Raman scattering studies of hexagonal rare‐earth RMnO3 (R = Tb,Dy, Ho,Er) thin films

We have studied the rare‐earth (R) dependence of the phonon and magnon scattering in hexagonal RMnO₃ (R = Tb, Dy, Ho, Er) thin films using Raman scattering spectroscopy. We found, as the ionic radius of R decreases from Tb to Er, the phonons shift to higher energies. Our results indicate that both the lattice constants a and c of hexagonal RMnO₃ would decrease when the ionic radius of R decreases, and the lattice constant c would have a weaker R dependence. The magnons also shift to higher energies when the radius of the R ion decreases, and they show faster upshift than the phonons. In addition, the Néel temperature also shows a systematic increasing behavior when the radius of the R ion decreases. The dependence of the rare‐earth R on the magnons and the Néel temperature can be explained by the rapid increase of the spin‐exchange integral when the Mn–Mn distance decreases. Copyright © 2011 John Wiley & Sons, Ltd.     

Study on new magnetization property and its micro‐mechanism that occurred in anti‐ferromagnetic NiO nanoflowers with nearly uniform size

Temperature‐dependent magnetization and magnon Raman spectra were measured for anti‐ferromagnetic NiO‐nanoflowers. The results show several new magnetic behaviors, including the appearance of a ferromagnetic phase, a reduced Néel temperature (T_N) and a reduced Curie temperature (T_C). The temperature dependencies of the double magnon (2M) Raman wavenumber and intensity are similar to those of magnetization. A magnetic granules model (MGM) consisted of a crystalline core enclosed by a shell is proposed. The model suggests that the large quantity of spins induced by specific surface effect in the shell plays a key role in nano‐magnetism. Based on the MGM, the micro‐mechanism of the observed new magnetic behavior is understood by the magnon Raman spectra. The MGM is based on the general features of magnetic nano‐particles, and thus it should be generally applicable to common magnetic nano‐particles. Copyright © 2014 John Wiley & Sons, Ltd.     

Identification of Mn‐related Raman modes in Mn‐doped ZnO thin films

This article aims to investigate the Raman modes present in Mn‐doped ZnO thin films that are deposited using the magnetron co‐sputtering method. A broad band ranging from 500 to 590 cm⁻¹ is present in the Raman spectra of heavily Mn‐doped ZnO films. The multi‐peak‐fitting results show that this broad band may be composed of six peaks, and the peak at 528 cm⁻¹ could be a characteristic mode of Mn₂O₃. The results of this study suggest that the origin of the Raman peaks in Mn‐doped ZnO films may be due to three major types: structural disorder and morphological changes caused by the Mn dopant, Mn‐related oxides and intrinsic host‐lattice defects. Copyright © 2010 John Wiley & Sons, Ltd.     

A Mössbauer study of the quasi two-dimensional antiferromagnet TlFe2−x Se2

TlFe_2?x Se₂ compounds withx from 0.36 to 0.40 have been examined with Mössbauer spectroscopy. The compounds order antiferromagnetically with broad magnetic transition regions whose width increases with decreasing Fe content. The Néel temperature decreases with x and the temperature variation of the magnetic hyperfine field indicates that the transition is of first order. In samples without vacancy ordering the Fe nuclei experience a different temperature variation of the hyperfine field than in compounds with ordered vacancies.     

Theoretical study of magnetic susceptibility of orbitally unquenched compound KCoF3

The effect of residual orbital magnetic moment of Co²⁺ in KCoF₃ on the magnetic susceptibility has been studied. For the calculation for both the ordered state and the paramagnetic state we have applied the correlated effective field approximation developed by Lines. An excellent value of the Néel temperature is obtained and, except near the Néel temperature, the calculated susceptibility agrees well with the experimental results over the whole temperature range.     

Raman spectroscopy studies of antiferromagnetic FeCO3 and related carbonates

Raman spectroscopy experiments were performed on antiferromagnetic siderite (natural FeCO₃). Weak lines at room temperature (in addition to the expected vibrational lines) were found to be seven well defined excitations at liquid helium temperature. Polarization tensor components of these new lines were examined at temperatures varying between room and liquid helium temperature. Frequency decreases upon cooling were observed for three of the lines (the greatest change occuring near the Néel temperature, 38 K). By comparison with infrared spectra, variable temperature Raman spectra and impurity analysis of two related crystals (antiferromagnetic MnCO₃ and CaMg(CO₃)₂ containing 6% iron), new explanations for two (741 and 1735 cm^?1) of three previously observed lines and for one (870cm^?1) of the remaining four are presented. The three variable frequency lines (440,1175 and 1225 cm^?1) are considered magnetic excitations between trigonal field, spin-orbit, and exchange split states of the ferrous ion. The frequency decreases upon cooling may be due to unquenched orbital angular momentum resulting in an exchange interaction of a non-Heisenberg form. Symmetry distortion due to magnetic ordering upon cooling may cause the infrared 741 cm^?1 vibration to become Raman-active.     

Low temperature properties of the metallic antiferromagnet ErZn12

The metallic antiferromagnet ErZn₁₂ orders magnetically at 2·76°K. We report measurements of the susceptibility, magnetisation, resistivity and specific heat of polycrystalline specimens of it in the vicinity of the magnetically ordered regime. We find evidence for a metamagnetic or spin-flop transition in fields of 3–7KOe. The resistivity increases monotonically from low temperature to the Néel point and has a power-law dependence on temperature of Tⁿ, where n～6·5. The specific heat shows a lambda anomaly at the Néel point and the divergences which appear above and below it are compared with those reported previously in the resistivity. The magnetic entropy indicates that the ordering process involves only one crystal-field doublet.     

Temperature dependent Raman scattering in polycrystalline Bi4Ti3O12 thin films

Polycrystalline Bi₄Ti₃O₁₂ thin films were prepared on quartz substrates by pulsed laser deposition. The films were crystallized in the orthorhombic layer perovskite structure confirmed by X-ray diffraction and Raman spectroscopy. The Raman spectra are strongly dependent on temperature. A subtle phase transition in the temperature range 473-573 K exists in polycrystalline BTO thin films, which is evidenced by the disappearance of the Raman band at 116 cm⁻¹ and appearance of a new Raman band at 151 cm⁻¹. The two broad Raman bands centered at the 57 and 93 cm⁻¹ at 300 K break up into clusters of several sharp Raman peaks at 77 K, due to monoclinic distortion of orthorhombic structure at low temperature in the as-prepared Bi₄Ti₃O₁₂ thin films.     

Structure and orbital ordering of ultrathin LaVO3 probed by atomic resolution electron microscopy and Raman spectroscopy

Orbital ordering has been less investigated in epitaxial thin films, due to the difficulty to evidence directly the occurrence of this phenomenon in thin film samples. Atomic resolution electron microscopy enabled us to observe the structural details of the ultrathin LaVO₃ films. The transition to orbital ordering of epitaxial layers as thin as ≈4 nm was probed by temperature‐dependent Raman scattering spectroscopy of multilayer samples. From the occurrence and temperature dependence of the 700 cm^–1 Raman active mode it can be inferred that the structural phase transition associated with orbital ordering takes place in ultrathin LaVO₃ films at about 130 K.     

Magnetic ordering in Co<Subscript><Emphasis Type="Italic">c</Emphasis></Subscript>Mg<Subscript>1−<Emphasis Type="Italic">c</Emphasis></Subscript>O solid solutions

The influence of dilution by diamagnetic ions on the magnetic ordering in single-crystal Co _c Mg_1−c O solid solutions was studied by Raman spectroscopy and magneto-optical microscopy in a wide range of temperatures (6 < T < 200 K). Far infrared absorption measurements of antiferromagnetic resonance (AFMR) were also performed for pure CoO. It was found that the domain structure and the contribution from Brillouin zone center magnons to Raman scattering and AFMR disappear well below the Néel temperature, whose value was determined from neutron diffraction and magnetic susceptibility measurements. The text was submitted by the authors in English.     

Study of spin–phonon coupling in LiFe1 − xMnxPO4olivines

LiFe_{1 − x}Mn_xPO₄ olivines are promising material for improved performance of Li‐ion batteries. Spin–phonon coupling of LiFe_{1 − x}Mn_xPO₄ (x = 0, 0.3, 0.5) olivines is studied through temperature‐dependent Raman spectroscopy. Among the observed phonon modes, the external mode at ~263 cm⁻¹ is directly correlated with the motions of magnetic Fe²⁺/Mn²⁺ ions. This mode displays anomalous temperature‐dependent behavior near the Néel temperature, indicating a coupling of this mode with spin ordering. As Mn doping increases, the anomalous behavior becomes clearly weaker, indicating the spin–phonon coupling quickly decreases. Our analyses show that the quick decrease of spin–phonon coupling is due to decrease of the strength of spin–phonon coupling, but not change of spin‐ordering feature with Mn doping. Importantly, we suggest that the low electrochemical activity of LiMnPO₄ is correlated with the weak spin–phonon coupling strength, but not with the weak ferromagnetic ground state. Our work would play an important role as a guide in improving the performances of future Li‐ion batteries. Copyright © 2015 John Wiley & Sons, Ltd.     

Micro‐Raman study of orbiton–phonon coupling in YbVO3

First‐order and multiphonon Raman active excitations are studied in YbVO₃ as a function of temperature in the orthorhombic and monoclinic phases. Below T ≃ 170 K, a G‐type orbital ordering with a concomitant monoclinic transition occurs. They enhance the phonon polarizabilities, allowing the resolution of room‐temperature bands, and activate new excitations around 700 cm⁻¹. Below T ∼ 65 K, the 700 cm⁻¹ excitations disappear, indicating a C‐type orbital ordering and a return to the orthorhombic structure. The observed phonon combinations around 1400 cm⁻¹ with a dominant Jahn‐Teller vibration at ∼690 cm⁻¹ reflect a possible orbiton‐phonon coupling. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of powders and thin films of bismuth ferrite from solution: a magneto-electric study

Metalorganic decomposition and coprecipitation from aqueous solution have been used to synthesize thin film and bulk bismuth ferrite (BiFeO₃) with perovskite structure. X-ray diffraction, thermomagnetic analysis, and scanning electron microscopy were used to analyze the material and identify spurious phases. The magnetic characterization at room temperature revealed remarkable differences between bulk and film samples. The results show that in BiFeO₃ bulk ceramics, spontaneous magnetization is not observed at room temperature. Nevertheless, in thin films, a well-defined ferromagnetic behavior is observed at room temperature. Dielectric measurements taken on ceramic samples present an anomaly around 643 K that can be associated with the Néel temperature.     

Specific features of local structural,valence, and magnetic states of iron ions in the perovskite Bi0.5Ca0.5FeO3

The perovskite Bi_0.5Ca_0.5FeO₃ has been investigated using the Mössbauer effect at temperatures of 295 and 675 K. The measured temperature of the magnetic phase transition (Néel temperature) is T _N = 640 ± 10 K. Above the Néel temperature, there are two nonequivalent structural states of iron ions. In the perovskite Bi_0.5Ca_0.5FeO₃ at room temperature, there are seven most probable nonequivalent magnetic states of iron ions with significantly different values of the hyperfine interaction parameters. Four iron states correspond to Fe³⁺ ions in the octahedral oxygen environment, and three iron states correspond to Fe³⁺ ions in the tetrahedral oxygen environment.     

Magnetic ordering in Ho‐doped Bi2Te3 topological insulator

We investigate the magnetic properties of Ho‐doped Bi₂Te₃ thin films grown by molecular beam epitaxy. Analysis of the polarized X‐ray absorption spectra at the Ho M₅ absorption edge gives an effective 4f magnetic moment which is ～45% of the Hund's rule ground state value. X‐ray magnetic circular dichroism (XMCD) shows no significant anisotropy, which suggests that the reduced spin moment is not due to the crystal field effects, but rather the presence of non‐magnetic or antiferromagnetic Ho sites. Extrapolating the temperature dependence of the XMCD measured in total electron yield and fluorescence yield mode in a field of 7 T gives a Curie–Weiss temperature of ?_CW ≈ –30 K, which suggests antiferromagnetic ordering, in contrast to the paramagnetic behavior observed with SQUID magnetometry. From the anomaly of the XMCD signal at low temperatures, a Néel temperature T_N between 10 K and 25 K is estimated. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Neutron diffraction study of RECo2Si2 intermetallics

A neutron diffraction study of polycrystalline RECo₂Si₂ intermetallics (RE = Pr, Nd, Tb, Ho, Er) carried out at liquid helium temperature shows the presence of a collinear antiferromagnetic ordering of +?+? type. Magnetic moment is localized on RE ions only and amounts to the RE³⁺ free ion value. In ErCo₂Si₂ the magnetic moment is normal to the tetragonal unique axis, whereas in the remaining compounds the magnetic moment is aligned along it. Néel points were determined from the temperature dependence of magnetic peak heights.     

Reduced magnetic hyperfine field at the surface of α-Fe2O3 and FeBO3 single crystals

The surface magnetic ordering of an α-⁵⁷Fe₂O₃ and ⁵⁷FeBO₃ single crystal was studied by Depth Selective Conversion Electron Mössbauer Spectroscopy (DCEMS). The depth selective Mössbauer data of ⁵⁷FeBO₃ up to the Néel temperature (T _N = 348.35 K) reveal the coexistence of the canted antiferromagnetic bulk phase and a magnetic surface phase that shows time relaxation. Both phases are separated by a wall (interim layer) and the thickness of the magnetic surface layer increases as the crystal is heated to T _N.     

Mössbauer study of fluorides: Ba2MFeF9 and NaBaFe2F9

The Mössbauer spectra of the compounds Ba₂NiFeF₉, Ba₂FeCrF₉ and NaBaFe₂F₉ have been studied as a function of temperature. Values of the Néel temperature are obtained and the effects of cationic inversion between the two sites of M^II and M^III in compounds Ni^IIFe^III and Fe^IICr^III are observed. In the latter compound, we observe broad lines at all temperatures and a smearing of the magnetic ordering temperature. However, the Fe^IIFe^III compound shows strict structural order. The two sites of Fe^III in NaBaFe₂F₉ have not been resolved.     

Long-range and short-range magnetic order in new compound NaVGe<Subscript>2</Subscript>O<Subscript>6</Subscript>

New metal oxide pyroxene compound NaVGe₂O₆ containing isolated edge-sharing VO₆ (S=1) chains undergoes transition into a long-range antiferromagnetic state at T _N =16 K. The broad maximum in the temperature dependence of magnetic susceptibility at T _M =26 K indicates the low-dimensional character of the magnetic subsystem. Even though the antiferromagnetic ordering is accompanied by a sharp peak of specific heat, significant magnetic entropy is released above the Néel temperature.     

Optical investigation of metamagnetic DyAlO3

We have investigated the optical absorption spectra of metamagnetic DyAlO₃ (T _N =3.4 °K) above and below the Néel temperature. We find that the magnetic interactions are predominantly between the ions along the crystallographicc-axis; the interaction energy between two ions isW _C =? (2.9±0.6) cm^?1. Additional line-shifts below 3.4 °K yield the Néel temperature. Zeeman effect studies give the magnetic moment of the groundstate as μ=(9.2 ± 0.9)μ _B . The direction of the magnetic moments is in thea-b plane, with angles of ± 33.5° and ± 146.5° from theb-axis. The Zeeman effect studies reveal two metamagnetic transitions (forH _ext∥μ) at 7.0 and 7.3 kOe respectively. Additional susceptibility and Mössbauer measurements confirm the Néel temperature and the magnetic moment.