elsevier SAS. All rights reserved.
PII: S1293- 2558( 02) 00030- 4
1414 O. Joubert et al. / Solid State Sciences 4 (2002) 14131418
by corner sharing to create an octahedral framework
to which Si
2
O
7
groups are linked via vertices. Within the
columnar arrangement of Si
2
O
7
groups along the c axis, the
inter-group SiSi distance is rather short (4.3 ), and the
empty site in between can be considered as an anion va-
cancy. Therefore, the cuspidine structure can also be viewed
as an M

4
X
8
(X = O, OH, F) octahedral framework de-
limiting channels wherein (SiOSi)
n
innite chains are
running parallel to the c axis [1], and its formula should
better be written Ca
4
(Si
2
O
7
)(OH,F)
2
. As already indi-
cated by Mamedov et al. [3], the cuspidine octahedral
framework appears also in a group of natural and synthetic
M

4
(B
2
O
6

2
)O
2
borates [46], the Si
2
O
7
group being re-
placed by two parallel BO
3
groups, leading to (BB)
n
in-
nite chains in the channels mentioned above.
Interestingly, we recently realized that the M

2
TiO
5
(M

=
La [7], Y [8], Nd [9], Eu [10]) structure also contains the
M

4
O
8
octahedral framework of the cuspidine structure,
and a more meaningful formula is therefore M

4
(Ti
2
O
8
)O
2
.
In this structure, the columnar arrangement of Si
2
O
7
or
BO
3
groups is replaced by a single chain of corner sharing
TiO
5
trigonal bipyramids, leading to (TiOTiO)
n
innite
chains. Together with cuspidine-like borates and silicates,
this family of titanates illustrates the exibility of the
cuspidine structure which can accommodate up to 20% of
anion vacancies per formula unit. This feature prompted us
to a preliminary evaluation of the potentialities of cuspidine-
like compounds as oxide ion electrolytes. In order to meet
the requirement of stability against either oxidative or
reductive atmosphere, we decided to investigate various
substitutions at the Ga site of Nd
4
(Ga
2
O
7
)O
2
, a group
member of M

4
(Ga
2
O
7
)O
2
gallates with the cuspidine
structure [11], and to analyze their inuence on the oxygen
ion conductivity of the corresponding materials.
2. Experimental
Nd
4
[Ga
2(1 x)
M
2x
O
7 +x

1x
]O
2
(M = Ti, Ge) com-
pounds were prepared by solid state reaction starting from
Nd
2
O
3
, Ga
2
O
3
, TiO
2
and GeO
2
. These reactants were
ground thoroughly in acetone and heated to 1200

C for 12 h.
The resulting products were compacted in pellets, heated in
air at 1400

C for 48 h and cooled down to roomtemperature

(RT) by switching off the furnace.
X-ray diffraction (XRD) patterns of these materials were
recorded at RT, using an INEL Position Sensitive Detector
(Cu K
1
: =1.540598 ). A very homogeneous thin layer
of powder was put on the external side of a thin Lindeman
capillary of 0.1 mm in diameter whose surface was made
sticky by means of modeling clay in order to minimize
absorption [12]. The structure renements were carried out
using the program FULLPROF [13].
Selected Area Electron Diffraction (SAED) studies were
performed on a Philips CM30 electron microscope operating
at 300 kV. EDX analyses were systematically performed
on numerous single crystals with a Link System OXFORD
analyzer.
Conductivity measurements were made with the use of
samples in the form of pellets using model 1260 High Fre-
quency Response Analyzer of M/s Solartron (Schlumberger,
UK) between RT and 800

C, in air.
Fig. 2. Projections of the cuspidine-like structures of Nd
4
(Ga
2
O
7
)O
2
along [010] and Nd
4
(Ti
2
O
8
)O
2
along [100].
O. Joubert et al. / Solid State Sciences 4 (2002) 14131418 1415
Table 1
Cell parameters of Nd
4
[Ga
2(1 x)
Ti
2x
O
7 +x

1x
]O
2
(rened as monoclinic for 0 x 0.8, see text)
x a
m
() b
m
() c
m
() (

) SG
0 7.7669(2) 10.9748(3) 11.4778(4) 109.1(1) P2
1
/c
0.1 7.7708(2) 10.9404(3) 11.5873(4) 109.9(1)
0.15 7.7694(2) 10.9177(3) 11.6118(4) 109.6(1)
a

m
() b

m
() c

m
()

)
0.3 3.8796(1) 11.0048(3) 10.8864(2) 89.94(9) P2
1
/n
0.4 3.8762(1) 11.0469(4) 10.8565(2) 89.96(8) likely
0.5 3.8751(1) 11.0965(3) 10.8502(2) 90.00(5) Pnam
0.8 3.8613(1) 11.2691(4) 10.7710(2) 90.01(4)
a
o
() b
o
() c
o
()
1 10.7325(2) 11.3525(2) 3.8465(1) Pnam
Table 2
Cell parameters of Nd
4
[Ga
2(1 x)
Ge
2x
O
7 +x

1x
]O
2
(rened as monoclinic, see text)
x a
m
() b
m
() c
m
() (

) SG
0 7.7669(2) 10.9748(3) 11.4778(4) 109.1(1) P2
1
/c
0.05 7.7713(2) 10.9608(3) 11.4901(4) 109.1(1)
a

m
() b

m
() c

m
()

)
0.1 3.8870(1) 10.9447(2) 10.8682(3) 89.56(9) P2
1
/n
0.15 3.8890(1) 10.9326(2) 10.8844(4) 89.96(8) likely
0.20 3.8892(1) 10.9203(2) 10.8825(3) 89.98(5) Pnam
0.25 3.8938(1) 10.9203(2) 10.8771(4) 90.00(4)
0.3 3.9004(1) 10.9025(2) 10.8730(4) 90.00(4)
Table 3
Nd
4
[Ga
2(1 x)
Ge
2x
O
7 +x

1x
]O
2
: selected interatomic distances
x Ga/GeGa/Ge () Ndbridging O () SG
0 3.45 (intra) 2.42, 2.59 P2
1
/c
4.33 (inter)
0.05 3.56 (intra) 2.34, 2.59
4.22 (inter) 3.11, 3.19
0.1 3.63 (intra) 2.74, 2.75
4.14 (inter) 3.01, 3.11
0.2 3.89 2.37, 2.84 Pnam
0.3 3.90 2.36, 2.85
3. Results and discussion
3.1. Structural studies
3.1.1. Nd
4
[Ga
2(1 x)
Ti
2x
O
7 +x

1 x
]O
2
(0 x 1)
compounds
Although they are both cuspidine-like compounds,
Nd
4
(Ga
2
O
7
)O
2
crystallizes in SG P2
1
/c with a
m
=
7.7669(4) , b
m
= 10.9748(6) , c
m
= 11.4778(8) and
= 109.1(3)

whereas Nd
4
(Ti
2
O
8
)O
2
crystallizes in SG
Pnam with a
o
= 10.7325(4) , b
o
= 11.3525(4) and
c
o
= 3.8465(2) . Their structures can be compared in
Fig. 2 which also illustrates the relationships between the
two cells, i.e., a
m
2c
o
, b
m
a
o
, c
m
b
o
/ sin and
90 + tan
1
c
o
/b
o
. It must be mentioned that in both struc-
tures, half of the Nd
3+
cations exhibit a seventh NdO bond
with the GaOGa and TiOTi bridging O atoms, respec-
tively.
Fig. 3. Evolution of the (

112) diffraction peak with x in the Nd

4
-
[Ga
2(1 x)
Ge
2x
O
7 +x

1x
]O
2
compounds.
For 0 x < 1 all the XRD patterns can be indexed in
a monoclinic cell similar to that of Nd
4
(Ga
2
O
7
)O
2
, thus
showing that the Nd
4
[Ga
2(1 x)
Ti
2x
O
7 +x

1x
]O
2
solid so-
lution is complete. However, for x 0.3 all reections
1416 O. Joubert et al. / Solid State Sciences 4 (2002) 14131418
Fig. 4. SAED patterns along the [001]
m
zone axis for (a) x =0.05, (b) x =0.1, and (c) along the [01

1]
o
zone axis for x =0.15.
with odd h values have completely vanished which sug-
gests a new cell twice as small along a
m
. It could arise as
a consequence of a statistical distribution of both Ga,Ti and
O, within the innite chains mentioned above, which en-
ables to describe the structure in a pseudo-orthorhombic
monoclinic cell (SG P2
1
/n) with a

m
a
m
/2, b

m
b
m
,
c

m
c
m
sin

1 (tan

)
2
and (tan

)
1
(tan)
1
+
a
m
/2c
m
sin. Upon renement of the cell parameters for
x 0.3, it appears that, within the esd,

= 90

suggest-
ing that these compounds adopt the orthorhombic structure
of Nd
4
(Ti
2
O
8
)O
2
(Table 1).
3.1.2. Nd
4
[Ga
2(1 x)
Ge
2x
O
7 +x

1 x
]O
2
(0 x 0.3)
compounds
As in the case of Ti, the substitution of Ge for Ga
increases the oxygen content, but its expected effect on
the crystal structure is of course different because Ge
4+
does not adopt the vefold coordination; Nd
2
GeO
5
[14] is a
monogermanate (i.e., its structural formula is Nd
2
O(GeO
4
)).
The cuspidine-like Nd
4
[Ga
2(1 x)
Ge
2x
O
7 +x

1x
]O
2
solid
solution is therefore limited by the capability of Ga
3+
to accept a larger coordination. An analysis of the XRD
patterns shows that this limit corresponds to x 0.3.
They can be indexed in a monoclinic cell similar to that
of Nd
4
(Ga
2
O
7
)O
2
. However for x 0.1 all reections
with odd h values have completely vanished (Fig. 3).
Consequently, for x 0.1, cell parameters corresponding to
a pseudo-orthorhombicmonoclinic cell (SGP2
1
/n) were
rened.

values reported in Table 2 show that for x =0.1

the cell remains monoclinic, whereas its symmetry is likely
orthorhombic for 0.1 <x 0.3.
In order to go further in the characterization these struc-
tural changes, SAED experiments have been undertaken on
x =0.05, 0.1 and 0.15 members.
For both x = 0.05 and 0.1, hk0 reections with odd
h values are observed on the SAED patterns along the
[001]
m
zone axis (c
m
) (Figs. 4a and 4b, respectively), thus
demonstrating that a monoclinic cell similar to that of
Nd
4
(Ga
2
O
7
)O
2
is maintained up to x =0.1, although re-
Fig. 5. SAED pattern along the [010]
o
for x =0.15 ((00l) reexions with
odd l values arise from multiple scattering).
ections with odd h values were not visible on the XRD pat-
tern corresponding to this latter composition (Fig. 3). On the
SAED pattern along the same direction for x = 0.15 (i.e.,
[01

1]
o
zone axis with respect to the orthorhombic cell), the
corresponding rows of reections are missing (as indicated
by white arrows on Fig. 4c). Note that (0k0)
m
reections
with odd k values (Figs. 4a and 4b) as well as (h00)
o
reec-
tions with h odd values arise frommultiple scattering. On the
SAED pattern along the [010]
o
zone axis (Fig. 5) weak satel-
lite reections (indicated by white arrows) are observed be-
tween h0l reections along the c
o
direction, indicating an in-
commensurate modulation of the structure. As the columnar
arrangement of [Ga
2(1 x)
Ge
2x
O
7 +x

1x
] entities is paral-
lel to this direction, this modulation is likely due to the dis-
tribution of both Ga,Ge and O, along c
o
. A comprehensive
O. Joubert et al. / Solid State Sciences 4 (2002) 14131418 1417
Fig. 6. Observed (crosses), calculated (solid line), Bragg reexions (ticks) and difference proles for Nd
4
[Ga
1.7
Ge
0.3
O
7.15

0.85
]O
2
.
analysis of this incommensurate modulation by HREM is
presently being performed and will be presented elsewhere.
A Rietveld analysis of the structure was undertaken
for several compositions (x = 0, 0.05, 0.1, 0.2 and 0.3),
although we knew (from the above SAED study) that for
x > 0.1 it would lead to an average description of the
actual structure. As can be seen in Fig. 6 for x = 0.15
as a representative example, satisfactory renements were
achieved which enable to follow the evolutions of some
specic features such as: distances between Ga/Ge sites
along a chain and NdO bond lengths corresponding to O
atoms within a chain (Table 3). In Nd
4
(Ga
2
O
7
)O
2
, the Ga
Ga distance (3.45 ) within a Ga
2
O
7
group is signicantly
shorter than inter-group distance (4.33 ). Upon substituting
Ge for Ga, oxygen atoms are introduced in the inter-group
vacancy and distances between cations tend to equalize,
which happens when the symmetry becomes orthorhombic
(x > 0.1). Meanwhile, new NdO bonds are created with
additional O atoms and in the orthorhombic structure all
Nd cations are bonded to (Ga,Ge)O(Ga,Ge) bridging O
atoms.
3.2. Conductivity measurements
Nd
4
[Ga
2(1 x)
M
2x
O
7 +x

1x
]O
2
(M = Ti, Ge) com-
pounds were subjected to conductivity measurements be-
tween RT and 800

C. The evolutions of the conductivity

at 800

C (
800
) and of the activation energy (E
a
) are dis-
played in Figs. 7 and 8, respectively. In all cases, there is
a linear evolution of the conductivity with temperature be-
tween 500 and 800

C.
For Nd
4
[Ga
2(1 x)
Ge
2x
O
7 +x

1x
]O
2
compounds, the
early stages of the substitution of Ge for Ga induce a
signicant increase of
800
which goes through a maximum
for x = 0.1. This improvement is probably mainly due to
additional O atoms which are introduced between two Ga
atoms of neighboring (Ga,Ge)
2
O
7
groups, i.e., in a rather
large cavity as long as the structure remains monoclinic
(Table 3). Asimultaneous increase of E
a
is also observed (its
maximumoccurring for x =0.15) as a possible consequence
of a more covalent framework when Ga
3+
is replaced
by Ge
4+
. However, that E
a
decreases slightly when x is
further increased 0.15 to 0.3 is rather puzzling and a better
Fig. 7. Nd
4
[Ga
2(1 x)
M
2x
O
7 +x

1x
]O
2
(M = Ti, Ge) compounds:
evolution of the conductivity vs. x at 800

C.
Fig. 8. Nd
4
[Ga
2(1 x)
M
2x
O
7 +x

1x
]O
2
(M = Ti, Ge) compounds:
evolution of the activation energy vs. x in the 500800

C range.
1418 O. Joubert et al. / Solid State Sciences 4 (2002) 14131418
knowledge of the modulated structure which appears in this
composition range will certainly be of great help in the
understanding of this evolution.
For Nd
4
[Ga
2(1 x)
Ti
2x
O
7 +x

1x
]O
2
compounds,
800
decreases signicantly upon substituting Ti for Ga, although
there is a concomitant lling of oxygen vacancies as in
the case of the Ga/Ge substitution (Fig. 7). This somewhat
unexpected effect is likely related to the clear preference of
Ti
4+
for a vefold coordination of O atoms in this structure.
As a consequence, additional oxygen atoms are trapped in
the Ti
4+
environment whereas they are forced to make a
much weaker bond with Ga
3+
when Ge
4+
is introduced.
4. Conclusion
Fromthe preliminary data reported here, we have demon-
strated that the cuspidine structure is compatible with fast
oxygen ion conduction. Thanks to its remarkable exibil-
ity (it can accommodate up to 20% of anion vacancies), it
offers many possibilities of cation substitutions. This is il-
lustrated by the Nd
4
[Ga
2(1 x)
M
2x
O
7 +x

1x
]O
2
(M=Ti,
Ge) compounds, which are cuspidine-like for 0 x 1
when M=Ti and for 0 x 0.3 when M=Ge. The high-
est conductivity at 800

C, 0.5 10
3
S/cm, obtained
for Nd
4
[Ga
1.8
Ge
0.2
O
7.1

0.9
]O
2
is promising and prompts us
to investigate cuspidine-like materials further.
Acknowledgements
VJ
1
gratefully acknowledges nancial support of the
Rgion des Pays de la Loire in the form of a post doctoral
fellowship for eleven months.
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1
Present address: Materials Chemistry Division, Indira Gandhi Centre
for Atomic Research, Kalpakkam 603 102, India.