Review Article  Open Access
Yu Ting Wang, Chih Wei Luo, Takayoshi Kobayashi, "Understanding Multiferroic Hexagonal Manganites by Static and Ultrafast Optical Spectroscopy", Advances in Condensed Matter Physics, vol. 2013, Article ID 104806, 13 pages, 2013. https://doi.org/10.1155/2013/104806
Understanding Multiferroic Hexagonal Manganites by Static and Ultrafast Optical Spectroscopy
Abstract
Multiferroic hexagonal manganites ReMnO_{3} studied by optics are reviewed. Their electronic structures were revealed by static linear and nonlinear spectra. Two transitions located at 1.7 eV and 2.3 eV have been observed and attributed to the interband transitions from the lowerlying Mn^{3+} and states to the Mn^{3+} state, respectively. These socalled dd transitions exhibit a blueshift as decreasing temperatures and an extra blueshift near . This dramatic change indicates that the magnetic ordering seriously influences the electronic structure. On the other hand, the ultrafast optical pumpprobe spectroscopy has provided the important information on spincharge coupling and spinlattice coupling. Because of the strongly correlation between electronic structure and magnetic ordering, the amplitude of the initial rising component in shows striking changes at the vicinity of . Moreover, the coherent optical and acoustic phonons were observed on optical pumpprobe spectroscopy. Both the amplitude and dephasing time of coherent phonons also exhibit significant changes at , which provide the evidence for spinlattice interaction in these intriguing materials.
1. Introduction
Multiferroic materials [1–4] with the coexistence of various ferroic order (ferromagnetic, ferroelectric, or ferroelastic) have attracted great attention in condensed matter research due to their great potential for applications in the fields of oxide electronics, spintronics, and even the green energy devices for reducing the power consumption. With multiferroic oxides (in single phase), the coupling interaction among various order parameters causes the socalled magnetoelectric effect [5–10]. In this, a polarization can be induced by applying a magnetic field or a magnetization can be induced by applying an electric field. Although the properties of electricity and magnetism were combined into one common discipline by the Maxwell equations, the electric and magnetic orderings in solidstate materials are always considered separately. This is because that the electric charges of electrons and ions are responsible for the charge effects, whereas the electron spins govern the magnetic properties.
Prellier et al. [11] classified the characteristics of multiferroic materials into three categories. The first is Bibased compounds, such as BiMnO_{3} and BiFeO_{3}. The second is perovskites and related ReMnO_{3} compounds (Re = Y, Ho, Er, Tm, Yb, and Lu). The third is ReMn_{2}O_{5} (Re is rare earth element). Additionally, Cheong and Mostovoy [12] summarized the classification of ferroelectrics into “proper” and “improper” according to their mechanisms of inversion symmetry breaking. In proper ferroelectrics, the main driving force toward the polar state was associated with the electronic pairing. On the other hand, the induced polarization in improper ferroelectrics involves a more complex lattice distortion or other accidental orderings. For example, the hexagonal manganite ReMnO_{3} compounds show a lattice distortion to enlarge their unit cell, which is the socalled geometric ferroelectricity [13–15].
The aim of this paper is to understand the multiferroic hexagonal manganites studied by some optical techniques. In Section 2, the overall features of manganites are introduced. The structure of rare earth manganite is strongly depending on the size of rare earth and also temperature. The environment of Mn ions significantly affects its electronic structure which was investigated by static linear and nonlinear spectra in Section 3. Section 4 is the main part of this paper. The ultrafast spectroscopies demonstrate the interaction between electron, phonon, and spin systems on multiferroic hexagonal manganites. Finally, the summary and future outlook will be given in Section 5.
2. The Characteristics of Multiferroic Manganites ReMnO_{3}
Recently, multiferroic rare earth manganites (ReMnO_{3}) have attracted a great deal of attention due to their manifestations of intriguing and significant couplings between the magnetic and electric order parameters. Generally, ReMnO_{3} has two kinds of multiferroic structures, that is, hexagonal and orthorhombic. The rare earth (Re^{3+}) ionic size shrinks from 1.11 Å to 0.94 Å with decreasing the atomic number and reducing the electrons residing in the 4f orbit, called the lanthanum contraction effect. The rare earth ions (Re^{3+}) have closely chemical properties because the same electronic configurations of 5s^{2}5p^{6} for outermost electrons. The coexistence of ferroic orders in ReMnO_{3} with hexagonal (smaller ionic radius of rare earth Re = Sc, Y, and from Ho to Lu) or orthorhombic (larger ionic radius of rare earth Re = La to Dy) (shown in Figure 1) structure yields complex physics in the intimate interactions among charge, orbital, lattice, and spin degrees of freedom. It also has fascinating physical properties which might lead to promising applications. The orthorhombic structure with a Pnma space group forms the stable crystal structure of ReMnO_{3} perovskite oxides with Re = La to Dy, which belongs to the magnetic ferroelectrics induced by magnetic ordering [8, 16]. Furthermore, another family of compounds with smaller ionic size (for Re = Y, Ho, Er, Yb, Lu, etc.) forms the stable hexagonal structure with cm space group. The critical point of the structure transition is located near YMnO_{3} (Y^{3+} = 1.06 Å) and HoMnO_{3} (Ho^{3+} = 1.05 Å). Consequently, the crystal structures of these two families have been transformed from hexagonal to orthorhombic (or vice versa) by many experimental techniques, for example, hightemperature and highpressure processes [17, 18], chemical solution deposition (CSD) [19], the metalorganic chemical vapor deposition (MOCVD) [20], molecular beam epitaxy (MBE) [21], sputtering [22], and pulsed laser deposition (PLD) [16, 23].
In the following, we are going to focus on recent studies on the multiferroic hexagonal manganites (ReMnO_{3}, Re = rare earth) which have properties similar to various rareearth elements, both electric transportation or magnetic behaviors. For example, the hexagonal HoMnO_{3} has ferroelectric ordering at Curie temperature = 875 K, the antiferroicmagnetic (AFM) Mn^{3+} ordering at Néel temperature = 76 K, and the magnetic Ho^{3+} ordering at = 4.6 K, in which the magnetically active ions are the high spin Mn^{3+} (3d^{4}, S = 2) and Ho^{3+} (4f^{10}) [5, 14, 33, 40–45]. The ferroelectricity in magnetoelectric ReMnO_{3} is caused by a buckling of the layered MnO_{5} polyhedral and is accompanied by displacements of the Re ions, which lead to a net electric polarization. In 2004, through Xray diffraction and first principle density functional calculations, Van Aken et al. [14] demonstrated the previous scenario in the hexagonal manganite YMnO_{3}, as shown in Figure 2 which presents the “geometric” generation of polarization and describes the tilting of a rigid MnO_{5} block with a magnetic Mn atom at the center. The magnetic structure has been studied by various experimental methods, such as neutron diffraction [45, 46] or second harmonic generation (SHG) [33, 47]. In cm hexagonal manganites, each Mn^{3+} ion is surrounded by five O^{2} ions, forming triangular planar sublattices in the basal plane (ab plane). The magnetic order of Mn^{3+} is mainly dominated by AFM inplane MnOMn superexchange interaction. Therefore, the triangular lattice of the Mn atoms exhibits strong geometrical frustration effect [48]. Furthermore, when the temperature cools to near , the strong superexchange leads to a 120° arrangement between neighboring Mn^{3+} spins in the basal plane which breaks the triangular frustration. In addition, the spins of Mn rotate with an angle of 90° at (e.g., for hHoMnO_{3}, ~ 33 K) due to the onset of the AFM order of the Re moments, indicating the interaction between Re^{3+} and Mn^{3+} spins. Another magnetic transition at involves the complete magnetic order of the Re^{3+} ions (e.g., for hHoMnO_{3}, ~ 5 K).
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In addition, there are many studies showing the anomaly around , such as the dielectric constant [49], specific heat measurements [50], and the lattice constant measurements [51], which are attributed to the indirect coupling via lattice strain (spinlattice coupling). Recently, Lee et al. [52] observed the giant magnetoelastic effect in hexagonal YMnO_{3} and LuMnO_{3} by using the highresolution neutron and synchrotron powder diffraction experiments. They further claimed that the magnetoelectric (ME) coupling can be interpreted by the giant magnetoelastic effect very well in ReMnO_{3}, that is, the magnetic longrange ordering induced the very large displacements of all atoms at . In other words, the magnetoelastic coupling allowed the atoms to undergo an isostructural transition, which has been regarded as the primary source of the magnetoelectric phenomena. In hexagonal ReMnO_{3}, this magnetoelastic effect is two orders of magnitude larger than those appearing in other magnetic materials. Therefore, the gigantic magnetoelastic coupling plays a crucial role in dominating many physical properties in hexagonal ReMnO_{3}.
Femtosecond pumpprobe spectroscopy has been established as a protocol for studying the interactions between electrons, phonons, and magnons [35, 53–59] and is therefore employed with these multiferroic ReMnO_{3} materials to gain insight into the magnetoelastic effect. By measuring the transient reflectivity () or transmittance (), we can observe the intricate correlation processes among the charge, lattice, and spin degrees of freedom, which are explicitly recognized in different characteristic time scales. Thus, the microscopic mechanism of the magnetoelectric coupling or magnetoelastic behavior in this kind of strongly correlated materials can be revealed.
3. Electronic Structure Revealed by Optical Spectroscopy
To understand the extensive physical properties in multiferroic ReMnO_{3} materials, it is crucial to realize the electronic band structure. With respect to the crystal structure of hexagonal ReMnO_{3} manganites with MnO_{5} bipyramids, in contrast with the MnO_{6} octahedron of orthorhombic structure which split to and , the crystal field symmetry leads the quintet d levels of Mn^{3+} ion splits into two low lying doublets of and (/ and /) states and one singlet () state. In general, optical spectroscopy is one of the powerful tools for investigating the electronic band structure in materials. Therefore, this structural difference between the hexagonal and orthorhombic phases could be disclosed by the optical spectra [60, 61].
3.1. Linear Optical Absorption Spectra
The first optical measurements in hexagonal YMnO_{3} were performed by Kritayakirana et al. in 1969 [62], who observed that a near infrared absorption edge moves to higher energy with lowering temperature. For the case of hexagonal ScMnO_{3} and ErMnO_{3}, the spectra of the real and imaginary parts of the dielectric function were also measured by Kalashnikova and Pisarev [63]. An abnormally drastic absorption peak in the region of 1.57–1.59 eV is the most pronounced feature in the dielectric spectra. This peak exhibits asymmetry and can be decomposed into two components by peak fitting with the Gaussian functions. Furthermore, the absorption intensity in the region above 2.2–2.4 eV increases with photon energy. In addition, hexagonal HoMnO_{3} [64] and LuMnO_{3} [31] also exhibit similar results. It is noteworthy that the near infrared absorption peak exhibits a substantial blueshift of ~0.16 eV from 300 K to 10 K as shown in Figure 3. Recently, Choi et al. [32] reported a systematic study on the hexagonal ReMnO_{3} (R = Gd, Tb, Dy, and Ho), and the overall features in the spectra are similar to previous results. The most surprising part of those results is that the temperaturedependent absorption peak at ~1.7 eV shows an unexpectedly large blueshift near among the rareearth ions of Re = Lu, Gd, Tb, Dy, and Ho, as shown in Figure 4(a).
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The assignment of the optical absorption peak at ~1.7 eV has also been an issue. One interpretation is that it comes from the charge transfer transition from the O 2p to the Mn 3d states [30, 63, 65, 66]. The photoemission spectroscopy (PES) study proposed that the O 2p is the highest occupied state, while the Mn state is mostly unoccupied. Other occupied Mn 3d states (/, and /) lie deep below [65]. The result of the firstprinciple electronic structure calculations also suggested that the top of the valence band is mainly determined by the O 2p states, and the lowest unoccupied band is formed by the of Mn [30, 66]. The other interpretation, which is also an extensively convincing explanation, is that it comes from onsite dd transition between the Mn 3d levels [31, 34, 64, 67]. The transition was attributed to the dd transition between occupied and (/, and /) orbitals and the unoccupied () orbit, as shown in Figure 4(b). Because of the selection rule, transitions between d orbitals are forbidden. However, the selection rule is relaxed through the strong hybridization between the O 2p bands and transition metal d bands, which was observed in the hexagonal phase but not in the orthorhombic phase [60]. Furthermore, the strong peak at ~5 eV is attributed to the charge transfer transition from the hybridized O 2p level to the Mn level.
The other feature of the near infrared absorption peak is that it shows the blueshift as decreasing temperatures accompanying the dramatic changes near , which indicates the effective coupling between the electronic structure and the magnetic ordering. Souchkov et al. [31] attributed this temperaturedependent blueshift to the effects of exchange interactions between the Mn^{3+} ions. The superexchange between Mn^{3+} neighbors leads to lower / levels, whereas the level is rarely affected (see Figure 4(b)). Moreover, together with the temperaturedependent and magneticdependent results [32] further implies that the magnetic ordering seriously influences the electronic structure.
3.2. Second Harmonic Generation Spectra
From the linear absorption spectra, the strong absorption caused by the dd transition from to was clearly observed in hexagonal manganites. But the transition from to is another question. Recently, the second harmonic generation (SHG) was successfully used to explore the hidden localized dd transitions, even those embedded in the much stronger absorption peaks [68]. The nonlinear polarization induced by optical waves is given by where is the nonlinear polarization induced in a medium. and are the electric field components of the fundamental light. and are the secondorder nonlinear susceptibility tensor which are uniquely defined by the crystalline and magnetic structure of the crystal, respectively. The subscripts, , and correspond to the Cartesian coordinate axes , , and . is the direction of the nonlinear polarization generated; and are the directions of applied optical field.
There are two types of optical SHG in multiferroic hexagonal manganites. One is caused by the noncentrosymmetric ferroelectric ordering of charges and the nonlinear susceptibility is time invariant (itype). The other is due to the centrosymmetric antiferromagnetic ordering of spins and the susceptibility is time noninvariant (ctype) [34]. Table 1 lists the allowed susceptibility tensor components in itype and ctype. Thus, the SHG contribution from ferroelectric and antiferromagnetic can be distinguished easily. Figure 5 summarizes the magnetic symmetries of all the hexagonal ReMnO_{3} compounds as derived from the SHG experiments [33].

The polarization with the space group cm below the Curie temperature is The contribution from antiferromagnetic below for the space group P6_{3}cm (e.g., YMnO_{3} [68, 69]) is
Figure 6(a) exhibits the SHG spectra of component in YMnO_{3} at 6 K [34]. The strong peak is centered at 2.7 eV, which could be assigned to (corresponds to ) transition. Figure 6(b) right panel shows the spectrum of . Peaks at 2.46 eV represent the (corresponds to ) transition. These assignments have been proved by several studies [47, 68, 69]. In the inset of Figure 6(b), the temperaturedependent intensity of 2.46 eV disappears once the temperature is higher than , which strongly indicates the closed correlation between the antiferromagnetic order parameter and SHG.
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Consequently, the electronic structure of hexagonal manganites has been clearly depicted by linear and nonlinear optical spectroscopy, which further provides the basis for the excitation and relaxation of electrons in pumpprobe spectroscopy.
4. Ultrafast PumpProbe Spectroscopy
Ultrafast optical pumpprobe spectroscopy has proven to be a powerful tool to investigate the dynamics of electronelectron interaction, electronphonon interaction, and electronspin interaction in various materials (see, e.g., [70–72]). To understand the underlying mechanisms in strongly correlated materials, the interactions between these order parameters should be derived first. Because of the different characteristic time scales and characteristic behavior for various degrees of freedom existing in these complex materials, ultrafast spectroscopy can determine the coupling between each order of parameters.
As shown in Figure 7, the general idea of the pumpprobe technique is that changes of a sample induced by a pump pulse are obtained by detecting the change in the reflectivity or transmissivity of probe pulses as a function of probe delay time. The femtosecond time evolutions are derived by delaying the relative arrival time between the pump and probe pulses using a mechanical delay line. The fluence of a probe pulse is usually much weaker than that of a pump pulse in order to avoid second excitation in the samples. The polarizations of pump and probe pulses are set perpendicular to avoid interference between pump and probe beams [73].
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Generally, this pumpprobe spectroscopy composes two kinds of signals of the decay background and the oscillation, which relates to the relaxation of carriers and the dynamics of phonons or spins, respectively. By the Fourier transform, the frequency of phonon modes can be doubly obtained from the oscillation signals in pumpprobe spectroscopy. Moreover, the phonon dynamics, that is, the timeevolution of oscillation signals, can be revealed by shorttime Fourier transform (STFT), which cannot be reached by common Raman spectroscopy. Thus, the pumpprobe spectroscopy is a powerful tool to provide the information in time and frequencydomain simultaneously.
4.1. SpinCharge Coupling
Since the magnetic ordering and the electronic structure of manganites are strongly correlated, as found in temperaturedependent absorption spectra, there is a strong coupling between charge and spin, which can be revealed by the timeresolved femtosecond spectroscopy [72]. Shih et al. observed the spincharge coupling by various photon energy excitations on hexagonal HoMnO_{3} single crystals [35]. As shown in Figure 8(a), the amplitude as a function of temperature shows a significant drop to cross zero amplitude line to become negative at some characteristic temperatures. The excitation photon energy used in the experiment changes from 1.52 to 1.68 eV, which is exactly the range covering the dd transition energy (transition from to ) in the hexagonal ReMnO_{3}. When the photon energy is larger than , the electrons in the orbit can transfer to the unoccupied orbital by absorbing pumping photons. Conversely, this onsite transition would be completely blocked when the transition energy becomes larger than the pumping photon energy. Thus, the amplitude vanishes at a certain temperature , which drops with increasing photon energy, indicating the blueshift of . Furthermore, Shih et al. found that the optical pumpprobe measurement is sensitive to shortrange magnetic order. In Figure 8(b), the as a function of demonstrates a gradual increase in the extent of antiferromagnetic (AFM) ordering. Moreover, this ordering starts to deviate from linearity around (~76 K), suggesting the prevalence of global longrange AFM ordering. The AFM correlation evolves with temperature as it is close to , shown as in Figure 8(c). Later, Wu et al. obtained similar results for hexagonal YMnO_{3} thin films [74]. Furthermore, they found that the straininduced changes of , which are difficult to be observed by the temperaturedependent magnetization measurements, can be clearly revealed by the shift of .
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As a result, the amplitude of the initial rising component of corresponding to the Mn^{3+} dd transition is caused by strong coupling between the electronic structure and magnetic ordering. Moreover, the emergence of longrange and shortrange magnetic orders can be clearly observed by optical pumpprobe spectroscopy.
4.2. SpinLattice Coupling
Optically induced lattice vibration can be observed through optical pumpprobe spectroscopy through a periodic oscillation. This periodic oscillation in reflectivity (or transmissivity), socalled coherent acoustic phonons, is caused by interference between the reflected probe beams from sample surface and the wave front of the propagating strain pulse generated upon the pump pulse [75, 76]. On the other hand, vibration with frequencies corresponding to optical phonon modes in various materials has been observed by pumpprobe spectroscopy. A number of mechanisms have been proposed to explain these oscillations, for example, the displacive excitation of coherent phonons (DECP) [77] and the impulsive stimulated Raman scattering (ISRS) [78, 79]. The simplest idea is that a pump pulse creates a standing wave which was generated by the coherent ionic motion. Then a following probe pulse senses the changes of refractive index which is modulated by the standing wave. In general, the reflectivity (or transmissivity) oscillation observed in pumpprobe spectroscopy always corresponds to the optical phonon modes observed in Raman spectroscopy. In conclusion, the measurements of coherent acoustic or optical phonons dynamics at various temperatures are useful to study the spinlattice coupling in multiferroic materials.
4.2.1. Coherent Optical Phonons
Figure 9 shows the reflectivity oscillation of ~3.6 THz (~120 cm^{−1}) in LuMnO_{3} [36, 37]. According to Raman studies, this vibration mode can be attributed to optical phonon of symmetry [80–82]. This fully symmetric mode corresponds to the Lu1 and Lu2 atomic motions in opposite directions along the caxis, as depicted in Figure 9(d) [36]. In temperaturedependent measurements, the optical phonon almost disappears below , as shown in Figures 9(e) and 9(f) [37]. Additionally, the structural change from highly symmetry space group /mmc to the tilted and distorted cm ferroelectric structure [14] in hexagonal manganites (see Figure 1) takes place at the Curie temperature (), which is much higher than . Since there is no structural transition near , the atomic motions of the optical phonon mode would be affected by the appearance of magnetic ordering. In other words, the disappearance of optical phonon mode might be attributed to the magnetoelastic coupling. In temperaturedependent Raman studies, the lowest frequency mode also shows anomaly at in YMnO_{3} [82], ErMnO_{3} [83], and LuMnO_{3} [80, 82] which support close relation between phonon and spin systems.
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4.2.2. Coherent Acoustic Phonons
Coherent acoustic phonons have been observed in many kinds of hexagonal manganites such as LuMnO_{3} [37, 84], YMnO_{3} [39], and HoMnO_{3} [38]. The damped oscillation behavior in reflectivity changes with time delay could be described as follows [76]: where is the wavelength of the probe pulses, is the refraction index of samples without strain, is the strained layer propagating sound speed, and is the penetration depth of probe pulses. The frequency of the oscillation is given as and the dephasing time is .
According to (4), the dephasing time is proportional to the penetration depth of probe pulses and the inverse sound velocity . However, the skin depth is much shorter than the propagating length of the strain pulse. Therefore, the dephasing time is dominated by the finite penetration depth of the probe [84]. The dephasing time of acoustic phonons shows strong temperature dependence (Figure 10), and the anomalous increase of the dephasing time near might be because of the photon energy being close to the edge of dd transition. In other words, the penetration depth increases and the absorption of probe photons for the dd transition decreases (due to the blueshift of as mentioned in Section 3.1) as the temperature decreases.
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The amplitude and period of the oscillation component in show strong temperature dependence as shown in Figure 11. Both of these parameters are clearly anomalous near the magnetic ordering temperature . The amplitude of the oscillation component in gradually increases with decreasing temperature and reaches the maximum near a characteristic temperature (~190 K for YMnO_{3} [39] and ~200 K for LuMnO_{3} [37]). Then it decreases when the temperature approaches , as shown in Figure 11(a). This may imply the appearance of AFM shortrange ordering, as mentioned in [35]. On the other hand, the period of the oscillation component in also slightly shrinks with decreasing temperature. Surprisingly, it dramatically shrinks around as shown in Figure 11(b). This strongly indicates the close correlation between AFM ordering and the propagation of thermal stress along caxis, which is consistent with the results in heat capacity measurements [13, 85]. In addition, the ferroelectric polarization along the caxis caused by polyhedron tilting of MnO_{5} and distortion of the rareearth ions [14] is well known. Thus, the propagation of a strain pulse with the modulation of dielectric constant (or ferroelectric polarization) along caxis is indeed affected by the appearance of AFM ordering. Neutron diffraction experiments also have demonstrated the extra displacement of the rareearth and oxygen atoms along caxis at [52]. Finally, these results in amplitude and period of the oscillation component in provide evidence for magnetoelastic coupling in these intriguing materials.
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5. Summary and Outlook
In this paper, the recent developments on the electronic structures and ultrafast dynamics of hexagonal manganites have been reviewed. The electronic structure can be clearly revealed by the static linear optical absorption spectra and nonlinear second harmonic generation spectra. The temperaturedependent dd transition energy exhibits an unexpected change near the spin ordering temperature . This strongly indicates the coupling between electronic structure and antiferromagnetism in hexagonal manganites. Fortunately, the photon energy of the pulse laser used in pumpprobe spectroscopy accidentally fits well the dd transition (from to ) energy. Therefore, the pumpprobe measurements can reveal the ultrafast dynamics through the spincharge coupling and spinphonon coupling.
However, those ultrafast dynamic experiments only present the charge dynamics between and . If the laser spectrum could cover the whole range of dd transition, that is, containing the transition from to and to , it could disclose all of the charge dynamics in these strongly magnetic influenced d orbitals. The optical parametric amplifier (OPA) is a suitable light source for this kind of study. Consequently, if all of the charge dynamics in the d orbitals could be completely revealed, it would shed light on the microscopic mechanism of the magnetoelectric coupling or magnetoelastic effect in this kind of strongly correlated material.
Acknowledgments
This work was supported by the National Science Council of Taiwan, under Grants nos. NSC982112M009008MY3, NSC1012112M009016MY2 and by the MOEATU Program at NCTU of Taiwan, Taiwan.
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