M.P. Fernndez-Garcia et al.

Nanostructured materials
128 Cincia & Tecnologia dos Materiais, Vol. 24, n. 3/4, 2012
1
st
Portuguese Meeting
SYNCHROTRON RADIATION USERS _ ENURS
January 2012, CENIMAT FCT / UNL, Caparica, Portugal
SYNCHROTRON RADIATION EXPERIMENTS ON
MULTIFERROIC, MAGNETOCALORIC AND MAGNETIC
NANOSTRUCTURED MATERIALS
M.P. FERNNDEZ-GARCIA
1*
, J. AGOSTINHO MOREIRA
1
, A.M. PEREIRA
1
, G.N.P. OLIVEIRA
1,2
,
J. AZEVEDO
1
, J. OLIVEIRA
1
, M.R.CHAVES
1
, D. MOTA
1
, C.T. SOUSA
1
, J.M. TEIXEIRA
1
,
A.M.L. LOPES
2
, M.M.R COSTA
3
, J.S. AMARAL
4
, T.M. MENDONA
1
, V.A. KHONCHENKO
3
,
V.H. RODRIGUES
3
, P.B. TAVARES
5
, A. MENDES
6
, J.G. CORREIA
7
, V.S. AMARAL
4
, A. ALMEIDA
1
,
J.B. SOUSA
1
, J.P. ARAJO
1
1
IFIMUP-IN Dep. de Fsica e Astronomia, Univ. do Porto, Rua do Campo Alegre s/n, 4169-007, Porto, Portugal
2
CFNUL - Centro de Fsica Nuclear, Univ. de Lisboa, Av. Prof. Gama Pinto, 2, 1649-003, Lisboa, Portugal
3
Dep. De Fisica, Univ. de Coimbra, Rua Larga, 3004-516 Coimbra, Portugal
4
CICECO e Dep. De Fisica, Univ. de Aveiro, 3810-193 Aveiro, Portugal
5
Centro de Qumica. Univ. de Trs-os-Montes e Alto Douro. Ap. 1013, 5001-801, Vila Real, Portugal
6
LEPAE-Dep.de Engenharia Quimica, Univ. do Porto, Rua Roberto Frias, s/n, 4200-465 Porto, Portugal
7
Instituto Tecnolgico e Nuclear, E.N. 10, 2686-953 Sacavm, Portugal
*maria.garcia@fc.up.pt
1. INTRODUCTION
This article is a compendium of studies that involved syn-
chrotron radiation experiments and were developed since
2007 by researchers of Instituto de Fsica dos Materiais da
Univ. do Porto Instituto de Nanotecnologa (IFIMUP-IN)
at several synchrotrons worldwide: European Synchrotron
Radiation Facility ESRF (France), Deutsches Elektronen
Synchrotron DESY (Germany), Advanced Photon Source
APS (USA) and Elettra (Italy). IFIMUP-IN researchers and
co-workers currently employed X-ray diffraction (XRD) and
X-ray absorption (XAS) synchrotron facilities for the struc-
tural characterization of a wide range of materials: magneto-
electric rare-earth manganites (GdMnO
3
and Eu
1-x
Y
x
MnO
3
)
and CdCr
2
S
4
, magnetocaloric Tb
5
Si
2
Ge
2
compound and mag-
netic -Fe
2
O
3
nanowires materials.
Rare-earth manganites display an extremely rich interplay be-
tween charge, spin, and lattice degrees of freedom [1] yield-
ing superconductivity with the highest critical temperatures,
ferroelectricity with high dielectric response, colossal mag-
netoresistance, magnetoelectric coupling and multiferroicity.
Perovskite rare-earth manganites are likely the most versatile
materials and engaging materials due to their simple crystal
structure, which can be tuned by substitution of the A-site ion,
and their impressive physical properties. Herein we report two
synchrotron XRD studies: Firstly, one on orthorhombic Gd-
MnO
3
versus pressure up to 53 GPa; Secondly, orthorhombic
Eu
1-x
Y
x
MnO
3
, with 0x0.5, versus temperature in the range
5 K to 300 K.
Another rare-earth based material with vital importance for
technology, particularly refrigeration applications, is the
R
5
(Si,Ge)
4
system, since they exhibit a giant magnetocaloric
effect. This giant magnetic effect arises essentially from the
strong competition/coupling between spin and lattice degree of
freedom that leads to coupled magnetostructural transition [2].
One major challenge nowadays is tuning the magnetic proper-
ties and, increasing the critical temperature to values near room
temperature, through the doping with Fe. In this work we have
employed synchrotron XRD measurements (as a function of
temperature) to unveil the role played by Fe on the decoupled
ABSTRACT: Synchrotron radiation experiments have been done for the structural characterization of: magnetoelectric
manganites (GdMnO
3
and Eu
1-x
Y
x
MnO
3
), multiferroic CdCr
2
S
4
, magnetocaloric Tb
5
Si
2
Ge
2
and hematite nanowires.
Keywords: manganites, multiferroic, nanomaterials, synchrotron radiation, X-ray diffraction, X-ray absorption
Nanostructured materials M.P. Fernndez-Garcia et al.
Cincia & Tecnologia dos Materiais, Vol. 24, n. 3/4, 2012 129
low 5 mW on the Diamond Anvil Cell. The XRD experiments
were performed at ESRF. High pressure angle dispersive ex-
periments were performed on the ID27 high-pressure beam
line. XRD patterns were collected on a MAR charge cou-
pled device detector with a focused monochromatic beam at
=0.3738 . Low temperature experiments were performed at
the BM01A beamline. For each composition, a powder sam-
ple prepared with uniform grain size was enclosed in a sealed
Lindemann glass capillary and mounted on a sample holder
attached to the LHe cryostat. Diffraction data were collected
using a =0.70 from a Si(111) double crystal monochroma-
tor and a MAR345 image plate detector. The powder diffrac-
tion data were analyzed by full Rietveld refnements using the
FullProf software.
The X-ray diffraction experiments of Tb
5
Si
2
Ge
2
were per-
formed on the 11-D-C instrument =0.1066 , at the APS
(Argonne National Laboratory, USA) in the temperature
range of 10250 K [3].
The PDFs obtained of total scattering experiments were ac-
quired in the 11-IDC beam line at APS in temperature range
of 220-80 K. The Fourier transforms (Ft) and fts were calcu-
lated using PDFgetX2 and PDFft2 respectively [9].
XAS measurements at the Fe K-edge (between 6812 7969
, k = 15
-1
) in both transmission and fuorescence modes
were developed at XAFS beamline of ELETTRA synchro-
tron. Fe metal foil spectra were also recorded simultaneously
to calibrate the energy. The absorption spectra were analyzed
according to standard procedures with commercial Athena
software (IFFEFIT package).
3. RESULTS AND DISCUSION
3.1. Structural and insulator-to-metal phase transition at
50 GPa in GdMnO
3

Figure 1(a) presents Raman spectra of GdMnO
3
at room tem-
perature for pressures up to 53 GPa. Mode assignment can be
obtained from results of previously published works [10-12].
Fig. 1. Evolution of the Raman spectra (a) and Raman shifts for all bands (b)
with increasing pressure.
magnetic and structural transition of Tb
5
Si
2
Ge
2
magnetocaloric
compound. We observed that the temperature of the structural
transition increase with the Fe amount. This behaviour seems
to be directly related to the complexity of the microstructure
observed in the samples strongly infuencing the frst order
magnetostructural transition which gives rise to long-range
strain felds in the grain boundaries on the interface [3].
Additionally, the quest for improved multiferroic materials is,
nowadays, a hot topic of research with promising routes for
the development of technological applications based on the
magneto-electric coupling. In this respect, the most appeal-
ing multiferroic materials are those, which display a strong
coupling between the magnetic and polar degrees of freedom.
In this kind of compound, the answers appear to be hidden at
a nanoscale level where local network distortions fundamen-
tally infuence the ferroelectric and ferromagnetic properties.
Herein, we focus our attention to CdCr
2
S
4
compound where
local characterization seems to be the key to unlock the an-
swers that are hidden within the atomic level [4].
Photoelectrochemical cells (PEC) for water splitting into H
2

are one of the most promising ways for converting solar into
chemical energy [5]. The dissociation of H
2
O occurs at an
energy cost of 1.229 V and thus, any semiconductor used for
water splitting should possess a band gap energy over 1.23
eV. Hematite (-Fe
2
O
3
) is the only promising Fe-oxide phase
candidate for PEC applications due to its narrow band gap
(about 2.0-2.2 eV). However, the poor electron mobility of
-Fe
2
O
3
materials results into high electron-hole recombina-
tion rate and, short hole diffusion length. In order to overcome
these drawbacks, hematite nanostructuring [nanowires (NWs)
and nanotubes (NTs)] have been proven very promising [6].
However, the controlled formation of hematite is challenging
due to the wide and complex diversity of Fe-oxides. In that
sense, synchrotron radiation experiments are very helpful due
to the high resolution of XAS spectra.
2. EXPERIMENTAL METHODS.
2.1. Synthesis of materials
High-quality ceramics Eu
1-x
Y
x
MnO
3
and GdMnO
3
samples
were prepared using the sol-gel urea combustion method [7].
The Tb
5
Si
2
Ge
2
polycrystalline samples studied in this work
were synthesized by arc melting [3]. The CdCr
2
S
4
polycrystal-
line samples studied in this work were prepared by solid-state
reaction [8]. Fe NWs (35 nm of diameter, length values be-
tween 5-10 m and interpore distances of 100 nm) were elec-
trodeposited into a porous alumina template using a pulsed
electrodeposition method. The Fe NWs were then thermally
oxidized under different annealing conditions: times between
6 and 19 h; heating rates in the range 0.5 5 C/min; an-
nealing temperatures between 400 and 1000 C and, Ar or O
2
atmospheres.
2.2. Experimental details
The Raman spectra were recorded on a LabRam spectrometer
using a He-Ne laser at 633 nm. The laser power was kept be-
M.P. Fernndez-Garcia et al. Nanostructured materials
130 Cincia & Tecnologia dos Materiais, Vol. 24, n. 3/4, 2012
Full Rietveld studies of all diffraction patterns up to a pres-
sure of 45 GPa in Pnma group yield reliable fts. Details of
the refnement procedure can be found in Ref. 13. Contrarily,
no cubic centered structure can explain the pattern obtained
at higher pressure. Based on the metric a
cubic
= b
Pnma
, with a
large primitive cell with V
cubic
= 2V
Pnma
and Z=8, the best ft
was achieved for the space group P2
1
3. A factor group analy-
sis predicts 49 Raman active optical modes at the -point of
the BZ, with
optical
=10A+10E+29F. Our interpretation of the
behavior of GdMnO
3
at high pressure is that it undergoes a
structural phase transition from an orthorhombic to a cubic
symmetry, which is simultaneously a transition from an insu-
lator to a metallic phase. The metallic nature of the high-pres-
sure phase ensures the disappearance of the Raman signal.
Phase coexistence was also evidenced in the 43 47 GPa
pressure range. This is clearly seen in Fig. 4. Simultaneous
emergence of the (200) peak at 2 = 8 of the Pnma phase
and the (221) peak at 2 = 9 of the P2
1
3 phase, evidences
phase coexistence which corroborates the frst order nature of
the phase transition.
Fig. 4. XRD patterns in the 7 to 10 2 range ( = 0.3738 ), from 37 and
52 GPa.
In order to evaluate Jahn-Teller distortion, pressure behav-
iour of Mn-O
2
bond lengths was studied (see Fig. 5). Since
broadening of Bragg refections at higher pressures reduces
reliability of oxygen positions, the study was limited to low
pressure range. Mn-O
2
distances merge with increasing pres-
sure yielding a reduction of Jahn-Teller distortion.
Fig. 5 Evolution of the Mn-O
2
bond lengths under pressure.
3.2. Magneto-elastic coupling in orthorhombic
Eu
1-x
Y
x
MnO3 manganite
In the following, we report an experimental study on the
temperature dependence of the Mn-O bond lengths and Mn-
Up to 45 GPa, all of the Raman bands shift to higher frequen-
cies, as it is expected [see Fig. 1(b)], and an increase of line
width, and decrease of intensity is observed. The absence of
anomalous behavior in the pressure evolution of the Raman fre-
quencies yields no phase transition below 45 GPa [Fig. 1(b)].
The extinction of the Raman signal at 53 GPa is a clear sign for
a phase transition. This is also seen from Fig. 2, where the in-
phase O
2
stretching mode intensity decreases, vanishing above
51 GPa. The intensity recovery with decreasing pressure shows
that transition is reversible, with a pressure hysteresis of 6 GPa,
characteristic for a frst-order phase transition.
Fig. 2. Intensity of the Raman mode at initially 610 cm
-1
upon increasing and
decreasing pressure.
Two possibilities can be assumed. Firstly, a phase transition
from the Pnma to the ideal perovskite Pm-3m structure, where
the loss of the Raman spectra is explained by symmetry of the
ideal perovskite structure. Secondly, a transition from an insu-
lator to a metallic phase. Free-electron screening in the metallic
phase will be the driving force for the absence of Raman signal.
A combination of the two possibilities is also possible.
In order to decide from the three possibilities, a synchrotron
x-ray diffraction experiment up to 52 GPa was carried out.
Fig. 3 displays X-ray patterns at room temperature for differ-
ent pressures. GdMnO
3
maintains patterns of the Pnma group
up to 45 GPa. Above this pressure, a pattern with fewer Bragg
refections is obtained, yielding an increase in symmetry.
Fig. 3. Evolution of the XRD pattern with increasing pressure.
Nanostructured materials M.P. Fernndez-Garcia et al.
Cincia & Tecnologia dos Materiais, Vol. 24, n. 3/4, 2012 131
Fig. 8. Temperature dependence of Mn-O1, Mn-O21, Mn-O22 bond lengths,
and the Mn-O1-Mn bond angle of Eu
0.6
Y
0.4
MnO
3
.
In Eu
1-x
Y
x
MnO
3
, the observed MnO
6
distortions evidence the
interplay between spins and lattice, yielding a large magneto-
elastic coupling.
3.2. Tb
5
Si
2
Ge
2
magnetocaloric compound
The temperature dependence of XRD data for Tb
5
Si
2
Ge
2y
Fe
y
is
presented in Fig. 9 From this fgure, it can be observed the pres-
ence and absence of specifc Bragg refections of the M phase
at high temperatures and the O(I) phase at low temperatures.
The Rietveld refnements indicate a complete conversion of the
O(I) phase into the M phase (on heating) namely through: i)
the appearance of the (-1 3 2), (0 4 2) and (-1 4 2) refections at
2.15
o
, 2.26
o
and 2.41
o
characteristic of the M phase and, ii)
the disappearance of the (1 2 3), (1 5 1) and (2 4 1) refections
at 2.17, 2.37 and 2.47 characteristic of O(I) phase.
Fig 9. Temperature dependence X-ray synchrotron data for Tb
5
Si
2
Ge
2y
Fe
y
in
the temperature range of 93-135 K (on heating) for a) y=0, b) 0.075, c) 0.15
and d) 0.20, respectively.
An increase of the structural transition is observed in Fig.9
(bright region) reveal that Fe are somewhat increasing the
structural transition. Nevertheless, it should be noteworthy
that the increase of the Fe concentration also leads to an in-
crease of intensity of the refection at ~ 2.41 which is related
to the (2 1 1) refection of the Tb
5
(Si, Ge)
3
secondary phase
(5:3 phase; Mn
5
Si
3
-type). One found that in fact it is the pres-
ence of this secondary phase that gives rise to long-range
strain felds in the grain boundaries or on the interface be-
tween two phases providing a similar effect as external pres-
sure [3]. This is supported by the morphological data showing
the absence of Fe in the main phase responsible for the MCE.
All these conclusions were complemented by magnetization,
linear thermal expansion and neutron diffraction measure-
ments. Further information can be found in Ref. 3.
3.3. Pair distribution function (PDF) measurements on
CdCr
2
S
4
multiferroic material
Local probe studies are of great importance for acquiring in-
formation about the electronic structure and understanding
O1-Mn bond angles in orthorhombic Eu
1-x
Y
x
MnO
3
system
at low temperatures, by using synchrotron x-ray diffraction
technique. Data on the phase diagram of this system and its
unit cell can be found elsewhere [10, 14].
As it is shown in Fig. 6 to 8, temperature dependence of Mn-
O1, Mn-O21, Mn-O22 bond lengths (BLs), and Mn-O1-Mn
bond angle shows signifcant x-dependence, and anomalies
at magnetic phase transitions. Mn-O21 and Mn-O22 BLs ex-
hibit the largest temperature variations, similar for both dis-
tances and increase with x. For x = 0.2, maximum Mn-O2 BL
variation is ~0.02 (see Fig. 6), while for x = 0.4 is ~0.08
(see Fig. 8). Change of Mn-O1 BL ranges from 0.01 (for
x = 0.2) to 0.04 (for x = 0.4). T-dependence of Mn-O1,
Mn-O21 and Mn-O22 BLs shows anomalies both at TN and
T
AFM-2
. The variations observed at T
AFM-3
are consistent with
earlier results. An examination of T-dependence of Mn-O21
and Mn-O22 BLs shows that, except for x = 0.2 in the AFM-
2 phase, these two BLs behave almost oppositely. Strikingly,
the difference between Mn-O21 and Mn-O22 BLs increases
with increasing x. The larger difference between Mn-O21 and
Mn-O22 BLs occurs for x = 0.4 at T
AFM-2
.
Temperature behaviour of Mn-O1-Mn tilt angle also exhibits
strong x dependence. For x = 0.2, T-dependence of Mn-O1-
Mn bond angle (BA) decreases as temperature decreases to
T
AFM-2
, showing a clear change of slope at T
N
. Below T
AFM-2
,
Mn-O1-Mn BA increases and reaches a maximum at ~T
AFM-3
.
Unlikely, for x = 0.3, Mn-O1-Mn BA increases as tempera-
ture decreases, showing a maximum at T
AFM-2
, and changing
its slope at T
N
. For x = 0.4, a broad anomaly is observed at
T
N
. In the incommensurate magnetic phase, Mn-O1-Mn BA
decreases, reaching an almost constant value at both T
AFM-2

and T
AFM-3
. The amplitude of Mn-O1-Mn BA anomaly also
increases with x, from 5 K to 80 K, strongly varying from
1.5 for x = 0.2 up to 4 for x = 0.4.
Fig. 6. Temperature dependence of Mn-O1, Mn-O21, Mn-O22 bond lengths,
and the Mn-O1-Mn bond angle of Eu
0.8
Y
0.2
MnO
3
.
Fig. 7. Temperature dependence of Mn-O1, Mn-O21, Mn-O22 bond lengths,
and the Mn-O1-Mn bond angle of Eu
0.7
Y
0.3
MnO
3
.
M.P. Fernndez-Garcia et al. Nanostructured materials
132 Cincia & Tecnologia dos Materiais, Vol. 24, n. 3/4, 2012
3.4. Fe K-edge XAS experiments on magnetic Fe-oxide
nanowires
The synthesis of hematite NWs for PEC applications requires
a high control over the oxidation process of metallic Fe. In or-
der to optimize the oxidation process into hematite different
oxidation conditions were tested (see experimental details).
Unfortunately, the structural characterization of the synthe-
sized nanostructures in the soft X-ray region was scarce due
to the complex mixture of Fe-oxide phases [19]. In that sense,
the higher sensitivity of XAS to the bonding geometry helped
us to differentiate among Fe
+2
and Fe
+3
local environments
and nay, between - and -phases of Fe
2
O
3
(see Fe-oxide
standards XAS spectra on Fig. 11). In order to quantify the
hematite percentage, different combinations of Fe-standards
were employed. We conclude that the shape, energy position,
relative energy separation and intensity ratio of the experi-
mental XANES spectra are better reproduced when around
90% of hematite is considered.
Fig. 11. Fe K-edge XANES spectra of Fe-bcc, maghemite (-Fe
2
O
3
), magnet-
ite (Fe
3
O
4
) and hematite (-Fe
2
O
3
) measured at room temperature
4. CONCLUSIONS
In summary, synchrotron XRD and XAS are proved to be
high-accuracy methods to study specifc details of (nano)ma-
terials structure for a variety of external parameters.
In the case of GdMnO
3
, synchrotron XRD enabled to choose
between different possible interpretations suggested by oth-
er techniques and still yielding distinct details of the driv-
ing forces tailoring the transition evidenced at 50 GPa. The
signifcance of this technique for structural analysis is also
shown in the study of the critical behavior of orthorhombic
Eu
1-x
Y
x
MnO
3
system at low temperatures, where it was evi-
denced both the existence of spin-lattice coupling and a sig-
nifcant magneto-elastic effect.
Synchrotron experiments on the magnetocaloric effect were
of crucial importance to unveil the mechanism played by iron
the mechanism inherent to the macroscopic properties. Lo-
cal probe characterization of the electric feld gradient has
been made through the analysis of pair distribution function
(PDF). The PDF method can yield precise structure and size
information of atomic structure based on probability of fnd-
ing pairs of atoms in the material at distance r, given by:
!
G r ( ) = 4"r # r ( ) $ #
0
[ ]

!
G r ( ) =
2
"
Q S Q ( ) #1
[ ]
sin Qr ( )
Q
min
$
%
dQ
(1)
Where (r) is the atomic pair-density and,
0
is the average
atomic number density. G(r) is the scattering-length weight
measure of the apart obtained via Fourier transform of the
reduced total scattering structure function F(Q):
!
G r ( ) = 4"r # r ( ) $ #
0
[ ]

!
G r ( ) =
2
"
Q S Q ( ) #1
[ ]
sin Qr ( )
Q
min
$
%
dQ

(2)
Where S(Q) is the structure function obtained after the dif-
fracted intensity (corrected and normalized) from the sample
and, Q is the magnitude of the scattering vector.
The cubic spinel CdCr
2
S
4
gained recently a vivid interest,
given the relevance of relaxor-like dielectric behaviour in
its paramagnetic phase [15]. A representative experimental
PDFs results for CdCr
2
S
4
, collected at 220 K (open dots), is
depicted in Fig.10, together with the corresponding refne-
ment ft. A cubic spinel symmetry Fd3m was used as a start-
ing point for the refnement ft (line above the experimental
point) and with the difference curve (below line) with offset
for clarity [16]. For the different temperatures similar quality
fts were obtained. The lattice parameters obtained are in ac-
cordance with literature [17].
Fig. 10. The PDF results at 220 K of the spinel CdCr
2
S
4
structure.
The analysis of the temperature dependence of isotropic
atomic displacement parameter (ADPs [U
iso
]) for Cr
3+
, Cd
2+

and S
2-
site, was performed. For the refnement of the PDF
spectra a cubic model for the spinel system was employed
as a starting point. The results seem to point to a clear linear
behaviour for both Cd and S atoms. However, a different pic-
ture seems to be in place in the case of the Cr atoms. Here, a
deviation from the linear thermal contraction expected behav-
iour as predicted by a Debye or Einstein model was observed.
These observations seems to point towards a key role played
by the Cr ion on the exotic phenomenon, namely on the pecu-
liar entanglement between the polar and magnetic degrees of
freedom parallel to the relaxor-like dielectric behaviour in its
paramagnetic phase [18].
Nanostructured materials M.P. Fernndez-Garcia et al.
Cincia & Tecnologia dos Materiais, Vol. 24, n. 3/4, 2012 133
[5] Y.C. Ling, G.M. Wang, D.A. Wheeler, J.Z. Zhang, Y.
Li, Nano Letters 11(5) (2011) 2119-2125
[6] S.K.. Mohapatra, S.E. John, S. Banerjee, M. Misra,
Chem. Mat. 21(14) (2009) 3048-3055
[7] J. Agostinho Moreira, A. Almeida, W.S. Ferreira,
M.R.Chaves, J.B. Oliveira, J.M. Machado da Silva,
M.A. S, S.M.F. Vilela, and P.B. Tavares, J. Electroce-
ram. 25 (2010) 203
[8] V. Samokhvalov, I. Burlakov, M. Dietrich, F. Schnei-
der, I.M. Tiginyanu, V. Tsurkan, S. Unterricker, J. Phys.
Chem. Solids 64 (2003) 2069-2073
[9] C.L. Farrow, P. Juhas, J.W. Liu, D. Bryndin, E.S. Boin,
J. Bloch, Th. Proffen and S.J.L. Billinge J. Phys.: Con-
dens. Matter 19 (2007) 335219
[10] J. Agostinho Moreira, A. Almeida, W.S. Ferreira, J.P.
Arajo, A.M. Pereira, M.R. Chaves, M.M.R. Costa, V.A.
Khomchenko, J. Kreisel, D. Chernyshov, S.M.F. Vilela,
and P.B. Tavares, Phys. Rev. B 82 (2010) 094418
[11] M.N. Iliev, M.V. Abrashev, J. Laverdire, S. Jandl, M.
M. Gospodinov, Y.-Q. Wang, and Y.-Y. Sun, Phys. Rev.
B 73 (2006) 064302
[12] J. Laverdire, S. Jandl, A.A. Mukhin, V. Yu. Ivanov,
V.G. Ivanov, and M.N. Iliev, Phys. Rev. B 73 (2006)
214301
[13] J. Oliveira, J. Agostinho Moreira, A. Almeida, V.H.
Rodrigues, M.M.R. Costa, P.B. Tavares, P. Bouvier,
M. Guennou, and J. Kreisel, Phys. Rev. B 85 (2012)
052101
[14] J. Agostinho Moreira, A. Almeida, W.S. Ferreira, M.R.
Chaves, J.B. Oliveira, J.M. Machado da Silva, M.A. S,
S.M.F. Vilela, P.B. Tavares, Solid State Commun 151
(2011) 368
[15] V. Gnezdilov, P. Lemmens, Yu. G. Pashkevich,
P. Scheib, Ch. Payen, K.Y. Choi, J. Hemberger, A. Loidl,
V. Tsurkan, Phys. Rev. B 84 (2011) 045106
[16] T.N. Borovskaya, L.A. Butman, V.G. Tsirelson, M.A.
Poraikoshits, T.G. Aminov, R.P. Ozerov Kristallograf-
ya 36 (1991) 612-616
[17] P.K Baltzer, H.W. Lehmann, M. Robbins, Phys. Rev.
Lett. 15 (1965) 493
[18] G.N.P. Oliveira, A.M. Pereira, A.M.L. Lopes, J.S. Ama-
ral, A.M. dos Santos, Y. Ren, T.M. Mendona, C.T.
Sousa, V.S. Amaral, J.G. Correia, and J.P. Arajo, Phys.
Rev. B 86 (2012) 224418.
[19] J. Azevedo, C.T. Sousa, M.P. Fernndez-Garca,
A. Apolinrio, J. Ventura, A.M. Pereira, J.D. Costa,
A. Mendes, and J.P. Arajo, in preparation
on these materials. Namely showing that Fe catalysis the sec-
ondary 5:3 phase that is responsible for the strain felds at the
interface leading to a pressure-like effect.
Pair distribution function analysis on the CdCr
2
S
4
system,
seems to be the answer for understanding the Physics behind
the exotic behaviour that this system has been demonstrating
in the past years. The Cr deviation from the linear thermal
contraction observed, brings new information, shedding light
on the origin of the magneto-electric coupling observed, and
also demonstrating why a polarization can occur when for-
bidden by its high temperature structure.
Finally, our study on hematite nanowires reveals the unique
capabilities of XAS to study and characterize these nanostruc-
tures. The higher sensitivity of XAS vs soft XRD helped
us to differentiate among the different Fe-oxide and also
quantify them. This determination is mandatory to optimize
-Fe
2
O
3
nanostructures on photoelectrochemical cells for H
2

hydrogen production from solar energy.
ACKNOWLEGEMENTS
We are grateful to ESRF, APS, DESY and Eletra for allocating
beam-time. Particularly we thank: G. Aquilanti and L. Olivi
(Elettra) for providing assistance during our experiments. Au-
thors appreciate collaboration of W.S. Ferreira, J.M. Machado,
J.B. Oliveira, M.A. S, S.M.F. Vilela, J. Kreisel, D. Cherny-
shov, P. Bouvier, M. Guennou, C. Magen, P.A. Algarabel, Y.
Ren, C. Ritter, L. Morellon, M.R. Ibarra, Y. Ren, A.M. dos
Santos and A. Apolinrio. MPFG, JA, JMT, CTS, JSA, AMP,
and GNPO are thankful for FICYT post-doctoral POST10-
31; SFRH/BD/79207/2011; SFRH/BPD/72329/2010;
FRH/BPD/82010/2011; SFRH/BPD/61942/2009; SFRH/
BPD/63150/2009 and, SFRH/BD/80112/2011 respec-
tively. Work supported in part by project PTDC/EQU-
EQU/107990/2008. JPA thanks Fundao Gulbenkian for its
fnancial support within the Programa Gulbenkian de Estim-
ulo a Investigacao Cientifca. Funding from FCT through the
Associated Laboratory-IN is acknowledged.
REFERENCES
[1] W. Eerenstein, N.D. Mathur, and J.F. Scott, Nature 442
(2006) 759
[2] V.K. Pecharsky, K.A. Gschneidner Jr., Adv. Mat., 13
(2001) 9
[3] A.M. Pereira, A.M. dos Santos, C. Magen, J.B. Sousa,
P.A. Algarabel, Y. Ren, C. Ritter, L. Morellon, M.R.
Ibarra, and J.P. Arajo, Appl. Phys. Lett. 98 (2011)
122501
[4] T. Kimura, T. Goto, H. Shintani, K. Ishizaka, T. Arima,
Y. Tokura, Nature 426 (2003) 55-58