Solid State Ionics 308 (2017) 27–33

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Solid State Ionics

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Effect of Fe content on atomic and electronic structure of complex oxides Sr MARK

(Ti,Fe)O3 − δ
Elena O. Filatovaa,⁎, Yulia V. Egorovaa, Kristina A. Galdinaa, Tobias Scherbb,
Gerhard Schumacherb, Henny J.M. Bouwmeesterc, Stefan Baumannd
a
Institute of Physics, St-Petersburg State University, Ulyanovskaya Str. 3, Peterhof, 198504 St. Petersburg, Russia
b
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, D-14109 Berlin, Germany
c
University of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands
d
Forschungszentrum Juelich, Wilhelm-Johnen-Straße, 52425 Juelich, Germany

A B S T R A C T

We present a study of the electronic and atomic structure of two series of SrTi1 − xFexO3 − δ (STFO) powders
with different Fe content produced by two different methods, spray pyrolysis or modified Pechini synthesis, by
means of soft X-ray absorption spectroscopy. Partial substitution of Ti by Fe atoms in SrTiO3 were found to cause
asymmetric distortion of TiO6 octahedrons, which increases with increasing Fe content that may violate the
cubic symmetry of STFO. The presence mainly of Fe3 + states in octahedral environment at small concentration
of Fe atoms along with essentially smaller content of Fe4 + states in octahedral environment where the latter
contribution increases with increasing Fe content was traced. It is found that the modified Pechini method allows
to synthesize more stable structures but a tendency of the SrOx formation in the structure prepared by this
technique was marked. The spray pyrolysis method gives the structure free of SrO precipitates but the presence
of Fe3 + states in tetrahedral environment with Fe content higher than 50% and even a certain amount of Fe2 +
ions in an octahedral environment at concentrations higher than 75% in the STFO prepared by this method was
established. The O1s (K)-absorption spectra point to increase in oxygen vacancy concentration with increasing
Fe content. The lowest degree of structure distortions with enough high oxygen vacancy concentration was
traced in STFO (x = 0.25 to x = 0.35) produced by modified Pechini synthesis, which makes it mostly
appropriate for technical applications, e.g., as gas sensors, oxygen separation membranes or as fuel cell material.

1. Introduction charge compensation by appearance of oxygen vacancies, whereas in

donor-doped STO the bulk conductivity is controlled by metal vacancies
Nowadays, solid oxide fuel cell (SOFC) cathodes are almost and therefore exhibits a long-term drift behavior due to cation
exclusively fabricated using perovskite type materials [1]. For a long diffusion.
time (La,Sr)MnO3 cathodes have gained broad popularity [2]. However, Recently, strontium titanium ferrite SrTi1 − xFexO3 − δ (STFO) solid
their main drawback is related to the primarily electronic nature of solution has attracted much attention because these materials exhibit a
conductivity and high activation energy for oxygen reduction reaction p-type conducting behavior at high temperatures and may thus be
[3,4]. Among other criteria, SOFC cathode materials should reveal good applied in resistive gas sensor devices for oxygen and hydrocarbons
ionic conductivity to form a mixed conducting electrode, which can [8–11]. It can also be used as cathodes for SOFC [12] and as oxygen
provide higher electrochemical performance. One possible candidate is separation membranes [13].
perovskite of the strontium titanate (STO) group. Due to its good The SrTi1 − xFexO3 − δ sequence forms a continuous solid solution
dielectric properties, STO has been extensively studied. SrTiO3 is between the end members SrTiO3 and SrFeO3. Pure SrFeO3 − δ under-
essentially a wide band gap semiconductor with low conductivity goes an order–disorder phase transition below 850 °C from disordered
[5,6] and is stable at high temperatures. STO can be either acceptor perovskite to ordered brownmillerite (Sr2Fe2O5), which limits its
or donor doped that allows us to vary its properties for many different application [14,15]. Notice that the ionic and electronic conductivities
applications. As follows from [7] acceptor doping, e.g. partial substitu- change over several orders of magnitude by partial substitution of
tion of titanium by iron results in high oxygen conductivity due to a titanium by iron in SrTiO3. The substitution of iron by titanium in

⁎
Corresponding author.
E-mail address: [email protected] (E.O. Filatova).

http://dx.doi.org/10.1016/j.ssi.2017.05.016
Received 13 January 2017; Received in revised form 19 April 2017; Accepted 25 May 2017
Available online 30 May 2017
0167-2738/ © 2017 Elsevier B.V. All rights reserved.
E.O. Filatova et al. Solid State Ionics 308 (2017) 27–33

SrFeO3 stabilizes the disordered perovskite phase retaining a high

electronic and ionic conductivity over a wide range of oxygen partial
pressures and temperatures [15,16]. Therefore, it is necessary to find
the optimal chemical composition of SrTi1 − xFexO3 − δ solid solution
that possesses a stable cubic perovskite phase while maintaining the
high electronic and ionic conductivity. Jung and Tuller [17–19] found
that a resistivity of SrTi1 − xFexO3 − δ with x = 0.35 and 0.5 is
significantly lower than resistivity for the typical SOFC electrodes, that
certainly makes this composition very important for the structural,
atomic and electronic analysis.
The current work focuses on the changes in atomic and electronic
structure of SrTi1 − xFexO3 − δ (0.25 ≤ x ≤ 0.90%) upon Fe substitu-
tion on the transition metal site produced by two different methods,
spray pyrolysis or modified Pechini synthesis.
All the studies were carried out using near edge X-ray absorption
fine structure (NEXAFS) spectroscopy. Fine structure arising in the
vicinity of absorption edges provides information about local (asso-
ciated with a hole localization in the core shell) and partial (allowed for
certain angular momentum symmetry) electronic density of states of
the conduction band. NEXAFS is dominated by multiple scattering of
low-energy photoelectrons in the valence potential set up by the nearest
neighbours that allows us to use a spectral “fingerprint” technique to
identify the local bonding environment that defines the highest
sensitivity of NEXAFS to distinguish chemical bonds and local coordi-
nation.
Fig. 1. Ti2p (L2,3)-absorption spectra of the SrTi1 − xFexO3 − δ (STFO) with different
2. Experimental methods content of substituted Fe atoms and SrTiO3 powders. (a–b) a group of samples with x: 0.3,
0.5, 0.7 and 0.9 at of Fe on Ti site produced by spray pyrolysis method. (c–d) a group of
samples with x: 0.25, 0.35, 0.50 and 0.75 of Fe on Ti site produced by modified Pechini
SrTi1 − xFexO3 − δ powders with partial Fe substitution for Ti
synthesis. Panels (b) and (d) show the Ti 2p3/2 (L3) absorption spectra normalized on the
cations (x = 0.3, 0.5, 0.7, 0.9) were prepared by spray pyrolysis intensity of feature a. The Ti L2,3-absorption spectrum of SrTiO3 measured under the same
(Norwegian University of Science and Technology (NTNU), Norway) experimental conditions is also shown.
in a continuous air flow at 860 °C, using precursor solutions containing
stoichiometric amounts of cations. The obtained raw powders were exist in the ground state [23–27]. The empty and antibonding Ti 3d
calcined at 950 °C for 12 h in stagnant air and ball-milled in ethanol for band is split under the field of surrounding oxygen atoms into t2g (π
24 h [20]. The phase purity was checked using X-ray powder diffraction bonds) and eg (σ bonds) sub-bands.
(D2 PHASER, Bruker AXS, Germany) with Cu Kα. A continuous scan According to the classical conception, the NEXAFS excitation at the
mode was used to collect diffraction date in the range 2θ = 20–90° with Ti 2p threshold should reflect the energies of the empty Ti 3d states,
a step size of 0.02° and counting time of 1 s/step. because it is dominated by the 2p → 3d dipole transitions in the Ti
A second series of SrTi1 − xFexO3 − δ powders with x = 0.25, 0.35, atoms. One can see that the Ti 2p absorption spectra of both series
0.5. 0.75 was produced by a modified Pechini synthesis [21]. The (Fig. 1a, c) reflect clearly the spin-orbit splitting of the Ti 2p level. The
obtained raw powders were calcined at 1100 °C for 5 h in stagnant air Ti 2p1/2 (L2-feature) structures are marked by asterisks in Fig. 1(a, c).
and ball-milled in ethanol for 24 h. The NEXAFS measurements were The L2-absorption spectra are characterized by a broad structure that is
performed at the RGL-station on the Russian-German beamline (RGBL) due to an additional damping channel caused by the L2L3V-Costere-
at the BESSY II synchrotron light source of the Helmholtz-Zentrum Kronig transition [28], which reduces the life time of L2-holes. There-
Berlin [22]. The spectra were measured at the incident angle of 45° in fore, we will focus on evolution of the 2p3/2-absorption spectra. The
the vicinity of Fe L2,3, Ti L2,3 and O K-absorption edges with energy peaks a and b in the Ti 2p3/2 spectrum stem from the dipole allowed
resolution better than E/ΔE = 2000. The spectra were obtained by transitions of the Ti 2p3/2 electrons to unoccupied 3d states split into
monitoring the total electron yield (TEY) from the samples in the 3dt2g (peak a) and 3deg (peak b) components by the octahedral crystal
current mode. The absolute energy calibration was carried out by field created mainly by the oxygen ions.
measuring the energies of the reference Au 4f 7/2 photoelectron peak A joint analysis of the Ti 2p-absorption spectra for all the studied
(83.95 eV) in different diffraction orders. samples reveals that the spectra are very similar in shape and energy
position of their main features but differ in their intensity (Figure1a,c).
3. Results and discussion The intensity of all the features of the Ti 2p-absorption spectra of STFO
decreases with increasing iron content. Besides, the dependence of the
3.1. Titanium 2p X-ray absorption width of the peaks a and b (most explicitly of b) on the content of Fe
atoms is traced. Panels (b) and (d) in Fig. 1 show the Ti 2p3/2 (L3)
The Ti 2p (L2,3)-absorption spectra of SrTi1 − xFexO3 − δ (STFO) absorption spectra normalized on the intensity of feature a.
powders with different Fe/Ti ratio for both of series of STFO samples Recall that ideal cubic SrTiO3 is characterized by a structure with
are plotted in Fig. 1. The Ti L2,3-absorption spectrum of SrTiO3 undistorted and unrotated TiO6 octahedra. The violation of the cubic
measured under the same experimental conditions is also shown in symmetry due to the asymmetric distortion of TiO6 octahedra leads to
Fig. 1. modifications in shape of the absorption spectrum. Calculations, carried
The ideal cubic SrTiO3 can be considered as a structure constructed out in ref. [29], revealed that lowering of the symmetry from cubic to
from the (TiO6)8 − clusters. In a simple ionic model, Ti in SrTiO3 is tetragonal or trigonal symmetry leads to the broadening of the features
tetravalent and has no 3d electrons. The bottom of the conduction band a and b. This effect is well known in case of Ti 2p–absorption spectra of
is formed by the Ti 3d states, which are strongly mixed with the oxygen TiO2 and more expressed in the shape of feature b connected with the
states. This leads to the situation in which non-vanishing 3d electrons

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E.O. Filatova et al. Solid State Ionics 308 (2017) 27–33

double-degenerate eg component [23,30–35].

The analysis of the measured spectra of the samples of the first
group (Fig. 1b) reveals that in an orderly sequence of SrTiO3, STFO
(x = 0.3), STFO (x = 0.5), STFO (x = 0.7), STFO (x = 0.9) the full
width at half maximum (FWHM) for peak b is equal to 0.8 eV, 1.2 eV,
1.3 eV, 1.4 eV and 1.5 eV, respectively. Hence, the FWHM value for
peak b increases with increasing Fe content. The uncertainty in peak
width is about 0.05 eV, and is specified by the accuracy determining the
values of the FWHM and also by the accuracy of background subtrac-
tion for Ti L2,3-absorption spectra features. It is plausible to assume that
the observed changes in feature b originate from distortions of the TiO6
octahedra in STFO occurred during the substitution of Ti atoms by Fe.
We therefore assume that during the doping process the iron atoms Fig. 3. Fe2p (L2,3)-absorption spectra of the reference structures FeO, α-Fe2O3, Fe3O4,
SrFeO3 and SrTi1 − xFexO3 − δ with x = 0.5 (STFO50) sample produced by a modified
replace the titanium atoms, thereby inducing structural distortions.
Pechini method. The Fe L2,3-absorption spectra of FeO and SrFeO3 were taken from [36].
As to the second group of STFO samples, the same tendencies can be
traced. Additionally, it is noteworthy that the shape of Ti 2p3/2
leads to increase of the integral intensity of the L3 absorption band
absorption spectra of STFO samples with x = 0.25 and 0.35 content
while maintaining the spin-orbit splitting. Noteworthy that unlike the
of the Fe are almost indistinguishable suggesting similar local structure
spectrum of pristine structure SrFeO3, the double-peaked Fe L3 absorp-
around the Ti atoms for these two samples.
tion band is traced in all the spectra of Fe substituted STFO systems.
Moreover, the contrast of feature a relative to feature b depends also on
3.2. Iron 2p X-ray absorption the Fe content in STFO.
To understand the nature of the observed evolution of the double-
The Fe 2p (L2,3)-absorption spectra of STFO systems with a partial peaked Fe L3 absorption band let us turn to the analysis of Fe 2p
substitution of Ti by Fe atoms are presented in Fig. 2. The Fe L2,3- absorption spectra of reference systems. The spectra for iron oxides
absorption spectrum of SrFeO3 taken from ref. [36] is also shown. characterized by different coordination sites and oxidation states for
According to the classical conception, the NEXAFS excitation at the iron ions are shown in Fig. 3. The Fe 2p-absorption spectra of α-Fe2O3
Fe 2p threshold should reflect the energies of the empty Fe 3d states, and Fe3O4 powders were measured under the same experimental
because it is dominated by the 2p → 3d dipole transition in Fe atoms conditions as it was carried out for Fe substituted STFO systems. The
[37]. Fe 2p-absorption spectra of FeO and SrFeO3 were taken from [36].
One can see that all the studied Fe 2p absorption spectra clearly A joint analysis of the Fe 2p-absorption spectra for the referred
reflect the spin-orbit splitting of the Fe 2p level on Fe 2p3/2 (L3 feature) structures reveals that the shape of the Fe L3 absorption band (the
and Fe 2p1/2 (L2 feature). A joint analysis of the spectra allows to appearance of feature a) depends strongly on the oxidation state and
conclude that growth of Fe content in both groups of STFO samples coordination number of Fe atoms. The observed tendency is due to the
different correlation between the relative energy differences resulting
from the ligand-field splitting (D) and exchange splitting (J) in different
systems. The former is determined by the energy difference between the
2t2g and 3eg orbitals. The latter is due to the exchange repulsion
between the d-electrons in the pairwise configuration. Notice that due
to a large number of unpaired spins a strong exchange splitting
interaction (D < J), which splits the 3t2g and 2eg orbitals into four
separate states occurs in all the above mentioned compounds [38].
One can see that the greatest splitting of the Fe L3 absorption band
on two features a and b occurs in Fe 2p absorption spectrum of α-Fe2O3.
α-Fe2O3 has a corundum type structure (α-Al2O3) where Fe ions occupy
nearly perfect octahedral sites with formally Fe3 + oxidation state [39]
that leads to formally 3d5 electronic configuration of Fe ions, which
corresponds to a half-filled d-subshell and is particularly most stable in
high-spin configuration [40].
As opposed to Fe 2p absorption spectrum of α-Fe2O3 the presence of
unsplit Fe L3 absorption band (no splitting of the Fe L3 absorption band
into features a and b) in the spectra of FeO and SrFeO3 oxides (Fig. 3)
with the formal oxidation states Fe2 + (3d6) and Fe4 + (3d4), respec-
tively [39], is traced. Analysis of the configuration energy difference,
including the crystal field and charge transfer parameters, allowed the
authors of [39,41,42] to conclude that the observed difference is mostly
due to the change in the number of occupations of d orbitals in high
spin configuration having formally [Ar]3d5, [Ar]3d6 and [Ar]3d4
ground-state electronic configurations for ions Fe3 +, Fe2 + and Fe4 +
in α-Fe2O3, FeO, SrFeO3, respectively. As compared with α-Fe2O3, a
Fig. 2. Fe 2p (L2,3)-absorption spectra of the SrTi1 − xFexO3 − δ (STFO) samples with larger value of the configuration energy difference (4.0 eV against
different content of Fe on B-site of perovskite structure: (a–b) a first group of samples with 2.2 eV in α-Fe2O3) and a larger iron-oxygen distance is traced in FeO
x: 0.3, 0.5, 0.7 and 0.9 of Fe atoms produced by spray pyrolysis method; (c–d) a second [39] that leads to less important charge transfers in this compound and
group of samples with x: 0.25, 0.35, 0.50 and 0.75 of Fe atoms produced by a modified can be seen in the smaller weight of the ligand hole (d7L) configuration.
Pechini method. Panels (b) and (d) show the Fe 2p (L2,3)-absorption spectra normalized L denotes a hole due to a charge transfer from ligand 2p to transition-
on the intensity of the feature b. The Fe L2,3-absorption spectrum of SrFeO3 is taken from
metal 3d state.
ref. [36].

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E.O. Filatova et al. Solid State Ionics 308 (2017) 27–33

According to [42,43], large overlap between Fe 3d and O 2p states absorption spectrum of Fe3O4. This indicates that besides Fe3 + (in
exists in SrFeO3, suggesting strong hybridization between these states. octahedral Oh and tetrahedral Td coordinations) and Fe4 + (in octahe-
In stoichiometric SrFeO3 the formally tetravalent Fe4 + ions (3d4) are in dral Oh coordination) ions in STFO (x = 0.9) structure the presence of
the high spin state, and they are successfully described by a sum 3d5L Fe2 + ions in octahedral sites is most likely leading to broadening of
and 3d4 electronic configurations. The occupation of the 3d5L config- feature a in the Fe 2p absorption spectrum, accompanied by a decrease
uration is larger than that of the 3d4 configuration and as a conse- in feature a contrast regarding to feature b.
quence, SrFeO3 is in the negative charge-transfer regime. This conclu- On the basis of the carried analysis of the Fe 2p absorption spectra
sion agrees well with conclusion made in 41 that in SrFeO3 the effective of STFO compounds one can conclude that in all the studied STFO
value of negative charge-transfer energy is Δ ~ −3 eV. structures Fe ions are present predominantly in Fe3 + oxidation state in
Fe3O4 has an inverse spinel structure [44], where Fe ions are in octahedral environment along with essentially smaller content of Fe4 +
mixed oxidation state Fe2 +/Fe3 + with a ratio of 0.5. In each unit cell, states in octahedral environment. However, with growth of Fe content
the tetrahedral sites are occupied by Fe2 + ions while the octahedral in STFO (x = 0.5–0.7) the Fe4 + states in octahedral sites (Oh) and
sites are occupied by a random distribution of Fe2 + and Fe3 + ions. As Fe3 + states in tetrahedral sites (Td) occurs additionally to the main
follows from the calculations [39], the global spectrum of Fe3O4 is a state (Fe3 + states in octahedral site). Moreover, the STFO (x = 0.9)
summation of the three associated spectra. structure contains most likely Fe2 + (Oh) ions besides the Fe3 + (Td
Let us turn to Fig. 2 where the Fe 2p absorption spectra of STFO + Oh) and Fe4 + (Oh) ions.
compounds with different Fe content are shown. As mentioned above, The obtained result is in a good agreement with results reported in
the SrTi1 − xFexO3 − δ sequence forms a continuous solid solution literature [48,49] according to that Fe ions in STFO have mixture of
between end members SrTiO3 and SrFeO3. The joint analysis of the Fe3 + (Oh) and Fe4 + (Oh) states. It should be also noted that according
Fe2p-absorption spectra of all the studied STFO structures reveals to [50] the Fe ions in STFO can have a mixed Fe2 +/Fe3 + (Oh + Td)
significant differences from the Fe 2p-absorption spectrum of SrFeO3. oxidation state.
One can conclude that incorporation of Fe in SrTiO3 structure leads Concerning the second group of the STFO samples, it should be
to the formation of Fe-sites with oxidation states and coordinations emphasized that in the spectra of these samples the dependence of the
differing from SrFeO3. The evolution of the intensity and shape shape of peak a on the Fe content is almost absent. The slight
(contrast) of feature a relative to feature b also points to a change in differences in the Fe dependence of the two sets of STFO powders can
the oxidation state or coordination of Fe ions in STFO with increasing probably be assigned to the different synthesis routes of the powders.
Fe content. One can see that the most pronounced peak a exists in the Due to the different calcination temperatures applied in the two
STFO sample with the minimal Fe content (x = 0.3) (Figure2a). The synthesis routes, the concentration of oxygen in the two sets might be
contrast of feature a decreases with growth of Fe concentration with slightly different reflected in the absorption spectra of Fe.
respect to the contrast of feature b. It should be also noted that the Fe 2p-absorption spectra of STFO samples with 25% and 35% of Fe
energy distance ΔΕ between features a and b in Fe2p-absorption spectra content look like quite similar. The energy distance (ΔΕ) between
is minimal in the STFO (x = 0.9) and equals to1.38 eV that is close to features a and b in Fe 2p absorption spectra of STFO (x = 0.25) and
the ΔΕ value for Fe3O4. For all other concentrations the distance STFO (x = 0.35) samples correlates with ΔΕ for α-Fe2O3. One can
between features a and b is about 1.52 eV that correlates well with assume that for these samples the Fe3 + states in octahedral sites (Oh)
the ΔΕ value for α-Fe2O3. state is most typical. The mean oxidation state of Fe depends on
The joint analysis of feature a and ΔΕ value for STFO compounds temperature. For all STF systems, the concentration of oxygen vacancies
and reference systems reveals the following tendencies in Fe2p-absorp- is assumed to increase with increasing temperature thus enhancing the
tion spectra of the STFO samples depending on Fe content. The Fe 2p- oxygen diffusivity. Gradual rise of charge compensation by increasing
absorption spectrum of STFO (x = 0.3) is similar to that of α-Fe2O3. the concentration of Fe2 + and Fe3 + on the expense of Fe4 + (3d4) and
That means that Fe ions in the STFO with a small Fe concentration are Fe3 + (3d5L) is thus expected with increasing temperature.
preferentially in the Fe3 + oxidation state (3d5) in octahedral coordina-
tion along with essentially smaller content of Fe4 + states in octahedral 3.3. Oxygen 1s X-ray absorption
environment.
With increasing Fe content in Fe L3-absorption spectra of STFO there O1s (K)-absorption spectra of the SrTi1 − xFexO3 − δ (STFO) with
are: different content of Fe atoms are shown in Figure4. OK- absorption
1) gradual decrease in the contrast of feature a regarding to feature spectra of SrTiO3, SrFeO3 and SrO are also shown. O K-absorption
b; spectra of SrTiO3 and SrO were measured under the same experimental
2) gradual broadening of feature b; conditions. The O K-absorption spectrum of SrFeO3 was taken from
3) broadening of feature a and a slight shift of feature a maximum [42].
towards higher energies. Let us firstly discuss the formation of the OK-absorption spectrum of
The broadening of feature b in Fe L3 absorption band, which is SrTiO3. Because the SrTiO3 can be described by stacking of TiO2 and
accompanied by small shift to higher energy indicates the growth of the SrO layers, the O 1s absorption spectrum of this structure is a super-
amount of Fe4 + ions in octahedral (Oh) coordinations in STFO with position of the TiO2 and SrO spectra displaying separately each
increasing the Fe atoms content in the structure. However, the structure. The analysis of energy position of O 1s-absorption spectra
contribution of Fe4 + states, most likely, is not significant, because of TiO2 [23,30,34,51] and SrO [52] indicates that these spectra differ
the overall shape of the Fe 2p absorption spectrum, the energy position significantly from each other in the energy positions of the main
and width of the Fe L3 absorption band for all the STFO samples are spectral details that allow their separate analysis.
very different from the Fe L3 absorption spectrum of SrFeO3 (Fe4 +). O 1s-absorption spectrum of TiO2 originates mainly from O 1s-to-
According to the calculations [45,46], the broadening of feature b in valence transitions located below and above the threshold. The
the Fe L3 absorption band towards lower energies is caused by an covalent bonding of the Ti 3d with the O 2p states forms the unoccupied
appearance of Fe3 + states in tetrahedral (Td) coordinations in STFO. t2g and eg orbitals in the octahedral field. In SrTiO3 the band
In addition, in the Fe 2p absorption spectra of STFO samples with Fe corresponding to the σ bonding of Ti 3d and O 2p atomic orbitals (eg
concentration ≥ 70% there is a broadening of feature a, that indicates component) is rather broad and is reflected in the O 1s–edge absorption
the appearance of some amount of Fe2 + ions in octahedral environment spectrum as the peak b. In contrast, the weak π bonding of the Ti 3d and
[45,47]. The effect is strongly expressed in the Fe 2p-absorption the O 2p orbitals (t2g component) results in a narrow and sharp peak a.
spectrum of STFO (x = 0.9) sample which is very similar to Fe 2p According to [52] the features c, d, and e are dominated by strontium p-

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E.O. Filatova et al. Solid State Ionics 308 (2017) 27–33

ideal cubic SrTiO3 structure. Also the feature f is to some extent the
indicator of the stoichiometric structure with signs of crystallinity. The
absence of this feature points to the violation of the STO structure. One
can presume that the structure of STFO (x = 0.35) sample is most
closely matched to the perovskite cubic phase. Analysis of FeL2,3-
absorption spectra of STFO indicates that for this sample the high
content of Fe3 + (3d5 electronic configuration) ions is typical. Due to
charge compensation, a high content of Fe3 + ions provides a large
number of oxygen vacancies in the STFO structure. As oxygen diffusions
proceeds via oxygen vacancies, a high concentration of oxygen
vacancies supports diffusivity. On the other hand, a large vacancy
concentration might lead to structural instability during longer expo-
Fig. 4. O1s (K)-absorption spectra of SrTi1 − xFexO3 − δ (STFO) with different Fe content: sure at high temperatures. The composition range of 25–35% Fe where
(a) a first group of samples with x: 0.3, 0.5, 0.7 and 0.9 of Fe atoms produced by spray local distortions are small seems, therefore, to be ideal with respect to
pyrolysis method; (b) a second group of samples with x: 0.25, 0.35, 0.50 and 0.75 of Fe stability and diffusivity.
atoms produced by a modified Pechini method. OK- absorption spectra of SrTiO3, SrFeO3 Thus, it is plausible to presume that the substitution of Ti atoms in
and SrO are also shown. O K-absorption spectra of SrTiO3 and SrO were measured under
STO by 25%–35% of Fe atoms creates the optimum conditions for high
the same experimental conditions. The O K-absorption spectra of SrFeO3 was taken from
electronic and ionic conductivity in the STFO, maintaining the cubic
[42].
perovskite phase. It should be mentioned here that Schulze-Kueppers
et al. [21] found 25–35% Fe substituting Ti seems to be a good
character mixing with O 2p states and the wide f band traced in
compromise between structural and functional properties of STFO.
between 547 eV and 553 eV can be assigned to titanium 4 sp. band
A particular attention is also attracted to a high intensity narrow
mixing with O 2p states. The strontium related feature c is slightly
feature B in the O 1s-absorption spectrum of STFO (x = 0.75). A joint
overlapping with Ti 3d → eg feature. Note that in octahedral complexes
analysis of this spectrum and the spectrum of SrO showed that the
the metal eg orbitals are directed towards the oxygen atoms and have a
energy position of feature α (this feature originates from the Sr 4d–O 2p
stronger overlap with the O 2p orbitals. As a result, the O 1s-near edge
hybridization in SrO) in the spectrum of the SrO is close to the energy
structure is very sensitive to changes in the local Ti geometry.
position of feature b (eg-component) in the O 1s-absorption spectra of
As follows from Fig. 4, the O 1s-absorption spectra of STFO with Fe
STFO. Moreover, in this energy region the feature C originated from
content of 30%, 50% and 70% are similar to that of SrTiO3. With
mixed O 2p and Sr 4d states in SrFeO3 is located. One can presume that
increasing the iron content: i) the spectra in general maintain the
presence of the high intensity feature B in the O 1s-absorption spectra
number of main features and their energy position; ii) contrast of all the
of STFO (especially in the sample STFO (x = 0.75)) is associated with
features of O 1s-absorption spectra of STFO decreases; iii) an additional
the formation of a large number of SreO bonds in these compounds.
feature a′ exists in all the spectra of STFO as opposed to SrTiO3. Its
Thereby, it is plausible to assume that there are SrO precipitates in the
intensity increases with growth of Fe content. Following the established
STFO (x = 0.75) sample. The segregation of Sr-rich layers at the surface
tendencies it is reasonable to expect that the feature a′ originates from
of complex perovskites is a well-known phenomenon largely investi-
the Fe states in the structure STO. It is important that the energy
gated in the course of solid oxide fuel/electrolysis cells (SOF/EC)
position of feature a′ does not depend on Fe content in STFO.
cathodes [56]. The segregation is observed in any kind of Sr-containing
Let us shortly turn to the OK-absorption spectrum of SrFeO3 (Fig. 4).
perovskites such as (La,Sr)-manganites or -cobaltites [57] as well as
This spectrum corresponds to transitions from the O 1s to unoccupied O
strontium titanates [58,59]. Its occurrence is highly accepted and its
2p states in the conduction band. Due to strong oxygen-metal hybridi-
impact on functional properties such as catalytic activity towards
zation the first double feature A-B has a mostly metal character and
oxygen reduction is still under investigation. The exact mechanisms,
originates from bonding of O 2p states with Fe 3d states forming the
however, are not totally understood and might differ for different
unoccupied t2g and eg orbitals in the octahedral field. The rising
compositions and conditions. One can conclude that in samples
structure C-D in O 1s-absorption spectrum of SFO in the vicinity of
prepared by the modified Pechini synthesis method the tendency of
535 eV corresponds to the Sr 4d band region, and the structure E in the
the formation of SrOx is traced.
region 540–545 eV originates predominantly from the Fe 4sp states
[42]. Comparison of energy positions of feature a′ in O 1s-absorption
4. Conclusions
spectra of STFO and the feature A in the spectrum of SrFeO3 reveals a
small shift of feature a′ towards higher energies with respect to A,
Two series of SrTi1 − xFexO3 − δ (STFO) powders with different Fe
which indicates a different oxidation state of Fe ions in STFO
content produced by two different methods, solid state reaction or
compounds from SrFeO3. Such conclusion agrees well with result
modified Pechini synthesis, have been investigated by soft X-ray
obtain by analysis of Fe L2,3-absorption spectra.
absorption spectroscopy. The O 1s (K)-, Fe2p (L2,3)- and Ti2p (L2,3)-
It should be also noted that according to [30,53–55], in the pre-edge
absorption spectra of STFO powders were analyzed. Joint analysis of
region of OK-absorption spectrum of non-stoichiometric SrTiO3 there is
the Ti2p (L2,3)-absorption spectra of STFO structures testified that
a feature connected with oxygen defect states. The intensity of this
partial substitution of Ti by Fe atoms in SrTiO3 hint to asymmetric
detail depends strongly on the concentration of oxygen vacancies in
distortion of TiO6 octahedrons, which may violate the cubic symmetry
SrTiOx. The energy position of this peak coincides with position of
of STFO. It was established that the distortion of TiO6 octahedrons are
feature a′ in O 1s-absorption spectra of STFO. This means that feature a′
minimal in STFO samples with 25%–35% Fe content and increases with
reflects both the presence of Fe atoms and oxygen vacancies states in
increasing Fe content.
STFO.
Analysis of the Fe2p (L2,3)-absorption spectra reveals that the main
Let us turn to the O 1s-absorption spectra of the second group STFO.
state of Fe ions for all STFO compounds is Fe3 + in an octahedral
The main trends established for first group can be also traced here. At
environment. Besides, a part of Fe ions presence in Fe4 + state in
the same time, the O 1s-absorption spectrum of the STFO (x = 0.35)
octahedral environment, and their concertation increases with the
sample drops out from the common sequence. This spectrum is
increase of iron content. Also the joint analysis of the spectra of STFO
allocated by manifestation of its main details, especially b and e.
with reference compounds reveals that high content of Fe atoms leads
According to [30] the sharp intensive features b and e correspond to the
to appearance of Fe3 + states in a tetrahedral environment and even to a

31
E.O. Filatova et al. Solid State Ionics 308 (2017) 27–33

certain amount of Fe2 + ions in an octahedral environment. properties of SrTi1 − xFexO3 − δ (0 ≥ x ≥ 1) for the use as oxygen transport
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Russian Interdisciplinary Science Center (G-RISC) funded by the [29] F.M.F. de Groot, M.O. Figueiredo, M.J. Basto, M. Abbate, H. Petersen, J.C. Fuggle,
German Federal Foreign Office via the German Academic Exchange 2p X-ray absorption of titanium in minerals, Phys. Chem. Miner. 19 (1992)
Service (DAAD) (projects P-2013a-8, P-2014a-11). We thank HZB for 140–147.
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