Prediction of the Curie temperature is of significant importance for the design of ferromagnetic materials. Even though the Curie temperature has been estimated using the Heisenberg model, magnetic exchange coupling parameters widely used is thus far based on first-principles calculations at zero temperature. In the explicit consideration of temperature effects, it is important to minimise the total free energy, because the magnetic and phonon free energies correlate with each other. Here, we propose a first-principles thermodynamic approach to minimise the total free energy considering both the influences of magnetism on phonons and the feedback effect from phonons to magnetism. By applying our scheme to bcc Fe, we find a significant reduction of the Curie temperature due to the feedback effect. This result inevitably enforces us to change our convention as follows: we should use exchange coupling constants for the disordered local moment state, not for the ferromagnetic state, in the prediction of the Curie temperature. Our results not only change the fundamental understanding of finite-temperature magnetism but also provide a general framework to predict the Curie temperature more accurately.
B20-type MnSi is the prototype magnetic skyrmion material. Thin films of MnSi show a higher Curie temperature than their bulk counterpart. However, it is not yet clear what mechanism leads to the increase of the Curie temperature. In this work, we grow MnSi films on Si(100) and Si(111) substrates with a broad variation in their structures. By controlling the Mn thickness and annealing parameters, the pure MnSi phase of polycrystalline and textured nature as well as the mixed phase of MnSi and MnSi1.7 are obtained. Surprisingly, all these MnSi films show an increased Curie temperature of up to …
A full phonon intensity cancellation is reported in a longitudinal polarized inelastic neutron scattering experiment performed on the magnetocaloric compound MnFe$_{4}$Si$_{3}$, a ferromagnet with $T_{Curie}$ $\approx$ 305 K. The TA[100] phonon polarized along the $c$-axis measured from the Brillouin zone center $\textbf{G}$=(0, 0, 2) is observed only in one ($σ_{z}^{++}$) of the two non-spin-flip polarization channels and is absent in the other one ($σ_{z}^{--}$) at low temperatures. This effect disappears at higher temperatures, in the vicinity of $T_{Curie}$, where the phonon is measured in…
BiFeO3 is the most famous multiferroic material, but its G-type antiferromagnetism is highly desirable to be replaced by strong macroscopic magnetism beyond room temperature. Here we obtain double perovskite Bi2FeMoO6 with R3 (#146) space group by substituting Mo for 50% Fe in BiFeO3. Our first-principles calculated results show that it is a semiconductor with gap reaching to 0.725 eV, its net magnetic moment is 2μ_B per formula unit, and its ferroelectric polarization is 85μC/cm^2. This ferroelctricity is comparable with that of BiFeO3, but here the magnetism is a strong ferrimagnetism with C…
In order to study the magnetic excitation behaviors in colossal magnetoresistance manganites, a magnon-phonon interacting system is investigated. Sudden broadening of magnon linewidth is obtained when a magnon branch crosses over an optical phonon branch. Onset of the broadening is approximately determined by the magnon density of states. Anomalous magnon damping at the brillouine zone boundary observed in low Curie temperature manganites is explained.
Magneto-optic phonon resonances in magnetic topological EuCd2As2 via helical Raman spectroscopy
University of California, Los Angeles（加州大学洛杉矶分校）；Oak Ridge National Laboratory（橡树岭国家实验室）；Max Planck Institute for Chemical Physics of Solids（马克斯·普朗克固体化学物理研究所）；Indian Institute of Science Education and Research Bhopal（博帕尔科学教育研究院）
We report inelastic neutron scattering measurements of the phonon spectra in a pure powder sample of the multiferroic material BiFeO3. A high-temperature range was covered to unravel the changes in the phonon dynamics across the Neel (T_N ~ 650 K) and Curie (T_C ~ 1100 K) temperatures. Experimental results are accompanied by ab-initio lattice dynamical simulations of phonon density of states to enable microscopic interpretations of the observed data. The calculations reproduce well the observed vibrational features and provide the partial atomic vibrational components. Our results reveal clear…
Phonon densities of states (DOS) of bcc $α$-$^{57}$Fe were measured from room temperature through the 1044K Curie transition and the 1185K fcc $γ$-Fe phase transition using nuclear resonant inelastic x-ray scattering. At higher temperatures all phonons shift to lower energies (soften) with thermal expansion, but the low transverse modes soften especially rapidly above 700K, showing strongly nonharmonic behavior that persists through the magnetic transition. Interatomic force constants for the bcc phase were obtained by iteratively fitting a Born-von Kármán model to the experimental phonon spec…
Magnetocaloric (MC) materials present an avenue for chemical-free, solid state refrigeration through cooling via adiabatic demagnetization. We have used inelastic neutron scattering to measure the lattice dynamics in the MC material Ni45Co5Mn36.6In13.4. Upon heating across the Curie Temperature (TC), the material exhibits an anomalous increase in phonon entropy of 0.22 +/- 0.04 kB/atom, which is ten times larger than expected from conventional thermal expansion. This transition is accompanied by an abrupt softening of the transverse optic phonon. We present first-principle calculations showing…
The band convergence strategy, which improves Seebeck coefficient by inducing multi-valley in bandstructures, has been widely used in thermoelectric performance (TE) enhancing. However, the phonon-assisted intervalley scattering effect is neglected and the mode-selection rules remain unclear. In this work, TE properties for $α$-, $β$- and $γ$-PbP are intestigated under the consideration of full mode-, energy- and momentum-resolved electron-phonon interactions (EPI). The group theory is used to analyze the selection rules for EPI matrix elements. Our calculations reveal that, the intervalley sc…
Utilizing magnetic susceptibility, specific heat, thermal expansion and IR spectroscopy we provide experimental evidence that the two subsequent antiferromagnetic transitions in ZnCr_2S_4 at T_N1 = 15 K and T_N2= 8 K are accompanied by significant thermal and phonon anomalies. The anomaly at T_N2 reveals a strong temperature hysteresis typical for a first-order transformation. Due to strong spin-phonon coupling both magnetic phase transitions induce a splitting of phonon modes, where at T_N1 the high-frequency and at T_N2 the low-frequency modes split. The anomalies and phonon splitting observ…
Observation of the Nernst effect driven by longitudinal spin fluctuations
National Institute for Materials Science（国立材料研究所）；Research Institute for Interdisciplinary Science, Okayama University（冈山大学交叉科学研究所）；Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo（东京大学前沿科学研究生院先进材料科学系）
The piezoelectric (PZ) polarization effect enhances the phonon group velocity in wurtzite nitrides. This enhancement influences the phonon relaxation rates. We calculate the modified phonon relaxation rates in binary wurtzite nitrides (GaN, AlN and InN) by considering process like umklapp process, point defect, dislocation, boundary and phonon-electron scattering. The result will be useful to study the effect of PZ polarization on thermal conductivity of binary wurtzite nitrides (GaN, AlN and InN).
Interfacial thermal transport is critical for many thermal-related applications such as heat dissipation in electronics. While the total interfacial thermal conductance (ITC) can be easily measured or calculated, the ITC spectral mapping has been investigated only recently and is not fully understood. By combining nonequilibrium molecular dynamics simulations and atomistic Green's function method, we systematically investigate the ITC spectrum across an ideal interface, i.e., the argon-heavy argon interface. Our results show that the ITC spectrum increases gradually with temperature as more ph…
In this article, we report negative thermal expansion and spin frustration in hexagonal GdInO$_{3}$. Rietveld refinement of the XRD patterns reveal that the negative thermal expansion in the temperature range of 50-100K stems from the triangular lattice of Gd$^{3+}$ ions. At low temperature, the downward deviation of the inverse susceptibility ($χ^{-1}$) vs. $T$ plot from the Curie-Weiss law indicates spin frustration which inhibits long-range magnetic ordering down to 2K. Magnetostriction measurements clearly demonstrate a strong spin-lattice coupling. Low temperature anomalous phonon softeni…
We report the structure, magnetic property and spin polarization of CoFeMnGe equiatomic quaternary Heusler alloy. The alloy was found to exist in the L21 structure with considerable amount of DO3 disorder. Thermal analysis result indicated the Curie temperature is about 711K without any other phase transformation up to melting temperature. The magnetization value was close to that predicted by the Slater-Pauling curve. Current spin polarization of P = 0.70 {plus/minus}0.1 was deduced using point contact Andreev reflection (PCAR) measurements. Half-metallic trend in the resistivity has also bee…
We have investigated the coupling of lattice with spin via strain interactions in the CoFe2O4/PMN-PT composite system. X-ray diffraction and Raman spectroscopic studies illustrate a remarkable modification in CoFe2O4lattice across Curie temperature (450 K) of PMN-PT. Subsequently, CoFe2O4/PMN-PT composite reveals a sudden drop in magnetic moment across Tc of PMN-PT (450 K). However,theindependent CoFe2O4phasedisplaystypical ferromagnetic behaviour across this temperature. These findings establish spin-lattice coupling owing to th interfacial strain transfer between CoFe2O4 and PMN-PT in compos…
Magnetic Signature of Chiral Phonons Revealed by Neutron Spectroscopy in Ferrimagnetic Fe$_{1.75}$Zn$_{0.25}$Mo$_3$O$_8$
Nanjing University（南京大学）；National Laboratory of Solid State Microstructures（固体微结构物理国家重点实验室）；Institute of High Energy Physics, Chinese Academy of Sciences (CAS)（中国科学院高能物理研究所）；Spallation Neutron Source Science Center（散裂中子科学中心）；Hubei Normal University（湖北师范大学）
Molybdenum disulphide, a diamagnetic layered dichalcogenide solid, is found to show magnetic ordering at room temperature when exposed to a 2 MeV proton beam. The temperature dependence of magnetization displays ferrimagnetic behavior with a Curie temperature of 895 K. A disorder mode corresponding to a zone-edge phonon and a Mo valence higher than +4, have been detected in the irradiated samples using Raman and X-ray photoelectron spectroscopy, respectively. The possible origins of long-range magnetic ordering in irradiated MoS2 samples are discussed.
Anharmonic decay of coherent optical phonons in semimetal Sb has been investigated by using a femtosecond pump-probe technique. The coherent $A_{1g}$ mode is observed in time domain in a wide temperature range of 7 - 290 K. The decay rate (the inverse of the dephasing time) systematically increases as the lattice temperature increases, which is well explained by anharmonic phonon-phonon coupling, causing decay of the optical phonon into two acoustic phonon modes. The frequency of the $A_{1g}$ mode decreases with the temperature, which is interpreted to the results of both thermal expansion and…
A two-dimensional double-metal oxide MnCoO4 was predicted to be an intrinsic ferromagnetic semiconductor by using density functional theory. The low cleavage energy 0.36 Jm-2, which is similar to that of graphene, indicates that it can be easily exfoliated. The bulk structure has an antiferromagnetic ground state while the ferromagnetic configuration is the ground state against two antiferromagnetic and three ferrimagnetic configurations in the two-dimensional structure. The spin flip gaps for valence and conduction bands are 0.41 and 0.10 eV calculated with the HSE06 density functional, which…
It is generally assumed in the thermoelectric community that the lattice thermal conductivity of a given material is independent of the electronic properties. This perspective is however questionable since the electron-phonon coupling could have certain effects on both the carrier and phonon transport, which in turn will affect the thermoelectric properties. Using SiGe compound as a prototypical example, we give an accurate prediction of the carrier relaxation time by considering scattering from all the phonon modes, as opposed to the simple deformation potential theory. It is found that the c…
At low temperatures, phonon scattering can become so weak that phonon transport becomes ballistic. We calculate the ballistic phonon conductance G for membranes using elasticity theory, considering the transition from three to two dimensions. We discuss the temperature and thickness dependence and especially concentrate on the issue of material parameters. For all membrane thicknesses, the best conductors have, counter-intuitively, the lowest speed of sound.
Probing phonons, quasi-particle excitations and their coupling has enriched our understanding of these 2D materials and proved to be crucial for developing their potential applications. Here, we report comprehensive temperature, 4-330 K, and polarization-dependent Raman measurements on mono and bilayer MoSe2. Phonon's modes up to fourth-order are observed including forbidden Raman and IR modes, understood considering Frohlich mechanism of exciton-phonon coupling. Most notably, anomalous variations in the phonon linewidths with temperature pointed at the significant role of electron-phonon coup…
We present a theory of the isotope effect of the Curie temperature $T_{\rm c}$ in itinerant ferromagnets. The isotope effect in ferromagnets occurs via the electron-phonon vertex correction and the effective attractive interaction mediated by the electron-phonon interaction. The decrease of the Debye frequency increases the relative strength of the Coulomb interaction, which results in a positive isotope shift of $T_{\rm c}$ when the mass $M$ of an atom increases. Following this picture, we evaluate the isotope effect of $T_{\rm c}$ by using the Stoner theory and a spin-fluctuation theory. Whe…
CuInP2S6 (CIPS) is an emerging layered material that exhibits ferrielectric ordering well above room temperature (Curie temperature TC ~ 315 K). When synthesized with Cu deficiencies, CIPS spontaneously segregates into CuInP2S6 and In4/3P2S6 domains (CIPS-IPS), which form self-assembled heterostructures within the individual lamellae. This re-structuring and resultant chemical pressure raises the Curie temperature and, depending on the Cu concentration, can be up to ~340 K for the highest Cu deficiency. In both CIPS and CIPS-IPS, the loss of polarization through the ferrielectric-paraelectric …
A Magnetic Cluster Expansion (MCE) model for ternary face-centered cubic Fe-Ni-Cr alloys has been developed using DFT data spanning binary and ternary alloy configurations. Using this MCE model Hamiltonian, we perform Monte Carlo simulations and explore magnetic structures of alloys over the entire range of alloy compositions, considering both random and ordered alloy structures. In random alloys, the removal of magnetic collinearity constraint reduces the total magnetic moment but does not affect the predicted range of compositions where the alloys adopt low temperature ferromagnetic configur…
Chiral Phonons Enable Ultrafast Magnetization Switching via Magnetoelastic Coupling
Nanjing University of Aeronautics and Astronautics (NUAA)（南京航空航天大学）；Instituto de Ciencia de Materiales de Madrid (ICMM), CSIC（马德里材料科学研究所，西班牙国家科学研究委员会）；The University of Manchester（曼彻斯特大学）；University of York（约克大学）
Collapse of Jahn-Teller Phonons in La$_{1-x}$Sr$_{x}$MnO$_3$ with Weak Magnetoresistance
University of Colorado Boulder（科罗拉多大学博尔德分校）；Oak Ridge National Laboratory（橡树岭国家实验室）；Japan Atomic Energy Agency（日本原子能机构）；High Energy Accelerator Research Organization (KEK)（高能加速器研究机构）；Comprehensive Research Organization for Science and Society（综合科学研究组织）；Karlsruhe Institute of Technology（卡尔斯鲁厄理工学院）
Historically, the soft mode theory of ferroelectric phase transitions has been developed for the high-temperature (paraelectric) phase, where the phonon mode softens upon decreasing the temperature. In the low-temperature ferroelectric phase, a similar phonon softening occurs, also leading to a bosonic condensation of the frozen-in mode at the transition, but in this case the phonon softening occurs upon increasing the temperature. Here we present a soft mode theory of ferroelectric and displacive phase transitions by describing what happens in the low-temperature phase in terms of phonon soft…
We investigate spectral behavior of phonon spectral functions in an interacting multi-component hot carrier plasma. Dielectric polarization functions are formulated so that they satisfy Dyson equations of the effective interactions among plasma components. We find a useful sum rule giving simple relation between plasma-species resolved dielectric functions. Spectral analysis of various phonon spectral functions is performed considering carrier-phonon channels of polar and nonpolar optical phonons, acoustic deformation-potential, and piezoelectric Coulomb couplings. Effects of phonon self-energ…
In this paper we present the microscopic origin of the ferromagnetism of Fe0.25TaS2 and its finite-temperature magnetic properties. We first obtain the band structures of Fe0.25TaS2 by the first-principles calculations and find that both conventional and Dirac carriers coexist in metallic Fe0.25TaS2. Accordingly, considering the spin-orbit coupling of Fe 3d ion, we derive an effective RKKY-type Hamiltonian between Fe spins in the presence of both the conventional parabolic-dispersion and the Dirac linear-dispersion carriers, which contains a Heisenberg-like, an Ising-like and an XY-like term. …
Inelastic light scattering spectra of Bi_2Se_3 and Sb_2Te_3 single crystals have been measured over the temperature range from 5 K to 300 K. The temperature dependence of dominant A^{2}_{1g} phonons shows similar behavior in both materials. The temperature dependence of the peak position and linewidth is analyzed considering the anharmonic decay of optical phonons and the material thermal expansion. This work suggests that Raman spectroscopy can be used for thermometry in Bi_2Se_3- and Sb_2Te_3-based devices in a wide temperature range.
The exciton-phonon coupling in highly oriented pyrolytic graphite is studied using resonant inelastic X-ray scattering (RIXS) spectroscopy. With ~ 70 meV energy resolution, multiple low energy excitations associated with coupling to phonons can be clearly resolved in RIXS spectra. Using resonance dependence and the closed form for RIXS cross-section without considering the intermediate state mixing of phonon modes, the dimensionless coupling constant g is determined to be 5 and 0.4, corresponding to the coupling strength of 0.42 eV +/- 40 meV and 0.21 eV +/- 30 meV, for zone center and boundar…
The traditional theory of magnetic moments for chiral phonons is based on the picture of the circular motion of the Born effective charge, typically yielding a small fractional value of the nuclear magneton. Here we investigate the adiabatic evolution of electronic states induced by lattice vibration of a chiral phonon and obtain an electronic orbital magnetization in the form of a topological second Chern form. We find that the traditional theory needs to be refined by introducing a $\bm{k}$ resolved Born effective charge, and identify another contribution from the phonon-modified electronic …
A theoretical model is presented for the phonon limited mobility of the Dirac-Fermion gas in a three-dimensional (3D) Dirac semimetal Cd$_3$As$_2$ considering scattering from both the acoustic and the optical phonons. Screening effects are taken into account and it is found that they lead to a significant enhancement of the mobility. Simple analytical equations and power laws are obtained in both the Bloch-Gruneisen and equipartition regimes. The dependence of mobility on the temperature $T$ and the electron density $n_e$ is investigated. It is found that optical phonon limited mobility $μ_{op…
Considering screeening of electron scattering interactions in terms of the finite-temperature STLS theory and solving the linearized Boltzmann equation (with no appeal to a relaxation time approximation), we present a theoretical analysis of the low-temperature Seebeck effect in two-dimensional semiconductors with dilute electron densities. We find that the temperature ($T$) dependencies of the diffusion and phonon-drag thermoelectric powers ($S_d$ and $S_g$) can no longer be described by the conventional simple power-laws. As temperature increases, $|S_d|/T$ decreases when $T\gtrsim 0.1 ε_F$ …
The strategy of band convergence of multi-valley conduction bands or multi-peak valence bands has been widely used to search or improve thermoelectric materials. However, the phonon-assisted intervalley scatterings due to multiple band degeneracy are usually neglected in the thermoelectric community. In this work, we investigate the (thermo)electric properties of non-polar monolayer $β$- and $α$-antimonene considering full mode- and momentum-resolved electron-phonon interactions. We also analyze thoroughly the selection rules on electron-phonon matrix-elements using group-theory arguments. Our…
By considering analytical expressions for the self-energies of intervalley and intravalley phonons in graphene, we describe the behavior of D, 2D, and D$'$ Raman bands with changes in doping ($μ$) and light excitation energy ($E_L$). Comparing the self-energy with the observed $μ$ dependence of the 2D bandwidth, we estimate the wavevector $q$ of the constituent intervalley phonon at $\hbar vq\simeq E_L/1.6$ ($v$ is electron's Fermi velocity) and conclude that the self-energy makes a major contribution (60%) to the dispersive behavior of the D and 2D bands. The estimation of $q$ is based on an …
In addition to mechanisms already proposed to account for the formation in manganites of a small-polaron superlattice above the Curie temperature Tc and to a metallic-like sea of large polarons below Tc, we now consider other observed colossal-resistance inducing fields, such as magnetic, electric, photon, or strain fields. We attribute the charge-ordered phase formation to the occurrence of strong dipolar binding of vibronic small polarons arising from the phonon coupling of highly polarizable two-level orbital systems. These species having associated inherent electric and magnetic off-center…
High temperature (T) studies of La_{1-x}Ca_{x}MnO_{3} show that charge and phonon transport is significantly suppressed in a narrow doping region of x~1/2 and in a wide T range up to 900 K, which accompanies anomalous broadening of x-ray Bragg peaks. Contrarily, ferromagnetic (FM) correlation above Curie T is sharply enhanced at x~3/8. All these observations indicate the presence of short-range charge ordering (CO) correlation at high T, possibly in the form of a FM "zigzag", a small segment of the CE-type CO state. The decoupling and coupling of the FM zigzags for x~3/8 and 1/2, respectively,…
Thermodynamic Approach for Deciphering Magneto-Structural Phase Transitions: Proof of Concept in Heusler Alloys
Institute of Materials for Magnetism and Electronics, National Research Council（磁性材料与电子研究所，国家研究委员会）；V.G. Baryakhtar Institute of Magnetism of the NAS of Ukraine（乌克兰国家科学院 V.G. 巴里亚赫塔尔磁学研究所）；University of Vienna, Faculty of Physics（维也纳大学物理学院）；University for Continuing Education Krems（克雷姆斯继续教育大学）；University of Parma, Department of Mathematical, Physical and Computer Sciences（帕尔马大学数学、物理和计算机科学系）
A generalized Dirac equation is derived in order to describe charge carriers moving in corrugated graphene, which is the case for temperatures above 10°K due to the presence of flexural phonons. Such interaction is taken into account by considering an induced metric, in the same spirit as the general relativity approach for the description of fermionic particle moving in a curved space-time. The resulting equation allows to include in a natural way the presence of other phonon branches as well as an external electromagnetic field. It also predicts non-linear effects which are not present in th…
The electronic and magneto transport properties of reduced anatase TiO2 epitaxial thin films are analyzed considering various polaronic effects. Unexpectedly, with increasing carrier concentration, the mobility increases, which rarely happens in common metallic systems. We find that the screening of the electron-phonon (e-ph) coupling by excess carriers is necessary to explain this unusual dependence. We also find that the magnetoresistance (MR) could be decomposed into a linear and a quadratic component, separately characterizing the transport and trap behavior of carriers as a function of te…
