Observation of electronic ferroelectric polarization in multiferroic YMn2O5

We report the observation of a magnetic polarization of the O 2p states in YMn(2)O(5) through the use of soft x-ray resonant scattering at the oxygen K edge. Remarkably, we find that the temperature dependence of the integrated intensity of this signal closely follows the macroscopic electric polarization, and hence is proportional to the ferroelectric order parameter. This is in contrast with the temperature dependence observed at the Mn L(3) edge, which reflects the Mn magnetic order parameter. First-principles calculations provide a microscopic understanding of these results and show that a spin-dependent hybridization of O 2p and Mn 3d states results in a purely electronic contribution to the ferroelectric polarization, which can exist in the absence of lattice distortions.     

Anisotropy of permittivity of the hexagonal multiferroic HoMnO<Subscript>3</Subscript> in the spectral range 0.6–5.0 eV

The anisotropy of the optical properties of a single crystal of the hexagonal manganite HoMnO₃ has been investigated by spectroscopic ellipsometry in the spectral range 0.6–5.0 eV. It has been demonstrated that the optical absorption edge for the polarization E ⊥ c is determined by the intense narrow transition O(2p) → Mn(3d) centered at 1.5 eV, whereas this transition for the polarization E ‖ c is strongly suppressed and shifted toward higher energies by 0.2 eV. It has been revealed that, at the temperature T = 293 K, the spectra for both polarizations E ‖ c and E ⊥ c exhibit a broad absorption band centered at ∼2.4 eV, which was earlier observed in nonlinear spectra during optical second harmonic generation.     

HRTEM and EELS study of Y2O3/MgO thin films

Y2O3 thin films deposited on (001)-MgO substrate have been investigated by high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy. Digital processing of the HRTEM images reveals the presence of grains with a crystallographic structure different from that of the rest of the film (Ia3). The spectrum imaging technique has been applied in vicinity of the Y2O3/MgO interface to get a better knowledge of the phases nucleated on the substrate surface. Fine structures of the O K-edge have been studied in detail; actually two kinds of spectra have been detected in the yttrium oxide thin film. These spectra have been compared to self-consistent full multiple scattering calculations (SC-FMS). One family of spectra has then been associated to the well-known Ia3 structure. The other family of spectra has been compared to calculations performed for the other known structures (such as hexagonal or monoclinic) of Y2O3 with a little success. We have finally compared these spectra to calculations performed with a particular atomic arrangement (octahedral) of Y and O atoms, which leads to a good match between experimental and calculated spectra. Our results emphasize the benefit of coupling several techniques such as HRTEM, EELS and SC-FMS for the determination of structures at the nanometric scale.     

Atomistic simulation of dynamical and defect properties of multiferroic hexagonal YMnO_3

Atomistic simulation has been performed to investigate the dynamical and defect properties of multiferroic hexagonal YMnO3 with newly developed interaction potentials. Dynamical calculation reveals that phonon vibrations of hexagonal YMnO3 are quite different from those of orthorhombic YMnO3. Defect calculation finds that O Frenkel is the most probable intrinsic disorder, and Mn antisite defect is favorable to exist, especially for Mn ions entering the Y2 sites. It is also found that holes prefer to localiz...     

Resonant photoemission at the L3 absorption edge of Mn and Ti and the electronic structure of 1T-Mn0.2TiSe2

Resonant valence band x-ray photoelectron spectra (ResPES) excited near the 2p(3/2) core level energies, 2p x-ray photoelectron spectra (XPS) and L(3,2) x-ray absorption spectra (XAS) of Ti and Mn in single crystals of 1T-Mn(0.2)TiSe(2) were studied for the first time. The ionic-covalent character of the bonds formed by the Mn atoms with the neighboring Se atoms in the octahedral coordination is established. From the XPS and XAS measurements compared with the results of atomic multiplet calculations of Ti and Mn L(3,2) XAS, it is found that the Ti atoms are in the ionic state of 4 + and the Mn atoms are in the state of 2 +. In ResPES of Mn(0.2)TiSe(2) excited near the Ti 2p(3/2) and Mn 2p(3/2) absorption edges the Ti 3d and Mn 3d bands at binding energies just below the Fermi level are observed. According to theoretical calculations of E(k) the Ti 3d states are localized in the vicinity of the Γ point and the Mn 3d states are localized along the direction K-Γ-M in the Brillouin zone of the crystal.     

X-ray absorption and photoemission spectroscopy of 3C- and 4H-SiC

We have studied the electronic properties of 3C- and 4H-SiC with X-ray absorption (XAS). Particular emphasis is placed on the conduction bands because they exhibit larger differences between the various SiC polytypes than valence bands. XAS spectra at the Si2p and C1s edges provide projections onto Si3d, 4s and C2p conduction band states. We explain the observed differences in the Si L_2,3 XAS data to arise from transition into dispersive bands which occur at the M and K point of the hexagonal Brillouin zone. The XAS data are sensitive to a difference in the dispersion of the two lowest conduction bands. For 3C-SiC the dispersion is larger than for 4H-SiC in agreement with theory. We compare the XAS data at the Si L edge with CFS and CIS spectra and find that the SiLVV Auger is dominant.     

Effect of alkali metals and superalkali species on electronic properties of graphdiyne with open hexagonal edges

In the present work, we study the new two dimensional materials with tunable bandgap and high chemical reactivity via locating the alkali metals and superalkalis (Li, Na, K, Li3O, Na3O, and K3O) on the graphdiyne (GDY) sheets with open hexagonal edges. Our density functional theory (DFT) calculations reveal that the bandgap energy of GDY with a different open zigzag or armchair edges (ZGDY and AGDY) is decreased by interacting with alkali metals and superalkali species. We found that the alkali metals and superalkalis lowered the bandgap energy of AGDY and ZGDY by more than 170% and converted them into the semimetals. Our results also show that the M3O/ZGDY systems show higher chemical reactivity as compared to the other studied systems. Among the studied M(M3O)/ZGDY(AGDY) systems, the maximum binding energy, maximum means static polarisability, minimum bandgap energy, and minimum chemical hardness are related to the K3O/ZGDY complex. Consequently, the K3O/ZGDY is a promising chemically reactive material for applications in various fields such as gas detectors, catalysts in the oxygen reduction reactions, and drug delivery application.     

Nd^3＋：La2Be2O5单晶的光谱特性

Ｎｄ（３＋）：Ｌａ２Ｂｅ２Ｏ５（Ｎｄ（３＋）：ＢＥＬ）是一种具有单斜结构的双轴晶体，发射线性偏振荧光谱，当Ｅ∥Ｘ时，荧光峰值波长为１．０７０μｍ，Ｅ∥ｙ（ｂ）时，＝１．０７９μｍ．本文测量了Ｎｄ（３＋）：ＢＥＬ单晶的吸收谱，偏振和非偏振荧光谱，低温荧光谱（７７Ｋ°）和荧光寿命，（τ＝１３５±５μｓ），并且分析了其光谱特性与Ｎｄ（３＋）：ＹＡＧ作了比较，认为Ｎｄ（３＋）：ＢＥＬ更适合激光二极管泵浦．     

Electronic structure of hexagonal rare-earth manganites RMnO<Subscript>3</Subscript>

The optical spectra of single crystals of hexagonal rare-earth manganites RMnO₃ (R=Sc, Y, Er) are studied in the range from 0.7 to 5.4 eV. It is found that the spectra substantially differ from the spectra of orthorhombic manganites in both the positions of spectral features and their polarization anisotropy. It is shown that the optical absorption edge is determined by an abnormally strong (k?1) and narrow electric dipole transition with the center at approximately 1.6 eV with light polarization in the basal plane of the crystal. This transition can be treated with confidence as charge transfer from oxygen to manganese. The experimental results are in many instances substantially different from the first-principles calculations of the electronic structure of YMnO₃ published recently and, hence, may serve as a reliable basis for the further improvement of computational methods.     

The crystal structures and physical properties of the solid solution compound Ba₅Y_8-xMn₄O_21-1.5x（x = 0,1）

New oxometallides with the formula Ba5Y8 xMn4O21 1.5x(x = 0,1) are prepared through an atmospherecontrolled solid-state reaction.Two single-phase samples with Ba/Y/Mn atomic ratios 5/8/4(Y8) and 5/7/4(Y7) are obtained.The crystal structures and the physical properties of the compounds are investigated by X-ray powder diffraction,magnetization,conductivity,and dielectricity measurements.The Ba5Y8 xMn4O21 1.5x compound is demonstrated to be a Y-deficient solid solution.The solid solution compound Ba5Y8 xMn4O21 1.5x crystallizes into tetragonal symmetry with the space group I4/m.Detailed structure analysis by Rietveld refinement of the X-ray powder diffraction data reveals that the Y vacancies occur preferentially at the Y(2) site.Thermal magnetization measurements indicate the presence of antiferromagnetic interaction between Mn ions in the compounds,and temperature-dependent resistivity measurements show that insulator-semiconductor transitions occur around 175 K and 170 K for the Y8 and Y7 samples,respectively.Strong frequency dependences of the dielectric constant are observed above ～175 K for the two compounds.     

Comparison of electronic structures of orthorhombic and hexagonal manganites studied by X-ray absorption spectroscopy

Electronic structures of orthorhombic perovskite-type manganites (OM) and hexagonal manganites (HM) are compared by using X-ray absorption near edge structure spectroscopy. This study reveals that the environments around Mn and O ions in both the systems are different. These are reflected primarily in the lifting of degeneracy of the Mn 3d orbitals. Interestingly, the unoccupied Mn 3dx²−y² orbital in HM is strongly hybridized with O 2p states and appears to be responsible for both long range orderings: ferroelectric ordering at high temperatures and ferromagnetic ordering at low temperatures.     

4d-5p orbital mixing and asymmetric In 4d-O 2p hybridization in InMnO3: a new bonding mechanism for hexagonal ferroelectricity

Recent studies on the ferroelectricity origin of YMnO(3), a prototype of hexagonal manganites (h-RMnO(3), where R is a rare-earth-metal element), reveal that the d(0)-ness of a Y(3+) ion with an anisotropic Y 4d-O 2p hybridization is the main driving force of ferroelectricity. InMnO(3) (IMO) also belongs to the h-RMnO(3) family. However, the d(0)-ness-driven ferroelectricity cannot be expected because the trivalent In ion is characterized by a fully filled 4d orbital. Here we propose a new bonding mechanism of the hexagonal ferroelectricity in IMO: intra-atomic 4d(z(2))-5p(z) orbital mixing of In followed by asymmetric 4d(z(2))(In)-2p(z)(O) covalent bonding along the c axis.     

Soft X-ray resonant scattering study of single-crystal LaSr<Subscript>2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Soft X-ray resonant scattering studies at the Mn L_{II, III}- and the La M_{IV, V}- edges of single-crystal LaSr₂Mn₂O₇ are reported. At low temperatures, below T_N ≈ 160 K, energy scans with a fixed momentum transfer at the A-type antiferromagnetic (0 0 1) reflection around the Mn L_{II, III}-edges with incident linear σ and π polarizations show strong resonant enhancements. The splitting of the energy spectra around the Mn L_{II, III}-edges may indicate the presence of a mixed valence state, e.g., Mn³⁺/Mn⁴⁺. The relative intensities of the resonance and the clear shoulder-feature as well as the strong incident σ and π polarization dependences strongly indicate its complex electronic origin. Unexpected enhancement of the charge Bragg (0 0 2) reflection at the La M_{IV, V}-edges with σ polarization has been observed up to 300 K, with an anomaly appearing around the orbital-ordering transition temperature, T_OO ≈ 220 K, suggesting a strong coupling (competition) between them.     

Polarization and orientational effect in the x‐ray reflection and absorption spectra of sulfur in hexagonal CdS

The reflection spectra of hexagonal CdS in the vicinity of the SK and SL_{2, 3} absorption edges were studied using polarized synchrotron radiation. The absorption spectra were calculated using the Kramers–Kronig relationship. It was established that both polarization dependence of the SL_{2, 3} absorption spectra and orientational dependence of the SK absorption spectra are caused by the transitions into the p symmetry states split by the crystal field and by the photoelectron scattering from the atoms disposed in distant coordination shells. Because of the low probability of the transition of the electrons from the S 2p level into the p symmetry final states of the conduction band, the polarization dependence of the SL_{2, 3} absorption spectra is weak. Copyright © 2007 John Wiley & Sons, Ltd.     

Polarized SSXANES study of spin ordering in ferromagnetic and paramagnetic phases of La1.2Sr1.65Ca0.15Mn2O7

Spin-selected polarized X-ray absorption near-edge structures (SSXANES) at the Mn K-edge from a bilayer La_1.2Sr_1.65Ca_0.15Mn₂O₇ single crystal have been studied with high resolution, both in the ferromagnetic (15 K) as well as paramagnetic phase (300 K). The orientation-dependent SSXANES spectra show unmistakable temperature dependence as the system makes the ferromagnetic to paramagnetic phase transition. The pre-edge structures are too intense to be ascribed to weak quadrupole transitions and are interpreted in terms of hybridization of Mn 3d orbitals with O2p and Mn 4p orbitals over and above similar onsite hybridization. The results also indicate possible existence of a small local (time-frozen) ferromagnetic ordering in the macroscopically disordered state. Need for further experimental and theoretical work on the SSXANES spectra from the bilayer system is emphasized.     

Soft X-ray magnetic circular dichroism of Heusler-type alloy Co2MnGe

Co and Mn 2p core absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectra have been measured for the ferromagnetic ternary alloy Co₂MnGe. The observed Co 2p XAS spectrum can be understood on the basis of the unoccupied Co 3d partial density of states, whereas the overall features of the Mn 2p XAS and XMCD spectra have been partly reproduced by the Mn 2p⁵3d⁶ final state multiplets. We have found that the orbital polarization of the Co 3d and even the Mn 3d states are recognizable, which suggests that a spin-orbit coupling should be taken into account in the energy band structure in order to reproduce the half metallic nature of this alloy.     

Effect of the J–J Interaction of Excited States of the Rare-Earth Ion Pr3+ on Magnetically Polarized Luminescence of Praseodymium-Yttrium Aluminum Garnet

Physics of the Solid State - The spectra of luminescence and magnetic circular polarization of luminescence of praseodymium–yttrium aluminum garnet Pr3+ : Y3Al5O12 (PrYAG) are studied in the...     

锂锰尖晶石红外光谱的研究

本文对锂锰尖晶石的红外光谱进行了研究。由于锂锰尖晶石的晶体结构属于Fd3m空间群,锂离子占据四面体空隙(8a位置),锰离子占据八面体空隙(16d位置)。根据群论的知识,对锂锰尖晶石晶体中离子的振动方式与红外活性之间的内在关系进行了讨论。并列出了锂锰尖晶石的红外光谱实验数据。通过理论分析,我们推断:位于618.6和501.5cm~(-1)的红外吸收带分别来源于Mn(Ⅳ)-O和Mn(Ⅲ)-O键在晶体中的不对称伸缩振动(单元为Mn(Ⅳ)O_6和Mn(Ⅲ)O_6八面体),位于1124cm~(-1)的弱红外吸收带来源于Li-O键的不对称伸缩(单元为LiO_4四面体)。还有一些低于400cm~(-1)的可能吸收带在400～4000cm~(-1)范围内未能检测到。这一结论的可靠性通过锂锰尖晶石和掺杂的锂锰尖晶石的红外光谱实验数据得到证实。     

Correlated giant dielectric peaks and antiferromagnetic transitions near room temperature in pure and alkali-doped BaMnO(3-δ)

We report structural, magnetic, dielectric and thermal properties of single-crystal BaMnO(2.99) and its derivatives BaMn(0.97)Li(0.03)O(3) and Ba(0.97)K(0.03)MnO(3). The hexagonal 15R-BaMnO(2.99) perovskite phase is a known antiferromagnetic insulator that orders at a Néel temperature T(N) = 220 K. We find dilute Li and K doping change the ratio of cubic to hexagonal layers and cause drastic changes in the dielectric and magnetic properties. Unusually large high-temperature magnetoelectric shifts (up to 85%) are observed near temperatures at which pronounced peaks in the dielectric constant are observed for applied electric fields along either the c or a axis, respectively. The temperatures of the dielectric peaks are strongly correlated with anomalies in the c- or a-axis magnetic susceptibility and the specific heat for all compositions studied. All our data suggest that the strongly anisotropic magnetic and dielectric anomalies (which occur near, or above room temperature) originate from the same Mn ion sites, which implies these materials form an exceptional class of magnetoelectrics.     

Resonant inelastic scattering in dilute magnetic semiconductors by soft X-ray fluorescence spectroscopy

1-x Mn_xS (where 0.05<x<1) were measured as the energy of the exciting radiation was tuned across the S and Mn-L_2,3 absorption edges of these compounds. Strong resonance peaks in Mn-L emission spectra and the systematic appearance of new spectral features in S-L emission spectra were observed. Partial substitution of Zn by a magnetic Mn ion results in strong hybridization of the Mn 3d orbitals with the sp band of the host semiconductor. A detailed study of resonant inelastic scattering in the vicinity of the S and Mn-L_2,3 absorption edges of these DMS is presented. Received: 6 March 1997