ARTICLE

pubs.acs.org/IC

Phase Transitions of AlFeO3 and GaFeO3 from the Chiral Orthorhombic

(Pna21) Structure to the Rhombohedral (R3c) Structure
Rana Saha, Ajmala Shireen, Sharmila N. Shirodkar, Mukta Shashi Singh, Umesh V. Waghmare,
A. Sundaresan, and C. N. R. Rao*
Chemistry and Physics of Materials Unit, New Chemistry Unit, Theoretical Science Unit and International Centre for Materials Science,
Jawaharlal Nehru Centre for Advanced Scientic Research, Jakkur, Bangalore 560064, India

ABSTRACT: AlFeO3 and GaFeO3, which crystallize in a chiral

orthorhombic (Pna21) structure, transform to a rhombohedral
(R3c) structure when subjected to ball-milling. There is a
distinct dierence between the transformations of AlFeO3
and GaFeO3. AlFeO3 rst transforms to an orthorhombic
P212121 structure followed by its transformation to the R3c
structure, while GaFeO3 goes directly to the R3c structure. The
transformations have been characterized by X-ray diraction
and Raman spectroscopy. Magnetic properties of Pna21 and the
transformed phases show signicant dierences. It is note-
worthy that partial substitution of aluminum by gallium in AlFeO3 as in Al0.5Ga0.5FeO3 eliminates the intermediate P212121
phase, causing direct transformation of the Pna21 structure to the R3c structure. All of the transformations are thermodynamically
rst-order associated with signicant changes in volume. We have used rst-principles simulations to determine the pressure-
dependent properties of AlFeO3 and GaFeO3 in orthorhombic and corundum structures and have estimated the critical pressures
for the structural phase transition between the two structures. On the basis of this information, we also comment on the dierences
in the behavior of AlFeO3 and GaFeO3 under ball-milling.

INTRODUCTION nature of the transformation. Besides characterizing the phase

AlFeO3 and GaFeO3 are members of a family of oxides with transitions by X-ray diraction (XRD) and Raman spectroscopy,
interesting dielectric and magnetic properties.1 3 Interestingly, we have studied the magnetic properties of the dierent phases.
AlFeO3 and GaFeO3 crystallize in the chiral orthorhombic We have also carried out rst-principles calculations to under-
structure (Pna21),4 although the component oxides possess stand the nature of the phase transitions.
dierent structures. Both R-Al2O3 and R-Fe2O3 crystallize in
the rhombohedral structure (R3c), while -Ga2O3 has a mono-
EXPERIMENTAL SECTION
clinic structure (C2/m). GaFeO3 has been reported to be
piezoelectric and ferromagnetic.5 It has been shown recently AlFeO3, GaFeO3, and Al0.5Ga0.5FeO3 were prepared by the copreci-
that members of the Al1 xGaxFeO3 family exhibit signicant pitation method or solid-state reaction starting with stoichiometric
magnetodielectric eects.6,7 There has been some interest in amounts of R-Fe2O3 (Aldrich, 99.98%), R-Al2O3 (Alfa-Aesar, 99.99%),
investigating the phase transitions of these oxides. Studies of and -Ga2O3 (Aldrich, 99.99%). Fe2O3 and Al(Ga2O3) powders were
AlFeO3 and GaFeO3 at high pressures and high temperatures dissolved separately in concentrated HCl to form the chlorides; the
seem to indicate the occurrence of decomposition, while there metal chloride solutions were mixed and stirred for 0.5 h, after which a
are also reports of a transition to the perovskite phase at high NH4OH solution was added dropwise with continuous stirring until
precipitation. The precipitate was ltered, washed with distilled water to
pressure.8,9 The studies of Nagai et al.,10 although not entirely
remove residual ammonium chloride salt until neutral pH was attained,
clear, seem to suggest that the structure of AlFeO3 transforms to
and dried at 80 C in an air oven for 24 h. The dried precipitates were
another form of the orthorhombic structure at high pressures and heated at 1350 C for 2 h in air with a heating rate of 3 C/min. These
comes back to the trigonal phase upon release of the pressure. compounds were also made by conventional solid-state reactions where
We were interested in exploring the phase transitions of AlFeO3 in mixtures of the component oxides were heated at 1400 C with
and GaFeO3 because of their unique structures and properties, repeated grinding, pelletizing, and heating. These oxides were subjected
especially to nd out whether the chiral orthorhombic structures to ball-milling using a planetary monomill (Fritsch Pulverisette-6, Berlin,
of these oxides transform to other structures when subjected to Germany). A batch of 2 g of each sample was taken separately in a 80 mL
grinding or ball-milling. To our surprise, we nd that ball-milling capacity agate (99.9% SiO2) bowl containing 10 15 agate balls of 10 mm
transforms these oxides from the chiral orthorhombic structure
(Pna21) to the rhombohedral structure (R3c), with signicant Received: June 9, 2011
dierences between AlFeO3 and GaFeO3 with regard to the Published: August 26, 2011

r 2011 American Chemical Society 9527 dx.doi.org/10.1021/ic201235h | Inorg. Chem. 2011, 50, 95279532
Inorganic Chemistry ARTICLE

Figure 1. XRD patterns of (a) the orthorhombic AlFeO3 sample, (b)

ball-milled AlFeO3 (12 h), (c) 12 h ball-milled AlFeO3 annealed at
700 C, (d) a mixture of R-Fe2O3 + R-Al2O3 (1:1), (e) ball-milled
AlFeO3 (24 h), and (f) 24 h ball-milled AlFeO3 annealed at 1350 C,
with the Pna21 space group.

diameter. Ball-milling was carried out without any additives (dry ball-
milling) at a speed of 400 rpm for 12 24 h. The ambient temperature
during ball-milling was around 400 C. It is important to note that no
contamination was found in the ball-milled samples from the ball-milled
vessel. The ball-milled samples were subjected to various methods of
characterization. They were also annealed in air at 700 C, and the annealed
samples were characterized similarly. The annealed samples were also Figure 2. XRD patterns of ball-milled AlFeO3 in (a) the -Al2O3
heated to 1000 1350 C in air for a period of 24 h. structure (P212121) and (b) the R3c structure along with prole ts,
XRD patterns of the powdered samples were recorded with a Bruker D8 dierence patterns, and Bragg positions.
Advance X-ray diractometer to conrm the phase purities of these oxides.
The software package Fullprof was used to analyze the structural data. RESULTS AND DISCUSSION
Raman spectra of powdered samples were recorded at room temperature AlFeO3 samples, subjected to ball milling at 300 K for a period
with a LabRAM HR 800 high-resolution Raman spectrometer (Horiba- of 12 h, were investigated by XRD and Raman spectroscopy. The
Jobin Yvon) using a He Ne laser ( = 632.8 nm). Magnetic properties of XRD patterns of the starting material and of the ball-milled
the samples were measured using a vibrating sample magnetometer in the
sample are shown in parts a and b of Figure 1, respectively. The
Physical Property Measurement System (PPMS) under zero-eld-cooled
ball-milled sample shows line broadening, and the crystallite size
(ZFC) and eld-cooled (FC) conditions in the temperature range of
5 390 K under a magnetic eld of 100 Oe. Magnetic hysteresis curves were
calculated from the line width is 20 nm. Annealing the ball-
recorded at 5 K in magnetic elds going up to 60 kOe. milled sample at 700 C showed no changes in the positions of
We have carried out rst-principles calculations to examine the the reections, as can be seen from Figure 1c. The XRD pattern
pressure dependence of the Pna21 and R3c structures of AlFeO3 and of the ball-milled AlFeO3 does not match that of R-Fe2O3.
GaFeO3. The calculations are based on density functional theory (DFT) Furthermore, a 1:1 mixture of R-Fe2O3 and R-Al2O3 exhibits a
with a spin-density-dependent exchange correlation energy functional of XRD pattern (Figure 1d) that is completely dierent from that of
a generalized gradient approximation [Perdew Wang 91 (PW 91)] ball-milled AlFeO3. Prole tting using the Fullprof package
form11 as implemented in the Vienna Ab initio Simulation Package.12,13 (Figure 2a) showed that the structure of ball-milled AlFeO3 was
The projector augmented wave method14 is used to capture the akin to -Al2O3 with the P212121 space group.15 The lattice
interaction between ionic cores and valence electrons. An energy cuto parameters of this P212121 were found to be a = 15.886 (11) ,
of 400 eV was used for the plane-wave basis, and integrations over the b = 11.408 (6) , and c = 7.803 (4) . The -Al2O3 phase is
Brillouin were sampled upon using a regular 4  2  2 mesh of k points related to the spinel structure and is dierent from that of
for the orthorhombic structure and a 3  3  2 mesh for the corundum
*-Al2O3 (P222)16 with lattice parameters a = 7.936 , b = 7.956
structure. The pressure dependence of these structures was studied by
homogeneously deforming the unit cell by up to (2% isotropic strain
, and c = 11.711 reported by Fargeot et al.16 It is, however,
and obtaining the corresponding pressure from the stress tensor dicult to dierentiate the P222 and P212121 structures based on
calculated as a derivative of the energy with respect to strain. To prole tting. It is possible that the * phase of Fargeot et al.16 is
determine the critical pressure, we dene an enthalpy H = E(V) + PV, actually the phase described by Levin and Brandon.15
where E(V) is the total energy function of a parabolic form tted to In order to examine whether ball-milling for extended periods
energies obtained in the DFT calculations and V is the volume of the unit gives rise to other structures, we ball-milled AlFeO3 for 24 h at
cell. For a given pressure, the equilibrium volume is obtained by 300 K. The XRD pattern of this sample (Figure 1e) is similar to
minimizing H with respect to V. The critical pressure is the pressure that of R-Fe2O3 (R3c). The lattice parameters of the rhombohe-
at which the minimum enthalpies of the two structures cross, which also dral AlFeO3 are a = 4.909(2) and c = 13.393(7) , as obtained
relates to the slope of a common tangent to the energy volume curves from prole tting (Figure 2b). Note that the lattice parameters
of two structures. of R-Fe2O3 are a = 5.032 and c = 13.733 , while those of
9528 dx.doi.org/10.1021/ic201235h |Inorg. Chem. 2011, 50, 95279532
Inorganic Chemistry ARTICLE

Figure 5. XRD patterns of (a) the orthorhombic GaFeO3 sample, (b)

GaFeO3 nanoparticles by the sol gel route, (c) ball-milled GaFeO3, (d)
Figure 3. Raman spectra of (a) the orthorhombic AlFeO3 sample, (b) ball-milled GaFeO3 annealed at 700 C, (e) a mixture of Fe2O3 + Ga2O3
ball-milled AlFeO3 (12 h), (c) 12 h ball-milled AlFeO3 annealed at 700 C, (1:1), and (f) ball-milled GaFeO3 annealed at 1000 C.
and (d) ball-milled AlFeO3 (24 h).

Figure 6. XRD patterns of ball-milled GaFeO3 along with the prole t,

dierence pattern, and Bragg positions.

the bands. Figure 3d shows the Raman spectrum of AlFeO3 ball-

milled for 24 h at 300 K. The spectrum is as expected for the R3c
space group. Thus, XRD and Raman studies of AlFeO3 clearly
establish that the chiral orthorhombic structure (Pna21) rst
transforms to the orthorhombic P212121 structure of -Al2O3
upon ball-milling for a period of 12 h and transforms to the
rhombohedral R3c structure upon further ball-milling. We have
carried out direct-current magnetization measurements to estab-
lish the magnetic behavior of AlFeO3 with dierent structures.
Figure 4. Temperature-dependent magnetization of ball-milled Al-
FeO3 in the (a) P212121 and (b) R3c structures under FC and ZFC Magnetization data of AlFeO3 ball-milled for 12 h were com-
conditions. Magnetic hysteresis at 5 K is shown in the inset. pared with those of the AlFeO3 structure with the Pna21 space
group. In Figure 4a, temperature-dependent magnetization data
of FC and ZFC of ball-milled AlFeO3 in the P212121 structure are
R-Al2O3 are a = 4.760 and c = 12.993 (JCPDS). The R3c shown. We observe divergence between the FC and ZFC data
sample of AlFeO3 transforms to the Pna21 structure upon below 390 K in the P212121 sample. Furthermore, the nature of
heating to 1350 C, as shown in Figure 1f. the magnetization curves of this sample is quite dierent from
The Raman spectrum of AlFeO3 ball-milled for 12 h at 300 K that of the Pna21 sample, which shows a sharp ferrimagnetic
with the P212121 structure is distinctly dierent from that of bulk transition (TN) at 250 K.2 4,6 The P212121 sample shows
AlFeO3 with the Pna21 structure (see Figure 3a,b). After magnetic hysteresis at 5 K, as shown in the inset of Figure 4a.
annealing ball-milled AlFeO3 at 700 C, the Raman spectrum Figure 4b shows the magnetization data of AlFeO3 in the R3c
did not change signicantly (Figure 3c) except for sharpening of structure obtained by ball-milling for 24 h. The FC data show a
9529 dx.doi.org/10.1021/ic201235h |Inorg. Chem. 2011, 50, 95279532
Inorganic Chemistry ARTICLE

Figure 7. Raman spectra of (a) the orthorhombic GaFeO3 sample, (b) Figure 9. XRD patterns of (a) the orthorhombic Al0.5Ga0.5FeO3
GaFeO3 nanoparticles by the sol gel route, (c) ball-milled GaFeO3, (d) sample, (b) ball-milled Al0.5Ga0.5FeO3, (c) ball-milled Al0.5Ga0.5FeO3
ball-milled GaFeO3 annealed at 700 C, and (e) ball-milled GaFeO3 annealed at 700 C, (d) a mixture of Fe2O3 + Al2O3 + Ga2O3 (1:0.5:0.5),
annealed at 1000 C. and (e) ball-milled Al0.5Ga0.5FeO3 annealed at 1200 C.

Figure 10. XRD pattern of ball-milled Al0.5Ga0.5FeO3 in the R3c structure

Figure 8. Temperature-dependent magnetization of ball-milled Ga- along with the prole t, dierence pattern, and Bragg positions.
FeO3 under FC and ZFC conditions. Magnetic hysteresis at 5 K is shown
in the inset.
completely dierent from that of ball-milled GaFeO3. Upon
annealing of the ball-milled GaFeO3 at 700 C, the XRD pattern
ferrimagnetic transition at a dierent temperature from that of remains the same (Figure 5d) but with smaller line width due to
the Pna21 structure, with TN of 225 K. We observe magnetic the increase in the crystallite size (estimated to be 40 nm). The
hysteresis at 5 K in the R3c sample as well but no saturation. The XRD pattern of ball-milled GaFeO3 is shown along with the
magnitudes of magnetization of both the P212121 and R3c prole t and dierence pattern in Figure 6. The lattice para-
samples are much lower than that of the chiral orthorhombic meters of ball-milled GaFeO3 are a = 5.022(2) and c =
Pna21 structure, showing a preponderance of antiferromagnetic 13.606(5) . Note that the lattice parameters of R-Fe2O3 and
interaction in these transformed phases. rhombohedral Ga2O3 are a = 5.032 , c = 13.733 and a = 4.979 ,
We next examined the eect of ball-milling on the structure c = 13.429 , respectively. Interestingly, upon heating of the
and magnetic properties of GaFeO3. XRD patterns of GaFeO3 in ball-milled GaFeO3 sample to 1000 C, it transformed back to
the Pna21 structure as well as of the GaFeO3 ball-milled for 12 or the orthorhombic chiral (Pna21) structure, as can be seen from
6 h at 300 K are shown in Figure 5. The XRD pattern of GaFeO3 the XRD pattern in Figure 5f.
nanoparticles prepared by the sol gel route is also shown in The Raman spectrum of ball-milled GaFeO3 (R3c) is com-
this gure. The XRD pattern of the nanoparticles prepared by pared with that of the chiral orthorhombic sample as well as that
the sol gel route is the same as that of the Pna21 GaFeO3 of the nanoparticles of GaFeO3 synthesized by the sol gel route.
(see Figure 5a,b) except for line broadening due to the small size. The Raman spectrum of the starting GaFeO3 sample (Figure7a)
Using the Debye Scherrer formula, the particle size was found is similar to that of the nanoparticles of GaFeO3 (Figure 7b), but
to be 25 nm. The XRD pattern of ball-milled GaFeO3 (Figure 5c) we see distinct dierences in the spectrum of ball-milled GaFeO3
is quite dierent from that of the starting material (Figure 5a) and (Figure 7c). After annealing of the ball-milled GaFeO3 at 700 C,
could be readily indexed on the basis of the rhombohedral unit the spectrum remained the same (Figure 7d) except for sharpen-
cell (R3c). The pattern has rather broad reections due to the ing of the bands. The Raman spectrum recorded after annealing
small particle size, estimated to be 20 nm. Furthermore, the XRD of the ball-milled sample at 1000 C (Figure 7e) is similar to that
pattern of a 1:1 mixture of Fe2O3 and Ga2O3 (Figure 5e) is of the starting GaFeO3 sample (Figure 5a). The XRD and Raman
9530 dx.doi.org/10.1021/ic201235h |Inorg. Chem. 2011, 50, 95279532
Inorganic Chemistry ARTICLE

results clearly show that chiral orthorhombic GaFeO3 (Pna21) R3c, rather than R3c, was conrmed by the absence of second
transforms directly to the rhombohedral R3c structure when harmonic generation by the material.
subjected to ball-milling, unlike AlFeO3, which goes through an In Figure 8, we show the temperature dependence of magnetiza-
intermediate phase of the P212121 space group. The space group tion of the R3c sample of GaFeO3 under FC and ZFC conditions.
There is divergence between the FC and ZFC data below 350 K,
and there is no sharp ferrimagnetic transition. Thus, the magnetiza-
tion curves are quite dierent from those of the chiral orthorhombic
structure GaFeO3, which shows a sharp ferrimagnetic transition at
210 K.6,17 The magnitude of magnetization of the R3c sample is
much smaller than that of the Pna21 sample showing the presence of
prominent antiferromagnetic interaction. Nanoparticles of GaFeO3,
however, show magnetic behavior similar to that of the Pna21
GaFeO3 sample but with higher TN.
Because AlFeO3 and GaFeO3 show dierent phase-transition
characteristics upon ball-milling, we have investigated the phase-
transition behavior of Al0.5Ga0.5FeO3. The structure of Al0.5Ga0.5FeO3
under ambient conditions is the same as that of AlFeO3 and
GaFeO3, with the space group being Pna21.6 Upon comparison
of the XRD pattern of Al0.5Ga0.5FeO3 (Pna21) with that of the
sample ball-milled for 24 h at 300 K (particle size, 25 nm), we nd
that the pattern of the latter is characteristic of the rhombohedral
structure (R3c) with lattice parameters a = 4.970(1) and c =
13.509(3) (see Figures 9 and 10). A similar change was observed
after ball-milling for 6 h as well. Upon heating of the ball-milled
sample to 1200 C, it reverts back to the Pna21 structure. The Raman
spectrum of the ball-milled sample of Al0.5Ga0.5FeO3 is consistent
with the R3c structure.
The magnetization behavior of Al0.5Ga0.5FeO3 (R3c) diers
signicantly from that of the starting Pna21 sample,6 in that we do
not see the sharp ferrimagnetic transition at 220 K. Instead, we
observe divergence between FC and ZFC data below 320 K, with
a narrower hysteresis at 5 K. It is interesting that partial
substitution of aluminum by gallium in AlFeO3 favors the direct
Figure 11. Crystal structures of AlFeO3 in (a) orthorhombic and transformation of the Pna21 phase to the R3c phase upon ball-
(b) corundum structures. milling without arriving at the P212121 phase.
In the present study, the most signicant structures encoun-
tered are the initial orthorhombic (Pna21) and the rhombohedral
Table 1. Structural Data of the Various Phases of Al1 xGax-
(R3c) structures of AlFeO3 and GaFeO3, as shown in Figure 11.
FeO3 (x = 0, 0.5, 1)
In Table 1, we list the strucural parameters of all of the phases. It
space a b c RBragg is useful to discuss the structural transformation of AlFeO3 in
structure group () () () (%) light of the various transformations of Al2O3.15 The most stable
structure of Al2O3 is the R form with the space group R3c. This
AlFeO3 structure can be treated as an HCP sublattice of oxygen anions in
orthorhombic Pna21 4.9806(3) 8.5511(6) 9.2403(6) 2.04
which two-thirds of the octahedral interstices are lled with
aluminum cations in an ordered array. The oxygen anions occupy
orthorhombic P212121 15.886(11) 11.408(4) 7.803(4) 0.26
18c Wycko positions, the coordinates of which are x, 0, 1/4 (x =
rhombohedral R3c 4.909(2) 13.393(7) 0.52
0.306), whereas the aluminum cations located at 12c positions
GaFeO3 have coordinates of 0, 0, z (z = 0.347). It has been found that
orthorhombic Pna21 5.0814(2) 8.7436(3) 9.3910(2) 2.74 Boehmite upon heating to 700 C and above gives rise to an
rhombohedral R3c 5.022(2) 13.606(5) 0.14 orthorhombic phase. The phase of Al2O3 is dierent from the *
phase mentioned by Fargeot et al.16 with regard to the structure of
Al0.5Ga0.5FeO3 AlFeO3. The phase derived from the spinel structure belongs to
orthorhombic Pna21 5.0306(1) 8.6461(2) 9.3175(2) 3.34 the P212121 space group.18 The orthorhombic chiral structures
rhombohedral R3c 4.970(1) 13.509(3) 0.23 found by us in AlFeO3 and GaFeO3 are akin to the k phase of Al2O3,
Table 2. Calculated Equilibrium Volumes (per Formula Unit), Binding Energies (per Formula Unit), Bulk Moduli for the
Orthorhombic (Ort) and Corundum (Cor) Structures of AlFeO3 and GaFeO3, and Their Critical Pressures for a Transition from
the Orthorhombic to Corundum Structure
compound V(Ort) (3/fmu) V(Cor) (3/fmu) E(Ort) (eV/fmu) E(Cor) (eV/fmu) B(Ort) (GPa) B(Cor) (GPa) Pcrit (GPa)

AlFeO3 50.1 44.3 37.59 37.29 192 259 9

GaFeO3 53.9 50.9 33.89 33.61 186 131.5 12.7

9531 dx.doi.org/10.1021/ic201235h |Inorg. Chem. 2011, 50, 95279532

Inorganic Chemistry ARTICLE

which has lattice parameters a = 4.69 , b = 8.18 , and c = 8.87 . CONCLUSIONS

The unit cell contains 16 cations, which are ordered in octahedral The present study demonstrates how simple ball-milling can
and tetrahedral sites. The packing of oxygen anions is expected to bring about interesting transformations of AlFeO3 and GaFeO3
remain nearly unaected in Al2O3 through the phase transforma- from the chiral orthorhombic (Pna21) structure. This transfor-
tions. Chemical ordering of cations in the FCC anion structure gives mation in AlFeO3 occurs through an intermediate P212121 phase.
rise to dierent structures with a partly disordered sublattice. While There is an increase in the density or a decrease in the molar
the orthorhombic structures are ordered, there will be considerable volume in the transformations, indicating their rst-order nature.
disorder in the R3c structure. Looking at the Al2O3 Fe2O3 phase It is noteworthy that partial substitution of aluminum by gallium
diagram,19,20 we nd that at 50% composition the orthorhombic in AlFeO3 eliminates the P212121 intermediate phase. While
phase is stable but decomposes to the R phase of the two XRD and Raman data suce to fully characterize the phase
component oxides upon heating. In our case of phase transforma- transitions, magnetic data also throw light on the transformed
tion, we obtain Pna21 as the stable room temperature phase, which phases. The phases with the Pna21 structure exhibit sharp
further transforms to the phase of Al2O3 or R3c upon ball-milling. ferrimagnetic transitions, but the R3c phases are antiferromag-
It appears that the phase transformation is favored by disorder netic with much smaller values of magnetization and a high
kinetics rather than the relative stability and pressure eects. It is to irreversibility temperature. Preliminary results suggest that other
be noted in our experiment that we did not observe any decom- properties such as the magnetodielectric characteristics are
position of the orthorhombic Pna21 phase. unique to the chiral orthorhombic phases of these materials. In
For the purpose of our calculations, we have used the lowest- the case of AlFeO3, it is noteworthy that the orthorhombic
energy structure of the chiral orthorhombic phase with the Pna21 structure seems to be more stable than the rhombohedral
space group based on our earlier work and have not considered structure, unlike in the case of Al2O3.
the possibility of antisite disorder between aluminum (or gallium)
and iron. On the other hand, we have considered the corundum AUTHOR INFORMATION
structure (R3c space group) with half of the cation sites randomly
chosen for occupation with iron because Al2O3 is known to take this Corresponding Author
structure and there are no distinct cation sites. We have taken into *E-mail: cnrrao@jncasr.ac.in. Tel: +91-80-22082761. Fax: +91-80-
account antisite disorder in the case of the corundum structure. Our 22082766.
calculations of the minimum-energy volume of the crystal cell (see
the results in Table 2) show that the corundum structure has a cell
volume about 12 and 6% smaller than that of the orthorhombic REFERENCES
structure of AlFeO3 and GaFeO3, respectively, suggesting a possible (1) Levine, B. F.; Nowlin, C. H.; Jones, R. V. Phys. Rev. 1968,
transition from the orthorhombic to corundum structure upon 174, 571.
application of pressure. Second, the corundum structure is higher in (2) Cotica, L. F.; De Medeiros, S. N.; Santos, I. A.; Paesano, A., Jr.;
energy than the orthorhombic one by about 0.3 eV per formula unit Kinast, E. J.; Da Cunha, J. B. M.; Venet, M.; Garcia, D.; Eiras, J. A.
for both compounds. Using the minimum energies, volumes, Ferroelectrics 2006, 338, 241.
and bulk moduli and a parabolic approximation to the energy (3) Cotica, L. F.; Santos, I. A.; Venet, M.; Garcia, D.; Eiras, J. A.;
function, our estimates of the pressure of transition from the Coelho, A. A. Solid State Commun. 2008, 147, 123.
(4) Bouree, F.; Baudour, J. L.; Elbadraoui, E.; Musso, J.; Laurent, C.;
orthorhombic to corundum structure are quite similar for
Rousset, A. Acta Crystallogr. 1996, B52, 217.
both AlFeO3 and GaFeO3 (slightly higher for GaFeO 3). We (5) Remeika, J. P. J. Appl. Phys. 1960, 31, 263S.
should note that the critical pressure for the orthorhombic (6) Saha, R.; Shireen, A.; Bera, A. K.; Shirodkar, S. N.; Sundarayya,
to corundum structure would reduce with disorder. We note Y.; Kalarikkal, N.; Yusuf, S. M.; Waghmare, U. V.; Sundaresan, A.; Rao,
that the estimated critical pressures for a transition from C. N. R. J. Solid State Chem. 2011, 184, 494.
the orthorhombic to corundum structure are relatively small (7) Shireen, A.; Saha, R.; Mandal, P.; Sundaresan, A.; Rao, C. N. R.
and readily achievable in the laboratory conditions. Before J. Mater. Chem. 2011, 21, 57.
we close, we nd a rather interesting coupling between (8) Gramsch, S. A.; Prewitt, C. T. Spring Meeting Suppl., Abstr. M22A-
magnetic ordering in the corundum structure and pressure. 07, EOS Trans. AGU 2002, 83, 19.
As the cell volume increases, our self-consistent solution (9) Gramsch, S. A.; Prewitt, C. T. Fall Meeting Suppl., Abstr. MR62B-
1084, EOS Trans. AGU 2002, 83, 46.
reveals the development of a magnetic moment at large
(10) Nagai, T.; Hamane, D.; Devi, P. S.; Miyajima, N.; Yagi, T.;
enough volumes (corresponding to negative pressures!) for Yamanaka, T.; Fujino, K. J. Phys. Chem. Lett. B 2005, 109, 18226.
both AlFeO3 and GaFeO3. While this may not be accessible (11) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.;
directly in experiments, we believe that epitaxial lms of these Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46, 6671.
materials on a substrate with a larger lattice constant may (12) Kresse, G.; Hafner, J. Phys. Rev. B 1993, 47, R558.
favor magnetism. (13) Kresse, G.; Furthmller, J. Phys. Rev. B 1996, 54, 11 169.
Thus, the contrast between the structural behavior of AlFeO3 (14) Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758.
and GaFeO3 upon ball-milling cannot be explained entirely using (15) Levin, I.; Brandon, D. J. Am. Ceram. Soc. 1998, 81, 1995.
a simple picture of pressure-induced structural phase transitions. (16) Fargeot, D.; Mercurio, D.; Dauger, A. Mater. Chem. Phys. 1990,
From the results of experiments and calculations reported here, 24, 299.
(17) Frankel, R. B.; Blum, N. A.; Foner, S.; Freeman, A. J.; Schieber,
we believe that a mechanism involving an intermediate phase has
M. Phys. Rev. Lett. 1965, 15, 958.
to be invoked that facilitates transformation of AlFeO3 from the (18) Bonevich, J. E; Marks, L. D J. Mater. Res. 1992, 7, 1489.
orthorhombic phase. Because Al2O3 is known to occur in the (19) Levi, C. G. Acta Mater. 1998, 46, 787.
structure with the P212121 space group,15 it is understandable (20) Polli, A. D.; Lange, F. F.; Levi, C. G J. Am. Ceram. Soc. 1996,
why this occurs as the intermediate structure in the transforma- 79, 1745.
tion of AlFeO3.
9532 dx.doi.org/10.1021/ic201235h |Inorg. Chem. 2011, 50, 95279532