Physica C 470 (2010) 1073–1076

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Compare of the electronic structures of F- and Ir-doped SmFeAsO

Y. Zhang a, C.H. Cheng b, Y.L. Chen a, Y.J. Cui a, W.G. You a, H. Zhang c, Y. Zhao a,b,*
a
Key Laboratory of Advanced Technology of Materials (Ministry of Education), Superconductivity R&D Center, Southwest Jiaotong University, Chengdu 610031, China
b
School of Materials Science and Engineering, University of New South Wales, Sydney 2052, NSW, Australia
c
Department of Physics, Peking University, Beijing 100871, China

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

Article history: The electronic structures of Fe-based superconductor SmFeAsO1 xFx and SmFe1 yIryAsO are compared
Available online 31 May 2010 through X-ray photoemission spectroscopy in this study. With fluorine or iridium doping, the electronic
structure and chemical environment of the SmFeAsO system were changed. The fluorine was doped at an
Keywords: oxygen site which introduced electrons to a reservoir Sm–O layer. The iridium was doped at an Fe site
X-ray photoemission spectroscopy which introduced electrons to a conduction Fe–As layer directly. In a parent material SmFeAsO, the mag-
Electronic structure netic ordering corresponding to Fe3d in the low-spin state is suppressed by both fluorine and iridium
Fe-based superconductor
doping through suppressing the magnetism of 3d itinerant electrons. Compared to fluorine doping, irid-
SmFeAsO1 xFx
SmFe1 yIryAsO
ium doping affected superconductivity more significantly due to an iridium-induced disorder in FeAs
layers.
Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction rectly introduces electrons into the superconducting layer of the

Since the discovery of superconductivity in layered iron-based
arsenide system [1], extensive efforts have been devoted to explore
the superconductivity mechanism in the REFeAsO (RE = rear earth)
[2–5] compounds. SmFeAsO1 xFx is the first non-copper oxide
superconductor with a superconducting transition temperature,
Tc, higher than 40 K [4]. The Tc of 55 K in SmFeAsO1 xFx higher than
the theoretical value predicted from the BCS theory [6] provides a
good system to investigate the layered oxypnictide superconduc-
tivity. Chemical substitution has played a very important role in
searching new superconducting compound in the FeAs-based sys-
tem. The previous researches indicated that superconductivity in
REFeAsO system could be induced by introducing charge carriers
into the system through doping at RE–O layers. For example, super-
conductivity of SmFeAsO1 xFx is achieved by substituting fluorine
for oxygen in the Sm–O charge reservoir layer since the fluorine
substitution is donating of electrons to the SmFeAsO system [4].
Recent researches also showed that superconductivity in REFeAsO
system could be induced by introducing carriers into the SmFeAsO
system through doping electrons at Fe–As layers, for example, the
superconductivity in SmFe1 xCoxAsO [7]. It is believed that Fe–As
layer is a conduction layer which takes responsibility of supercon-
ductivity for the REFeAsO system. Therefore, doping electrons at
Fe–As layer is different from at Sm–O layer since the former di-
* Corresponding author. Address: Superconductivity R&D Center (SRDC), Mail
Stop 165, Southwest Jiaotong University, Sichuan 610031, China. Tel.: +86 28
87600786; fax: +86 28 87600787.
E-mail address: yzhao@swjtu.edu.cn (Y. Zhao).
REFeAsO system. The superconductivity transition temperature in
Co-doped REFeAsO system is not as high as the system with the
electron doping at the RE–O charge reservoir layer [7].
In order to further understand the superconductivity mecha-
nism in the system with the electron doped Fe–As layer, it is inter-
esting to study Ir-doped SmFeAsO. Since Fe and Co are 3d elements
whereas Ir is 5d element, magnetism is less common in 4d and 5d
based materials than in 3d based compounds due to the more ex-
tended d-orbital as well as the weaker Coulomb interaction. For
this reason, the compounds including Fe and Co present the ferro-
magnetic ordering while those including Ir are paramagnetic [8].
Therefore, studying Ir substitution for Fe could be helpful to under-
standing the electric structure of this new Fe-based superconduc-
tivity system. In this paper, the electronic state around the Fermi
energy, EF, and the chemical environment of the component ele-
ments were studied by X-ray photoemission spectroscopy (XPS)
for pure SmFeAsO and doped SmFeAsO with dopant at either RE–
O or Fe–As layer sites, such as fluorine doped sample SmFeAsO1 xFx
and iridium doped samples SmFe1 yIryAsO.
The fluorine and iridium substitution induces superconductivity
in SmFeAsO in our previous study [9,10]. Typical results [9,10] of
superconducting transition temperatures determined from a resis-
tance measurement of SmFeAsO1 xFx and SmFe1 yIryAsO are shown
in Table 1. The superconductivity occurs in the SmFeAsO1 xFx sam-
ples with doping level of x = 0.2 and 0.25. The superconducting tran-
sition temperature Tc is 52.5 K and 49.3 K, respectively [9]. In the
SmFe1 xIrxAsO samples, a clear superconducting transition can be
identified in the samples with doping levels of 0.05, 0.10 and 0.2,
whose onset temperatures of superconducting transition Tc were

0921-4534/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physc.2010.05.039
1074 Y. Zhang et al. / Physica C 470 (2010) 1073–1076

Table 1
Lattice parameters and Tc for SmFeAsO1 xFx and SmFe1 yIryAsO systems [9,10].

SmFeAsO1 xFx x 0 0.07 0.13 0.20 0.25

Tc (K) NS a NS a NS a 52.5 49.3
a (nm) 0.39369 0.39351 0.39335 0.39321 0.39305
c (nm) 0.85037 0.84973 0.84926 0.84870 0.84847
SmFe1 yIryAsO y 0 0.05 0.10 0.20 0.30
Tc (K) NS a 15.6 16.5 17.2 NS a
a (nm) 0.3937 0.3942 0.3946 0.3956 0.3972
c (nm) 0.8504 0.8490 0.8471 0.8424 0.8356
a
NS represents non-superconductivity.

15.6, 16.5 and 17.2 K, respectively. Similar to the cobalt doping [7],
the transition temperature in iridium doped SmFeAsO system was (a)
significantly lower than that in the SmFeAsO1 xFx, which may be SmFeAsO
600
due to a strong disordering effect induced by Ir doping at Fe–As lay-
ers. In addition, the threshold of the doping level to induce supercon- SmFeAsO0.8F0.2
ducting transition in Ir- or Co-doped SmFeAsO was smaller than that
of F-doped analog, which demonstrated that doping electrons di- 400

Intensity
rectly into the Fe–As layer was a more effective way to induce super-
conductivity in SmFeAsO. It is interesting to note that for both F- and
Ir-doped samples, the optimal doping level is 0.20. Therefore, we 200
chose SmFeAsO0.8F0.2 and SmFe0.8Ir0.2AsO as the samples for this
XPS study.
SmFe0.80Ir0.20AsO
0
2. Experiments

SmFeAsO1 xFx compounds with x = 0, 0.07, 0.13, 0.2, and 0.25 -10 0 10 20 30
were synthesized by a solid reaction method. SmAs was prepared Binding Energy (eV)
by reacting Sm pieces and As powder at 500 °C for 15 h and then
at 900 °C for 12 h in evacuated quartz tubes under vacuum. Then 120
fine, well ground powder mixtures of SmAs, Fe, Fe2O3, and FeF3 (b)
(all have purity better than 99%) were pressed into pallets and SmFeAsO
sealed into the quartz tubes in vacuum, heated at 1150 °C for
90
EF
48 h, and then quenched to room temperature [9].
The SmFe1 yIryAsO (y = 0, 0.05, 0.1, 0.2, and 0.3) samples were
Intensity

prepared by the solid-state reaction using SmAs, Fe, Ir, and Fe2O3
with high purity (P99%). SmAs was obtained by reacting Sm pieces
and As powder at 500 °C for 15 h and then 900 °C for 12 h. Well
ground powder mixtures of the raw materials were then pressed
into pallets and sealed into the quartz tubes in vacuum, and re-
acted at 1150 °C for 36 h, followed by quenching at room temper-
ature [10].
The superconducting transition temperature of the samples was
determined by four-probe resistance measurements using a phys-
ical property measurement system (Quantum-Design PPMS 9T).
The XPS data were taken on an AXIS-Ultra instrument from Kra-
tos Analytical using monochromatic Al Ka (hm = 1486.71 eV) radia-
tion (225 W, 15 mA, 15 kV) and low energy electron flooding for
charge compensation. The shift of the binding energy (BE) due to
the surface charge effect was calibrated by assuming the BE of
C1s to always be 284.8 eV. The base pressure in the spectrometer
was 3  10 9 Torr. All the XPS measurements were performed at
room temperature in order to avoid the charge effect in the insulat-
ing phase, while the samples were flooded with low energy elec-
trons to neutralize the surface charge during spectra acquisition.
3. Results and discussion
Fig. 1a and b show the XPS valence-band spectra of parent com-
pound SmFeAsO, F-optimally-doped sample SmFeAsO0.8F0.2, and Ir-
optimally-doped sample SmFe0.8Ir0.2AsO. The spectra consist of
two main bands centered at 0–15 and 15–30 eV. The peak centered
at 0–15 eV can be assigned to Fe3d (around 1 eV), Sm4f (around
7 eV), As4p (around 9.1 eV) and O2p valence band electrons
60
SmFeAsO0.8F0.2
30
SmFe0.8Ir0.2AsO
0
-2 -1 0 1 2 3
Binding Energy (eV)
Fig. 1. XPS spectra of valence band of SmFeAsO, SmFeAsO0.8F0.2, and SmFe0.8Ir0.2-
AsO samples. The spectra consisted of two main bands centered at 0–15 and
15–30 eV, and the top of the main bands of the superconductivity samples became
much flatter than that of parent compound SmFeAsO. The small peak at 0.2 eV for
SmFeAsO disappeared in both fluorine and iridium doping superconductivity
samples.
(around 7 eV). The peak centered at 15–30 eV can be assigned to
Sm5p (around 19 eV) and O2s valence band electrons (around
23 eV). The XPS valence-band spectra for SmFeAsO samples consist
of four main bands centered at about 5, 7.5, 20, and 24.5 eV, and a
small peak centered at 0.2 eV. The peak at 5 eV below the EF may
be reasonably assigned to the hybridization of Fe3d with As4p elec-
tric orbital. The 7.5 eV band structure can be due to the hybridiza-
tion of Sm4f (7 eV) with O2p (7 eV) electric orbital. The 20 eV and
24.5 eV band structure may be due to the hybridization of Sm5p3/2
and Sm5p1/2 with O2s (23 eV) electric orbital. It can be seen from
 Y. Zhang et al. / Physica C 470 (2010) 1073–1076 1075

the structure of the valence-band spectra that the FeAs layer in the
SmFeAsO crystal structure dominates the electronic properties
Fe2p
since the band associated with the hybridization of Fe3d with SmFeAsO
As4p is the nearest to the Fermi level of the system. A clear peak
position shift away from EF after fluorine and iridium doping is ob-

Intensity (arb. unit)

served at 5 eV bands in the valence-band spectra. This is due to the
facts that the BE of F2p (9.0 eV) is higher than that of O2p(7.0 eV)
and the BE of Ir5d (4.0 eV) is higher than that of Fe3d (1.0 eV). Fur- SmFeAsO0.8F0.2
thermore, the top of the main bands centered at 0–15 eV and 15–
30 eV of the superconducting samples become much flatter than
that of non-superconductivity parent compound SmFeAsO, indicat-
ing the band interactions are stronger in the superconducting sam- SmFe0.8Ir0.2AsO
ples. The top of the main bands of SmFe0.8Ir0.2AsO is much flatter
than that of SmFeAsO0.8F0.2, indicating that the former sample
has a stronger interaction than that of the latter one. This may be
attributed to the strong correlation between Ir5d electrons and
Fe3d electrons. 700 710 720 730 740
Another obvious characteristic except the peaks shift of this va- Binding Energy (eV)
lence band is the decreased intensity of these peaks after fluorine
and iridium doping. This is due to the increase of the shallow BE, Fig. 2. XPS spectra of the Fe2p core level of SmFeAsO, SmFeAsO0.8F0.2, and
which results in the ability of X-ray excited electrons decreasing. SmFe0.8Ir0.2AsO samples. It shows an almost unchanged position for the Fe2p core
The intensity of the main peaks of SmFe0.8Ir0.2AsO is much lower level after fluorine doping, but the peaks shifted towards much higher BE after
iridium doping.
than that of SmFeAsO0.8F0.2. This can be attributed to the facts that
in the SmFe0.8Ir0.2AsO sample the Fe atoms is partially substituted
by Ir atom and the atomic sensitivity factor of Ir is much higher closer radius to arsenic ion than iron ion, iridium doping may de-
than that of Fe [11], which decreases the peaks intensity. crease the crystal lattice aberrance degree and consequently nar-
One more interesting feature of the valence-band spectra for rowing the band width.
SmFeAsO is the occurrence of a small peak centered at around Fig. 3 shows the O1s core-level spectra of SmFeAsO, SmFe-
0.2 eV, which is very close to the Fermi level. Our previous study AsO0.8F0.2, and SmFe0.8Ir0.2AsO samples. It is observed that the
[12] indicated the low-spin transition produced this peak at XPS spectra of Ols are cleaved in SmFeAsO and SmFeAsO0.8F0.2 sam-
0.2 eV below the Fermi level, and deduced that the Fe3d electron ples. However, the spectra of Ols show a single and symmetric peak
spin state of SmFeAsO was mainly in the low-spin state. After fluo- for SmFe0.8Ir0.2AsO. The O1s peak in SmFeAsO and SmFeAsO0.8F0.2
rine and iridium doping, the peak at 0.2 eV disappears, indicating a samples are deconvoluted into three peaks which correspond to
change of the Fe3d states from low-spin to high-spin state. This the various oxygen-containing compounds in the samples. Accord-
may be due the decrease of the crystal-field energy gap induced ing to the Ols peak position of SmFe0.8Ir0.2AsO, it is reasonable to
by fluorine or iridium doping, which is helpful for suppressing both deduce the middle peak can be assigned to the oxygen associated
the magnetic ordering and John–Teller distortion of the structure with the Sm–O bond and the other two peaks can be assigned to
in the system, thus is in favor of superconductivity [13]. The radius the oxygen affiliated with contaminations.
of Ir ion is bigger than that of Fe ion and more close to As ion, As seen from Fig. 3, the BE positions of the middle peak are
resulting in a decrease of the FeAs tetrahedron crystal-field energy found to shift towards a higher BE with the fluorine doping. The
gap after iridium doping, and a transition from low-spin to the
high-spin state for the Fe3d electron in SmFe1 xIrxAsO.
The density of states at Fermi level, N(EF), is also depressed sig-
nificantly with fluorine and iridium doping. The decrease of the
N(EF) in SmFeAsO0.8F0.2 or SmFe0.8Ir0.2AsO reflects that the contri-
bution of the relatively localized Fe3d low-spin states to the
O1s
N(EF) decreases and the more itinerant Fe3d high-spin states dom-
inates the behavior of the system.
SmFeAsO
Intensity (arb. unit)

As shown in Fig. 2, the position related to the Fe–As band peak

shows an almost unchanged position for the Fe2p core level after
fluorine doping, which indicates that the fluorine doping position
is far away from Fe–As layer. With iridium doping the positions SmFeAsO0.8 F0.2
of the peaks are found to shift towards much higher BE, which is
about 5 eV. The chemical shift associated with the photoelectron
transitions is intimately linked with the effective atomic charge
on the atoms probed. The shift of the peak position is quite under-
standable, because the Ir atom electrons are more than Fe atom
electrons. The substitution of Ir at the Fe site leads to extra elec- SmFe0.8Ir0.2 AsO
trons introduced into the system. The increase of the electron den-
sity in the Fe–As layer may improve the screen ability of the
520 524 528 532 536 540 544
electrons to the Fe atom and consequently increase the BE of
Fe2p. Moreover, the band width decreases with iridium doping. Binding Energy (eV)
In SmFeAsO parent compound, there are two kinds Fe–As bond
Fig. 3. XPS spectra of the O1s core level of SmFeAsO, SmFeAsO0.8F0.2, and
with different length, every Fe ion with four As ions forms aber- SmFe0.8Ir0.2AsO samples. The Sm–O bond O1s peak of Ir doping sample was
rance tetrahedron conjugant, resulting in broadening bands. Be- symmetry and did not move relative to SmFeAsO, indicating that the Ir doping
cause the radius of Ir ions is bigger than that of Fe ions, with a position was far away from the Sm–O layer.
1076 Y. Zhang et al. / Physica C 470 (2010) 1073–1076
Sm3d5/2
Intensity (arb. unit)
SmFeAsO
SmFeAsO0.8F0.2
SmFe0.8Ir0.2AsO
1070 1075 1080 1085 1090 1095
Binding Energy (eV)
Fig. 4. XPS spectra of the Sm3d5/2 core level of SmFeAsO, SmFeAsO0.8F0.2, and
SmFe0.8Ir0.2AsO samples. After doping, all the peaks shifted to higher BE, which
implied that the environment of Sm atoms had been changed.
chemical shift associated with the photoelectron transitions is inti-
mately linked with the effective atomic charge on the atoms
probed. The shift in the BE position is quite understandable as
the substitution of fluorine in the oxygen site leads to the change
in the carrier concentration and so extra electrons are injected into
the system, which increases the screen ability of the O1s electrons
and results in a shift of BE of O1s with a value of 0.56 eV. As a
comparison, the O1s peaks are symmetry and do not move with
Ir doping, indicating the Sm–O bond is not affected during Ir-
doped. It is consistent with the fact that the Ir doping position is
far away from Sm–O layer and Ir doping do not affect the chemical
environment of Sm–O bands.
Fig. 4 shows the Sm3d5/2 core-level spectra of SmFeAsO, SmFe-
AsO0.8F0.2, and SmFe0.8Ir0.2AsO samples. Actually, the Sm3d photo-
emission should split into two peaks: one at around 1083 eV BE,
attributed to Sm3d5/2 lines, and the other at around 1110 eV BE,
attributed to Sm3d3/2 lines. In order to observe the changes clearly,
here only the Sm3d5/2 core-level spectra are shown. After the fluo-
rine and iridium doping, all the peaks shift to higher BE, which im-
ply that the environment of Sm atoms has been changed. For
SmFeAsO0.8F0.2 sample, this result is also in consistence with the
changes of the chemical environment of O1s mentioned above,
since fluorine occupies in the Sm–O planes in the crystal structure
of SmFeAsO0.8F0.2. Similar to the shift of O1s core level BE, the BE of
Sm3d core level also shifts towards higher energy direction with a
value of 0.54 eV, very close to 0.56 eV for the O1s core level. How-
ever, Ir doping position was far away from Sm–O layer, and Ir dop-
ing should not affect both Sm3d and O1s electrons. Why Ir doping
affect Sm3d electrons in this compound? This may be attributed to
the strong correlation between electrons, especially between d
electrons and f electrons. It is highly possible that the strong corre-
lation between Ir5d and Sm3d electrons leads to the increase of
electron density around Sm atoms, as a result, the screen ability
to the inner shell electrons increased, leading to the Sm3d BE
increased.
4. Conclusion
In this work, XPS is used to investigate the band structure fea-
tures of parent compound SmFeAsO, optimally F-doped sample
SmFeAsO0.8F0.2, and the optimally Ir-doped sample SmFe0.8Ir0.2AsO.
The valence band of parent compound SmFeAsO shows a peak at
0.2 eV below the Fermi level, which corresponds to the low-spin
state of the Fe3d electrons. In the superconducting samples with
the fluorine or iridium doping, the peak at 0.2 eV near the Fermi le-
vel disappeared, indicating a transition from the low-spin to the
high-spin state for the Fe3d electron in SmFeAsO system. The un-
changed Fe2p core levels and obvious change of O1s core levels
in F-doped samples can be attributed to the doping position that
is just at the Sm–O layer but far away from Fe–As layer. The obvi-
ous changes of Fe2p core levels and unchanged O1s core levels in
Ir-doped samples can be due to the doping position that is just in
the Fe–As layer and far away from Sm–O layer, which introduces
electrons to the Fe–As layer directly and thus enhances the screen-
ing effect of the conduction electrons of the Fe ions.
Acknowledgments
The authors are grateful for the financial support of the National
Natural Science Foundation of China under Grant Nos. 50588201
and 50872116, the National Application Research Program of China
(Program 863 under Grant No. 2007AA03Z203), the PCSIRT of the
Ministry of Education of China (IRT0751), the Specialized
Research Fund for the Doctoral Program of Higher Education
(200806130023), the Science Foundation of Southwest Jiaotong
University under Grant No. 2008B15, and the Australian Research
Council under Grant Nos. DP0559872 and DP0881739. Y. Zhang
and Y.L. Chen are also grateful for the financial support of the Inno-
vation Fund for PhD Students of Southwest Jiaotong University.
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