Second-order nonlinear optical and linear UV-VIS absorption properties of type-II multiferroic candidates RbFe(AO4)2 (A = Mo, Se, S)
Rachel Owen, Elizabeth Drueke, Charlotte Albunio, Austin Kaczmarek, Wencan Jin, Dimuthu Obeysekera, Sang-Wook Cheong, Junjie Yang, Steven Cundiff, Liuyan Zhao
备注：
22 pages total: 12 pages of main text, 3 pages of appendix, 1 page of references, 6 pages of figures. 7 figures total: 4 figures in the main body, 3 figures in the appendix. All figure and figure captions are listed at the end of the manuscript
Motivated by the search for type-II multiferroics, we present a comprehensive optical study of a complex oxide family of type-II multiferroic candidates: RbFe(MoO4)2, RbFe(SeO4)2, and RbFe(SO4)2. We employ rotational-anisotropy second harmonic generation spectroscopy (RA SHG), a technique sensitive to point symmetries, to address discrepancies in literature-assigned point/space groups and to identify the correct crystal structures. At room temperature we find that our RA SHG patterns rotate away from the crystal axes in RbFe(AO4)2 (A = Se, S), which identifies the lack of mirror symmetry and in-plane two-fold rotational symmetry. Also, the SHG efficiency of RbFe(SeO4)2 is two orders of magnitude stronger than RbFe(AO4)2 (A = Mo, S), which suggests broken inversion symmetry. Additionally, we present temperature-dependent linear optical characterizations near the band edge of this family of materials using ultraviolet-visible (UV-VIS) absorption spectroscopy. Included is experimental evidence of the band gap energy and band gap transition type for this family. Previously unreported sub-band gap absorption is also presented, which reveals prominent optical transitions, some with an unusual central energy temperature dependence. Furthermore, we find that by substituting the A-site in RbFe(AO4)2 (A = Mo, Se, S), the aforementioned transitions are spectrally tunable. Finally, we discuss the potential origin and impact of these tunable transitions.
We have investigated the magnetic structure and ferroelectricity in RbFe(MoO$_4$)$_2$ via first-principles calculations. Phenomenological analyses have shown that ferroelectricity may arise due to both the triangular chirality of the magnetic structure, and through coupling between the magnetic helicity and the ferroaxial structural distortion. Indeed, it was recently proposed that the structural distortion plays a key role in stabilising the chiral magnetic structure itself. We have determined the relative contribution of the two mechanisms via \emph{ab-initio} calculations. Whilst the struct…
The symmetry properties, order parameters, and magnetoelectric phase diagrams of multiferroics are discussed. After brief reviews of Ni$_3$V$_2$O$_8$, TbMnO$_3$, and RbFe(MoO$_4$)$_2$, we present a detailed analysis of RMn$_2$O$_5$ (with R=Y, Ho, Dy, Er, Tb, Tm).
Competing interactions and geometric frustration provide favourable conditions for exotic states of matter. Such competition often causes multiple phase transitions as a function of temperature and can lead to magnetic structures that break inversion symmetry, thereby inducing ferroelectricity [1-4]. Although this phenomenon is understood phenomenologically [3-4], it is of great interest to have a conceptually simpler system in which ferroelectricity appears coincident with a single magnetic phase transition. Here we report the first such direct transition from a paramagnetic and paraelectric …
Unusual domains with curved walls and failure to satisfy the Landau-Lifshitz-Kittel Law are modeled as folding catastrophes (saddle-node bifurcations). This description of ballistic motion in a viscous medium is based upon early work by Dawber et al., Appl. Phys. Lett. 82, 436 (2003). It suggests that ferroelectric films can exhibit folds or vortex patterns but not both.
Different methods of texturing polycrystalline materials are developed over years to use/probe anisotropic material properties with relative ease, where complicated and expensive single crystal growth processes could be avoided. In this paper, particle morphology assisted texturing in multiferroic MnWO$_4$ has been discussed. Detailed powder x-ray diffraction vis-a-vis scanning electron microscopic studies on differently annealed and processed samples have been employed to probe the giant texturing effect in powdered MnWO$_4$. A quantitative measure of the texturing has been carried out by mea…
The ferro-rotational order, whose order parameter (OP) is an axial vector invariant under both time reversal (TR) and spatial inversion (SI) operations, is the last remaining category of ferroics to be observed after the ferroelectric, ferromagnetic, and ferro-toroidal orders. This order has become increasingly popular in many new quantum materials, especially in complex oxides, and is considered responsible for a number of novel phenomena such as polar vortices, giant magnetoelectric coupling, and type-II multiferroics. However, physical properties of the ferro-rotational order have been rare…
Optimal materials to induce bulk photovoltaic effects should lack inversion symmetry and have an optical gap matching the energies of visible radiation. Ferroelectric perovskite oxides such as BaTiO$_3$ and PbTiO$_3$ exhibit substantial polarization and stability, but have the disadvantage of excessively large band gaps. We use both density functional theory and dynamical mean field theory calculations to design a new class of Mott multiferroics--double perovskite oxides $A_2$VFeO$_6$ ($A$=Ba, Pb, etc). While neither perovskite $A$VO$_3$ nor $A$FeO$_3$ is ferroelectric, in the double perovskit…
Multiferroic bismuth ferrite Bi_2Fe_4O_9 (BFO) ceramic was synthesized by conventional solid state reaction route. X-ray diffraction and Rietveld refinement show formation of single phase ceramic with orthorhombic crystal structure (space group Pbam). The morphological study depicted a well-defined grain of size $\simeq$2μm. The optical studies were carried out by using UV-Vis spectrophotometer which shows a band gap of 1.53 eV and a green emission spectrum at 537 is observed in the Photoluminescence study. The frequency dependent dielectric study at various temperature revealed that the diele…
Using first-principles density functional calculations, electronic and optical properties of ferromagnetic semiconductor EuO are investigated. In particular, we have developed a way to obtain the spin-dependent optical response of the magnetic materials, which is helpful to verify the spin-dependent band structure of EuO. Significantly different optical responses from spin-up and spin-down channels are obtained in both linear and nonlinear cases, making it possible to distinguish contributions from different spin-channels in the optical absorption spectra if spin-flip process can be neglected.…
In this paper, the photocatalytic activity of multiferroics BiFeO3 (BFO) and Bi0.8La0.2FeO3 (BLFO) nanocrystals with two different morphologies which were synthesized by two different sol-gel (SG) and hydrothermal (HT) methods have been studied. All the obtained samples were characterized using X-ray diffractometer, Fourier transform infrared spectroscopy, transmission electron microscopy, UV-vis spectroscopy and vibrating sample magnetometer. Differential thermal analysis (DTA) measurements were probed ferroelectric- paraelectric first-order phase transition (TC) for all samples. Addition of …
Combining ferroelectricity with other properties such as visible light absorption or long-range magnetic order requires the discovery of new families of ferroelectric materials. Here, through the analysis of a high-throughput database of phonon band structures, we identify a new structural family of anti-Ruddlesden-Popper phases A$_4$X$_2$O (A=Ca, Sr, Ba, Eu, X=Sb, P, As, Bi) showing ferroelectric and anti-ferroelectric behaviors. The discovered ferroelectrics belong to the new class of hyperferroelectrics which polarize even under open-circuit boundary conditions. The polar distortion involve…
Magnetoelectric multiferroic composite of two types of multiferroic (Type I and II) consisting BiFeO3 and TbMnO3 is studied for enhanced magnetic and transport properties. A narrower band gap is estimated from the UV-visible absorption spectrum from that of BiFeO3 and TbMnO3. With known value of band gap, the band structure was estimated from the valence band x-ray photoemission spectra (XPS) and ultra violet photoemission spectra (UPS). The valence and conduction band was found at 1.0 eV and 0.45 eV above and below the Fermi level respectively. Thus the insulating behavior of the system is un…
Multiferroics have received intense attention due to their great application potential in multi-state information storage devices and new types of sensors. Coupling among ferroic orders such as ferroelectricity, (anti-)ferromagnetism, ferroelasticity, etc. will enable dynamic interaction between these ordering parameters. Direct visualization of such coupling behaviour in single phase multiferroic materials is highly desirable for both applications and fundamental study. Manipulation of both ferroelectric and magnetic domains of Bi5Ti3FeO15 thin film using electric field and external mechanica…
