4f Moments Research Articles

Giant magnetocaloric effect in the antiferromagnet GdScO3 single crystal

We have investigated the magnetic properties and the magnetocaloric effect of GdScO3 single crystal. A paramagnetic-antiferromagnetic magnetic phase transition has been observed in GdScO3 single crystal at low temperature, with Gd3+ sublattice in [001] direction (TN = 2.6 K) and [010] direction (TN = 2.8 K). This compound shows noticeable giant magnetocaloric effect with the maximum value of magnetic entropy change that come up to 47.3 J/kg K in [001] direction and 52.5 J/kg K in [010] direction for a field change of 70 kOe around its Néel temperature. The large magnetocaloric effect is due to the localized 4f moment of Gd3+ (J = S = 7/2) ions. Taking the interactions of the system into consideration, the magnetization and magnetic entropy change can both be well fitted by the molecular field theory based on mean field approximation. The giant magnetocaloric effect suggest that GdScO3 could be a potential material for magnetic refrigeration in low-temperature region.

Emerging 2D-ferromagnetism and strong spin-orbit coupling at the surface of valence-fluctuating EuIr2Si2

The development of materials that are non-magnetic in the bulk but exhibit two-dimensional (2D) magnetism at the surface is at the core of spintronics applications. Here, we present the valence-fluctuating material EuIr2Si2, where in contrast to its non-magnetic bulk, the Si-terminated surface reveals controllable 2D ferromagnetism. Close to the surface the Eu ions prefer a magnetic divalent configuration and their large 4f moments order below 48 K. The emerging exchange interaction modifies the spin polarization of the 2D surface electrons originally induced by the strong Rashba effect. The temperature-dependent mixed valence of the bulk allows to tune the energy and momentum size of the projected band gaps to which the 2D electrons are confined. This gives an additional degree of freedom to handle spin-polarized electrons at the surface. Our findings disclose valence-fluctuating rare-earth based materials as a very promising basis for the development of systems with controllable 2D magnetic properties which is of interest both for fundamental science and applications.

Low-Temperature Properties of CePt3P Tuned by Magnetic Field**Supported by the Zhejiang Provincial Natural Science Foundation of China under Grant No LQ19A040006, and the Scientific Research Fund of Zhejiang Provincial Education Department under Grant No Y201840160.

We present low-temperature magnetization, magnetoresistance and specific heat measurements on the Kondo lattice compound CePt3P under applied magnetic fields up to 9.0 T. At zero field, CePt3P exhibits a moderately enhanced Sommerfeld coefficient of electronic specific heat γCe = 86 mJ/mol·K2 as well as two successive magnetic transitions of Ce 4f moments: an antiferromagnetic ordering at TN1 = 3.0K and a spin reorientation at TN2 = 1.9 K. The value of TN1 shifts to lower temperature as magnetic field increases, and it is ultimately suppressed around Bc ∼ 3.0T at 1.5 K. No evidence of non-Fermi liquid behavior is observed around Bc down to the lowest temperature measured. Moreover, γ decreases monotonously with increasing the magnetic field. On the other hand, the electrical resistivity shows an anomalous temperature dependence ρ ∝ Tn with the exponent n decreasing monotonously from ∼2.6 around Bc down to ∼1.7 for B = 9.0 T. The T–B phase diagram constructed from the present experimental results of CePt3P does not match the quantum criticality scenario of heavy fermion systems.

Strain-induced spontaneous Hall effect in an epitaxial thin film of a Luttinger semimetal

Pyrochlore iridates have provided a plethora of novel phenomena owing to the combination of topology and correlation. Among them, much attention has been paid to [Formula: see text], as it is known as a Luttinger semimetal characterized by quadratic band touching at the Brillouin zone center, suggesting that the topology of its electronic states can be tuned by a moderate lattice strain and external magnetic field. Here, we report that our epitaxial [Formula: see text] thin films grown by solid-state epitaxy exhibit a spontaneous Hall effect that persists up to 50 K without having spontaneous magnetization within our experimental accuracy. This indicates that the system breaks the time reversal symmetry at a temperature scale that is too high for the magnetism to be due to Pr 4f moments and must be related to magnetic order of the iridium 5d electrons. Moreover, our analysis finds that the chiral anomaly induces the negative contribution to the magnetoresistance only when a magnetic field and the electric current are parallel to each other. Our results indicate that the strained part of the thin film forms a magnetic Weyl semimetal state.

Pressure Effects on the 4f Electronic Structure of Light Lanthanides.

Using the satellite structure of the Lγ_{1} line in nonresonant x-ray emission spectra, we probe the high-pressure evolution of the bare 4f signature of the early light lanthanides at ambient temperature. For Ce and Pr the satellite peak experiences a sudden reduction concurrent with their respective volume collapse (VC) transitions. These new experimental results are supported by calculations using state-of-the-art extended atomic structure codes for Ce and Pr, and also for Nd, which does not exhibit a VC. Our work suggests that changes to the 4f occupation are more consistently associated with evolution of the satellite than is the reduction of the 4f moment. Indeed, we show that in the case of Ce, mixing of a higher atomic angular momentum state, driven by the increased hybridization, acts to obscure the expected satellite reduction. These measurements emphasize the importance of a unified study of a full set of microscopic observables to obtain the most discerning test of the underlying, fundamental f-electron phenomena at high pressures.

Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal\u2013metal bond

Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical bridges is a fruitful strategy towards stronger coupling. In this work we explore the limiting case when the role of a radical bridge is played by a single unpaired electron. We synthesize an array of air-stable Ln2@C80(CH2Ph) dimetallofullerenes (Ln2 = Y2, Gd2, Tb2, Dy2, Ho2, Er2, TbY, TbGd) featuring a covalent lanthanide-lanthanide bond. The lanthanide spins are glued together by very strong exchange interactions between 4f moments and a single electron residing on the metal–metal bonding orbital. Tb2@C80(CH2Ph) shows a gigantic coercivity of 8.2 Tesla at 5 K and a high 100-s blocking temperature of magnetization of 25.2 K. The Ln-Ln bonding orbital in Ln2@C80(CH2Ph) is redox active, enabling electrochemical tuning of the magnetism.

Identification of spin wave resonances and crystal field levels in simple chromites RCrO3 (R = Pr, Sm, Er) at low temperatures in the THz spectral region

We report on THz absorption spectroscopy combined with high magnetic fields of polycrystalline RCrO3 (R = Pr, Sm, Er) aiming understanding spin wave resonances at their low temperature magnetic phases.Our measurements show that the temperature, and the implicit anisotropies at which the Cr3+ spin reorientation at TSR takes place, are determinant on the ferromagnetic-like (FM) and the antiferromagnetic-like (AFM) spin modes being optically active. It is found that they are dependent on Rare Earth 4f moment and ion size.We also studied temperature and field dependence of crystal field levels in the same spectroscopic region. Pr3+ non-Kramers emerges at 100 K and Zeeman splits. An observed absence of spin wave resonances in PrCrO3 is attributed to Pr3+ remaining paramagnetic. In SmCrO3 near cancelation of the spin and orbital moments is proposed as the possible reason for not detecting Sm3+ ground state transitions. Here, the FM and AFM resonant modes harden when the temperature decreases and split linearly under applied fields at 5 K and below. In ErCrO3 the Er3+ Kramers doublet becomes active at about the TSR onset. Each line further experiences Zeeman splitting under magnetic fields while an spin reversal induced by a ∼2.5 T field, back to the Γ4 (Fz) from the Γ1 phase at 2 K, produces a secondary splitting.The 5 K AFM and FM excitations in ErCrO3 have a concerted frequency-intensity temperature dependence and a shoulder pointing to the Er3+ smaller ion size also disrupting the two magnetic sublattice approximation. Both resonances reduce to one when the temperature is lowered to 2 K in the Γ1 representation. Our findings have important implications on the complex interplay in the magneto-electrodynamics associated with the Rare-Earth 4f – 3d transition metal spin coupling and the structural A site instabilities in perovskite multiferroics.

Evolution of the spin hall magnetoresistance in Cr2O3/Pt bilayers close to the Néel temperature

We study the evolution of magnetoresistance with temperature in thin film bilayers consisting of platinum and antiferromagnet Cr2O3 with its easy axis out of the plane. We vary the temperature from 20 °C to 60 °C, in the vicinity of the Néel temperature of Cr2O3 of approximately 37 °C. The magnetoresistive response is recorded during rotations of the external magnetic field in three mutually orthogonal planes. A large magnetoresistance having a symmetry consistent with a positive spin Hall magnetoresistance is observed in the paramagnetic phase of Cr2O3, which however vanishes when cooling to below the Néel temperature. Compared to analogous experiments in a Gd3Ga5O12/Pt bilayer, we conclude that a paramagnetic moment in the insulator induced by an applied magnetic field is not sufficient to explain the observed magnetoresistance. We speculate that the type of magnetic moment at the interface qualitatively impacts the spin angular momentum transfer, with the 3d moments of Cr sinking angular momentum much more efficiently as compared to the more localized 4f moments of Gd.

Radical-lanthanide ferromagnetic interaction in a TbIII bis-phthalocyaninato complex

Recent studies have highlighted the importance of organic ligands in the field of molecular spintronics, via which delocalized electron-spin density can mediate magnetic coupling to otherwise localized 4f moments of lanthanide ions, which show tremendous potential for single-molecule device applications. To this end, high-field/high-frequency electron paramagnetic resonance (EPR) spectroscopy is employed to study a neutral terbium bis-phthalocyaninato metalorganic complex, [TbPc2]0, with the aim of understanding the magnetic interaction between the Ising-like moment of the lanthanide ion and the unpaired spin density on the coordinating organic radical ligand. The measurements were performed on a previously unknown [TbPc2]0 structural phase crystallizing in the Pnma space group. EPR measurements on powder samples of [TbPc2]0 reveal an anisotropic spectrum, which is attributed to the spin-12 radical coupled weakly to the EPR-silent TbIII ion. Extensive double-axis rotation studies on a single crystal reveal two independent spin-12 signals with differently oriented (albeit identical) uniaxial g-tensors, in complete agreement with x-ray structural studies that indicate two molecular orientations within the unit cell. The easy-axis nature of the radical EPR spectra thus reflects the coupling to the Ising-like TbIII moment. This is corroborated by studies of the isostructural [YPc2]0 analog (where Y is nonmagnetic yttrium), which gives a completely isotropic radical EPR signal. The experimental results for the terbium complex are well explained on the basis of an effective model that introduces a weak ferromagnetic Heisenberg coupling between an isotropic spin-12 and an anisotropic spin-orbital moment, J=6, that mimics the known, strong easy-axis TbPc2 crystal-field interaction.

Strong coupling between localized 5f moments and itinerant quasiparticles in the ferromagnetic superconductor UGe2**Project supported by the National Natural Science Foundation of China (Grant No. 11404297), the Science Challenge Project (Grant No. TZ2016004), and the Science and Technology Foundation of China Academy of Engineering Physics (Grant Nos. 2013B0301050 and 2014A0301013).

The heavy fermion physics arises from the complex interplay of nearly localized 4f/5f electrons and itinerant band-like ones, yielding heavy quasiparticles with an effective mass about 100 times (or more) of the bare electrons. Recently, experimental and theoretical investigations point out a localized and delocalized dual nature in actinide compounds, where itinerant quasiparticles account for the unconventional superconductivity in the vicinity of a magnetic instability. Here we report the strong coupling between localized 5f moments and itinerant quasiparticles in the ferromagnetic superconductor UGe2. The coupling is nearly antiferromagnetic. As embedded in the ferromagnetic matrix of localized 5f moments below , this coupling leads to short-range dynamic correlations of heavy quasiparticles, characterized by fluctuations of magnetic clusters. Those cluster-like spins of itinerant quasiparticles show a broad hump of magnetization at , which is typical for the spin-glass freezing. Thus, our results present the direct observation of itinerant quasiparticles coexisting with localized 5f moments by conventional magnetic measurements, providing a new route into the coexistence between ferromagnetism and superconductivity in heavy fermion systems.

Correlating Itinerant Magnetism in RCo2Pn2 Pnictides (R = La, Ce, Pr, Nd, Eu, Ca; Pn = P, As) to Their Crystal and Electronic Structures.

Rare-earth cobalt pnictides, RCo2Pn2 (Pn = P, As), belong to the ThCr2Si2 structure type, which is ubiquitous among intermetallic compounds. The structural and magnetic properties of simple ternary RCo2P2 phosphides, which combine partially delocalized (itinerant) 3d magnetic moments of cobalt and localized 4f magnetic moments of lanthanides, were investigated extensively in 1980-1990s, predominantly by the Jeitschko group. Those studies established that LaCo2P2 shows ferromagnetic (FM) ordering of Co moments, while the other members of the series, with R = Ce, Pr, Nd, or Sm, exhibit antiferromagnetic (AFM) ordering in both R and Co magnetic sublattices. This observation also correlated with the larger separation between the [Co2P2] layers in the crystal structure of LaCo2P2 as compared to the decreased interlayer distances in the other structures of the RCo2P2 series. Our work over the past decade has focused on unraveling the rich magnetic behavior that can be observed in these systems when internal chemical and external physical factors are used to perturb their crystal and electronic structures. We began our foray into these materials by demonstrating that the preservation of FM ordering of Co 3d moments in the mixed La1-xR'xCo2P2 phases also forces the R 4f moments to adopt FM arrangement, although antiparallel to the Co moments. As an example, in La0.75Pr0.25Co2P2 such mutual influence of the 3d and 4f moments leads to a cascade of magnetic phase transitions. All these changes were traced back to the modification of the crystal structure and, consequently, the electronic band structure of these materials. The substitution of smaller R3+ ions for the La3+ ions leads to structural compression along the tetragonal c axis, perpendicular to the [Co2P2] layers, and an increase in the Co-Co distances within the layer. This structural effect is translated into more localized Co magnetic moments, stronger magnetic exchange between Co sites, and higher ordering temperatures. A more dramatic change in properties is observed in EuCo2Pn2, which exhibit AFM ordering of the localized 4f moments of Eu2+ ions and only paramagnetic behavior in the Co sublattice. Under applied pressure, these compounds undergo structural collapse, which causes a dramatic decrease in the separation between the [Co2Pn2] layers, an increase in the oxidation state of Eu, and magnetic ordering of Co moments. We further demonstrated that similar effects can be stimulated by chemical compression, which is achieved by doping Eu into the more constrained lattice sites, for example, in PrCo2P2 or CaCo2As2. In both cases, the induced mixed valence of Eu results in the change from AFM to FM ordering in the Co sublattice. A series of solid solutions Ca1-xEuxCo2As2 shows a fascinating evolution of magnetic behavior from AFM ordering of Co 3d moments to simultaneous FM ordering of Co 3d and Eu 4f moments to AFM ordering of Eu 4f moments as one proceeds from CaCo2As2 to EuCo2As2. Importantly, all these changes in magnetic properties are well justified by the analysis of electronic density of states and crystal orbital Hamilton population, providing the understanding of how chemical factors can be leveraged, in general, to modify properties of itinerant magnets.

Probing Magnetism in the Vortex Phase of PuCoGa_{5} by X-Ray Magnetic Circular Dichroism.

We measure x-ray magnetic circular dichroism (XMCD) spectra at the Pu M_{4,5} absorption edges from a newly prepared high-quality single crystal of the heavy-fermion superconductor ^{242}PuCoGa_{5}, exhibiting a critical temperature T_{c}=18.7 K. The experiment probes the vortex phase below T_{c} and shows that an external magnetic field induces a Pu 5f magnetic moment at 2K equal to the temperature-independent moment measured in the normal phase up to 300K by a superconducting quantum interference device. This observation is in agreement with theoretical models claiming that the Pu atoms in PuCoGa_{5} have a nonmagnetic singlet ground state resulting from the hybridization of the conduction electrons with the intermediate-valence 5f electronic shell. Unexpectedly, XMCD spectra show that the orbital component of the 5f magnetic moment increases significantly between 30 and 2K; the antiparallel spin component increases as well, leaving the total moment practically constant. We suggest that this indicates a low-temperature breakdown of the complete Kondo-like screening of the local 5f moment.

Strain Engineering of the CeNi5 System

The effect of strain on the CeNi5 system has been investigated using density functional theory (DFT). The studies have shown that localised Ce 4f and Ni 3d states carry the magnetic moment of the material. The Ce 4f moment remains relatively unchanged during strain whereas the Ni 3d moment increases as the strain becomes increasingly tensile in both the basal and non-basal directions. A significant strain-dependent interaction exists between delocalised, non-magnetic Ce 6s–Ni 4s states. A weaker group of Ni 3d–Ce 6s/Ni 4s and Ni 3d–Ni 3d interactions exist, indicating that competing localised and delocalised mechanisms act on the Ni 3d states during strain.

A density functional theory study of electronic and magnetic properties of rare earth doped monolayered molybdenum disulphide

The effects of Rare Earth (RE) atoms Sm, Eu, Gd, Tb, and Dy doping on structural, electronic, and magnetic properties of single layer MoS2 were investigated using first principles calculations. The analysis of electronic properties pointed out the appearance of host-impurity hybrid states on the edges of principal bands of the material, which appeared to cause narrowing of its bandgap. The values of total magnetic moment were calculated as 3.3 μB, 8.1 μB, 8.5 μB, 6.8 μB, and 6.4 μB for Sm-, Eu-, Gd-, Tb-, and Dy-doped MoS2, respectively. The underestimation of magnetic moment in the case of Sm doping is found which is assigned to shielding of 4f moments and quenching of angular momentum caused by Sm 4f–S 3p hybridization. On the other hand, the observed overestimation of magnetic moments for Eu and Gd cases is likely to be due to increase in angular momentum due to indirect exchange interaction of highly localized 4f states via 5d or 6s conduction electrons. The findings of this work point out the possibilities of tuning the band gap and magnetic properties of monolayer MoS2 upon RE doping for realization of p-type ferromagnetic semiconductors.

Evolution of magnetic properties in the solid solution [formula omitted

We have investigated the evolution of magnetic properties in pseudo-ternary UCo1−xPdxGe (x=0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) intermetallics by measurements of ac-magnetic susceptibility and dc-magnetization. The measured samples have been prepared by arc-melting and characterized by powder X-ray diffraction and X-ray energy-dispersive electron spectroscopy technique. Rietveld refinements of the X-ray patterns indicate that the pseudo-ternaries crystallize in the orthorhombic TiNiSi-type structure with Pnma space group as the parent UCoGe and UPdGe compounds do. The magnetic measurements reveal that in addition to an increase in 5f-electron localization degree with increasing Pd concentration, an interesting magnetic phase diagram, which is more complex than that expected from the gradual change in magnetic ground state due to the substitution. Three compositional ranges with different magnetic properties have been established; the coexistence of spin-glass and itinerant-electron ferromagnetic orderings for x≤0.3, antiferromagnetic order occurs in the range 0.4≤x≤0.7, and a complex ferromagnetic structure of more localized 5f moments takes place in x≥0.8. The evolution of magnetic ground states in UCo1−xPdxGe is discussed in terms of interplay between cooperative magnetic interactions. We consider also implications of increasing conduction electrons upon the Pd substitution in Ruderman-Kittel-Kasuya-Yosida interactions, which would give rise to the evolution of magnetic properties in UCo1−xPdxGe pseudo-ternaries.

Interplay of 4f and 3d moments in EuFe2As2 iron pnictides

AbstractEuFeAs is unique among 122 iron pnictides due to its 4f magnetic moments. We review its properties with particular emphasis on the interplay between 4f and 3d moments. After discussing the parent compound, we first focus on the evolution of magnetism and superconductivity for hole‐doped EuKFeAs as well as for chemical and hydrostatic pressure in EuFe(AsP) . Non‐Fermi liquid behavior for optimally doped superconducting systems is highlighted in the electrical resistivity and thermoelectric power. We also discuss the in‐plane anisotropy and how the indirect magnetoelastic coupling between Eu 4f moments and the crystal structure can be used for persistent detwinning of EuFeAs in the orthorhombic state by small magnetic fields.

Large adiabatic temperature and magnetic entropy changes inEuTiO3

We have investigated the magnetocaloric effect in single and polycrystalline samples of quantum paraelectric EuTiO3 by magnetization and heat capacity measurements. Single crystalline EuTiO3 shows antiferromagnetic ordering due to Eu2+ magnetic moments below TN = 5.6 K. This compound shows a giant magnetocaloric effect around its Neel temperature. The isothermal magnetic entropy change is 49 Jkg-1K-1, the adiabatic temperature change is 21 K and the refrigeration capacity is 500 JKg-1 for a field change of 7 T at TN. The single crystal and polycrystalline samples show similar values of the magnetic entropy change and adiabatic temperature changes. The large magnetocaloric effect is due to suppression of the spin entropy associated with localized 4f moment of Eu2+ ions. The giant magnetocaloric effect together with negligible hysteresis, suggest that EuTiO3 could be a potential material for magnetic refrigeration below 20 K.

Synthesis, crystal structure, and magnetism of A2Co12As7 (A=Ca, Y, Ce–Yb)

Ternary intermetallics, A2Co12As7 (A=Ca, Y, Ce–Yb), have been synthesized by annealing mixtures of elements in molten Bi at 1223K. The materials obtained crystallize in the P63/m variant of the Zr2Fe12P7 structure type. The unit cell volume shows a monotonic decrease with the increasing atomic number of the rare-earth metal, with the exception of Ce-, Eu-, and Yb-containing compounds. An examination of these outliers with X-ray absorption near edge structures (XANES) spectroscopy revealed mixed valence of Ce, Eu, and Yb, with the average oxidation states of +3.20(1), +2.47(5), and +2.91(1), respectively, at room temperature. Magnetic behavior of A2Co12As7 is generally characterized by ferromagnetic ordering of Co 3d moments at 100–140K, followed by low-temperature ordering of rare-earth 4f moments. The 3d-4f magnetic coupling changes from antiferromagnetic for A=Pr–Sm to ferromagnetic for A=Ce and Eu–Yb. Polarized neutron scattering experiments were performed to support the postulated ferro- and ferrimagnetic ground states for Ce2Co12As7 and Nd2Co12As7, respectively.

Nuclear Quadrupole Resonance Measurement of the Ferromagnetic Filled-Skutterudite Compound EuRu4Sb12

We report the detailed analysis of the 101Ru nuclear quadrupolar resonance spectrum in the ferromagnetically ordered state of EuRu4Sb121 and propose that Eu 4f moments align in the [111] direction. The localized character of Eu 4f electrons is suggested from the temperature dependence of the nuclear spin–lattice relaxation rate.

Magnetic Field-Induced Insulator-Semimetal Transition in a Pyrochlore Nd2Ir2O7.

We investigate magnetotransport properties in a single crystal of pyrochore-type Nd2Ir2O7. The metallic conduction is observed on the antiferromagnetic domain walls of the all-in-all-out-type Ir 5d moment ordered insulating bulk state that can be finely controlled by an external magnetic field along [111]. On the other hand, an applied field along [001] induces the bulk phase transition from insulator to semimetal as a consequence of the field-induced modification of the Nd 4f and Ir 5d moment configurations. A theoretical calculation consistently describing the experimentally observed features suggests a variety of exotic topological states as functions of electron correlation and Ir 5d moment orders, which can be finely tuned by the choice of rare-earth ion and magnetic field, respectively.