Local structure and polarization resistance of Ce doped SrMnO3 using extended x-ray

fine structure analysis

Jiseung Ryu and Heesoo Lee

Citation: Applied Physics Letters 105, 111903 (2014); doi: 10.1063/1.4896107

View online: http://dx.doi.org/10.1063/1.4896107
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 APPLIED PHYSICS LETTERS 105, 111903 (2014)

Local structure and polarization resistance of Ce doped SrMnO3 using

extended x-ray fine structure analysis
Jiseung Ryu and Heesoo Leea)
School of Materials Science and Engineering, Pusan National University, Busan 609-735, South Korea
(Received 27 June 2014; accepted 29 August 2014; published online 17 September 2014)
Changes to the local structure of Sr and Mn atoms in Sr1xCexMnO3 (SCM) according to
increasing Ce content and the effect of the structural change on the polarization resistance of SCM
were investigated. The reduction of manganese was confirmed by the absorption edge shift of the
Mn K-edge toward lower energies. The noise of oscillation in extended X-ray absorption fine struc-
ture k3v data at Mn K-edge reveals the distortion of the local structure of Mn atoms, and the peak
that indicates the bonding length of Mn-O, Sr/Ce, and -Mn decreased with the addition of Ce con-
tent in Fourier transformations of the Mn K-edge. The distortion of the local structure at Mn atoms
was affected by the reduced manganese ions having larger ionic radii than Mn4þ. Meanwhile, few
distortions of local atomic structures of Sr atoms occurred, and the average nearest neighboring dis-
tances of Sr-O and Sr-Mn are 2.13 Å and 2.95 Å, respectively. The average bonding lengths of
the Ce-O and Ce-Mn increased because the ionic radius of substituted Ce ion with 12 coordination
number is smaller than that of Sr ion, which leads the reduction of Mn ions and the distortion of
local structure at the substituted A-site. Therefore, we reasoned that the distortion of the local
atomic structure at Mn atoms in MnO6 and Ce atoms in A-site is one of the causes for interrupting
oxygen ion transfers as a geometric factor, which results in an increase in the polarization resist-
ance of SCM within the Ce composition range from 10 mol. % to 30 mol. %. V C 2014
AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4896107]

Cerium-doped SrMnO3 (SCM) with a perovskite struc- Sr, Ce, and Mn cations within SCM system with different Ce
ture has received attention as a cathode material for interme- content using X-ray absorption near edge structure (XANES)
diate temperature solid oxide fuel cells (IT-SOFCs), due to and EXAFS analysis, and investigate the effect of a change
its high electrical conductivity and similar thermal expansion of the local structure on the polarization resistance of SCM.
coefficients with CeO2 based electrolytes.1,2 Substituting Ce Sr1xCexMnO3 powders (SCM, x ¼ 0.1, 0.2, and 0.3)
for Sr affects the stability of perovskite structures and were synthesized by the ethylendiaminetetraacetic (EDTA)
increases charge carriers, but decreases overall oxygen ion citrate complexing process using nitrate solutions that con-
conductivity.3 tained Sr, Ce, and Mn acetate; the detailed procedure for
In the previous study of the effects of Ce doping on synthesis process was given in a preceding paper.3
polarization resistance using O K-edge near edge X-ray X-ray absorption spectroscopy (XAS) experiments were
adsorption fine structure (NEXAFS) analysis, strong hybrid- performed at the Sr K-edge, Ce L3-edge, and Mn K-edge
ization between unoccupied Ce 4f and/or 5d and O 2p orbi- using the EXAFS facility installed at the 7D beam line in the
tals can suppress the formation of oxygen vacancies, which Pohang Accelerator Laboratory (PAL, Korea). The storage
contributes to an increase in polarization resistance.4 ring operated at 2.5 GeV with an injection current of
Meanwhile, it is reported that Mn3þ ions that are formed by 200 mA. All the samples were ground to a fine powder in a
Ce doping in SCM systems change the entire crystal and mortar and then were packed into a 0.5 mm thick cell. The
MnO6 octahedral structures.5–7 Because this change to the XAS data of Sr/Mn K-edge and Ce L3-edge were collected at
crystal structures can geometrically affect the conductivity room temperature in transmission mode and fluorescence
properties of materials, an investigation of conductivity mode, respectively, using Ar/He gas-ionization detectors. In
properties in terms of crystal structure change is also neces- order to accurately retrieve the XANES spectra, data were
sary. For this investigation, we can understand the cause for recorded at a step size of 0.2 eV in the edge region, where a
the change of polarization resistance (shown in Table I) Si (1 1 1) double crystal monochromator was employed.
through the analysis of changes in local atomic structures Each value of spectral energy was calibrated by using Mn
that occur when Ce atoms are substituted for Sr atoms. The foil as a reference.
investigation of the mechanism, which is for oxygen ion con-
duction is low with an increase in Ce content, will be used to
TABLE I. Denotation and polarization resistance of Sr1xCexMnO3 cathode
design of better SrMnO3 based cathode materials. materials measured at 800  C.3
Extended X-ray absorption fine structure (EXAFS) anal-
ysis can directly probe local atomic structure around a meas- Composition x ¼ 0.1 x ¼ 0.2 x ¼ 0.3
ured atom.8,9 As a result, we examine the local structure of Denotation SCM10 SCM20 SCM30

Polarization resistance (X cm2) 6.26(8) 13.97(4) 16.42(6)

a)
Email: heesoo@pusan.ac.kr. Tel.: þ82-51-510-2388

0003-6951/2014/105(11)/111903/4/$30.00 105, 111903-1 C 2014 AIP Publishing LLC

V

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 111903-2 J. Ryu and H. Lee Appl. Phys. Lett. 105, 111903 (2014)

FIG. 1. Normalized Mn K-edge X-ray absorption near edge structure spectra

of SCM powders and its inset figure depict the magnified view of the edge
region.

Figure 1 shows the whole Mn K-edge XANES spectra

and pre-edge region of SCM powder to investigate the way,
in which the Mn valence state is affected by the addition of
Ce content. The whole shapes of Mn K-edge for SCM sam-
ples originate from dipole transitions of the Mn 1s core elec-
trons into the unoccupied Mn 4p orbitals. All of these
spectra are similar to each other, which is as expected for
compounds with a similar perovskite structure in Fig. 1(a),
which means they are similar mixed-valence manganites.10 FIG. 2. (a) EXAFS k3v data and (b) Fourier transform of the EXAFS k3v
data at Mn K-edge of Ce-doped SrMnO3 powders at room temperature (k
The absorption edge of SCM shifts to a lower energy region range from 2 to 12.5 Å1).
as the Ce content increases (inset, Fig. 1). It is well known
that, for manganite, the position of the absorption edge can The average nearest neighbor distances of the Mn-Sr/Ce and
be correlated with the valence state of Mn ions.11–13 The the Mn-Mn bonding are 2.91 Å and 3.41 Å, respectively.
edge shift toward lower energy presents a decrease in the va- Among the three indicated peaks, the Mn-Sr/Ce peak has
lence state of Mn ions, which is a reduction of Mn ions. As a more amplitude change between compositions than that of
result, the substitution of Ce3þ and/or Ce4þ ions for Sr2þ the other two peaks, because the Mn-Ce distance has
ions can cause a reduction from Mn4þ ions to Mn3þ (and/or increased with the substitution of Ce ions having smaller
Mn2þ) ions to adjust charge neutralities in SCM systems. ionic radius. With an increase in the Ce content, the intensity
Figures 2(a) and 2(b) display the EXAFS k3v data and of Mn-Sr/Ce and Mn-Mn has also decreased, similar to the
Fourier transformation (FT) of the Mn K-edge, respectively, Mn-O bonding intensity. Hence, the substituted Ce ions for
which describes the local atomic structure at the Mn atoms. Sr ions can incur the structural distortion, and its behavior
It is well known that the crystal structure of doped-ABO3 follows the hypothesis associated with the lattice distortion
type perovskite undergoes Jahn-Teller (JT) distortion of in our previous study of Ce-doped SrMnO3.
MnO6 octahedra. Kumar et al. reported that the reduced Oxygen vacancy provides a diffusion path for oxygen
symmetry by distortion generates an oscillation noise in the ions in oxides, and the oxygen vacancies in MnO6 octahedral
EXAFS k3v data.14 The EXAFS k3v data of the Mn K-edge structure of perovskite plays a role of the pathways for oxy-
for SCM shows a severe noise, which indicates that the SCM gen ions.16 Oxygen ion transfers are affected by lattice dis-
system has structural distortion in the lattice. tortion, which impedes the movement of oxygen vacancies.
The FT shown in Fig. 2(b) provides information on the We suppose that the distortion of the MnO6 structure in Ce-
average bonding length between Mn atoms and the surround- doped SrMnO3 as a geometrical factor impedes the diffusion
ing atoms of the Mn atoms. The amplitude of the Mn-O process of oxygen vacancies, which is a reason for the
peak, related to the first oxygen coordination shell, decreases increase in the polarization resistance of SCM with the addi-
with an increase in Ce content. The increase in the amplitude tion of Ce atoms.
of R-space indicates a reduction in the local atomic distortion EXAFS k3v data at the Sr K-edge shown in Fig. 3(a)
of the MnO6 octahedral structure in Ca-doped LaMnO3.15 In presents less oscillation noise than that of the Mn K-edge,
the case of an SCM system, the intensity of R-space was which indicates that less distortion of the local atomic struc-
decreased by increasing Ce content, which reveals an ture around Sr ion occurs than around Mn ions. The Sr-O
increase in the local atomic distortion of the MnO6 structure. and the Sr-Mn distances are 2.05 Å and 2.79 Å,
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 111903-3 J. Ryu and H. Lee Appl. Phys. Lett. 105, 111903 (2014)

FIG. 3. (a) EXAFS k3v data and (b) Fourier transform of the EXAFS k3v
data at Sr K-edge of Ce-doped SrMnO3 powders at room temperature (k FIG. 4. (a) EXAFS k3v data, (b) Fourier transform of the EXAFS k3v data,
range from 3 to 10 Å1). and (c) X-ray absorption near edge structure of Ce L3-edge for Ce-doped
SrMnO3 powders at room temperature (k range from 0.5 to 6 Å1).

respectively. The Sr-Mn bonding length corresponds to the The Ce-O and the Ce-Mn distance of SCM system are
Mn-Sr bonding length shown in Fig. 2(b). The peak intensity 2.15 Å and 3.05 Å, respectively. They indicate longer
that indicates the Sr-O bonding length decreases with distance than Sr-O and Sr-Mn distance shown in Fig. 3. It is
increasing Ce content, and is affected by not only the distor- the reason that the increase in the average nearest neighbor
tion of Sr-O local structure but also a decrease in Sr-O bond- distance of Ce-O and Ce-Mn is attributed by substituting Ce
ing according to an increase in Ce atoms at the Sr-site. ions for Sr ions (1.44 Å) because the ionic radii of Ce3þ
EXAFS k3v data and Fourier transform based on (1.34 Å) and Ce4þ (1.14 Å) ions with 12 coordination num-
EXAFS analysis of the Ce L3-edge of SCM system was con- ber,18 which is also one of the cause for changing of the local
ducted and shown in Fig. 4 and the XANES data are also atomic structure at A-site.
presented in inset of Fig. 4(b). EXAFS k3v data of SCM Changes to the local atomic structure of Sr, Ce, and Mn
specimens (Fig. 4(a)) present the large noise due to the weak atoms in Ce-doped SCM according to increasing Ce content
energy of the Ce L3-edge and the low doping level, and and the effects of structural changes on the polarization resist-
therefore, the EXAFS analysis of L3-edge of SCM specimen ance of SCM were investigated. The absorption edge of Mn K-
gives limit information in this study. Especially, Ce L3-edge edge shifted to lower energies with increasing Ce content,
of SCM10 presents much noise than other samples because which means an increase in mixed-valence state with Mn4þ
SCM10 has much low doping level, which is most pro- and Mn3þ (and/or Mn2þ). A decrease in the peak intensity of
nounced on the spectra with significant noise. Fourier transformation of the EXAFS k3v data at Mn K-edge
There are two peaks in the XANES spectra obtained at reveals the distortion of local structures for the Mn-O and the
the Ce L3-edge. A double white line (WL) characteristic Mn-Sr/Ce bonds. The distortion of the local structure of Mn
peak reveals a mixture of the two Ce ground-state electronic atoms occurred as a geometrical factor, through the reduction
configuration, Ce3þ–4f1 and Ce4þ–4f 0.17 The XANES spec- of manganese, and impedes the transfer of oxygen ions.
tra of Ce L3-edge (inset, Fig. 4(b)) indicate the presence of a Meanwhile, few distortions of local structures of Sr atoms
bimodal WL feature and a strong high energy shift of the occurred, and the distances of Sr-O and Sr-Mn are 2.13 Å
edge from the E0 (5723 eV) of Ce L3-edge, which supports and 2.95 Å, respectively. Substituted Ce ions were a mixed
the mixed state of Ce3þ (peak A) and Ce4þ (peak B) state in state of Ce3þ and Ce4þ, and the distances of the Ce-O and Ce-
this system. Mn increased because the ionic radii of substituted Ce ion is
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 111903-4 J. Ryu and H. Lee Appl. Phys. Lett. 105, 111903 (2014)

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