Two-dimensional heavy fermions in the van der Waals metal CeSiI.

Heavy-fermion metals are prototype systems for observing emergent quantum phases driven by electronic interactions1-6. A long-standing aspiration is the dimensional reduction of these materials to exert control over their quantum phases7-11, which remains a significant challenge because traditional intermetallic heavy-fermion compounds have three-dimensional atomic and electronic structures. Here we report comprehensive thermodynamic and spectroscopic evidence of an antiferromagnetically ordered heavy-fermion ground state in CeSiI, an intermetallic comprising two-dimensional (2D) metallic sheets held together by weak interlayer van der Waals (vdW) interactions. Owing to its vdW nature, CeSiI has a quasi-2D electronic structure, and we can control its physical dimension through exfoliation. The emergence of coherent hybridization of f and conduction electrons at low temperature is supported by the temperature evolution of angle-resolved photoemission and scanning tunnelling spectra near the Fermi level and by heat capacity measurements. Electrical transport measurements on few-layer flakes reveal heavy-fermion behaviour and magnetic order down to the ultra-thin regime. Our work establishes CeSiI and related materials as a unique platform for studying dimensionally confined heavy fermions in bulk crystals and employing 2D device fabrication techniques and vdW heterostructures12 to manipulate the interplay between Kondo screening, magnetic order and proximity effects.

Giant and Tunable Out-of-Plane Spin Polarization of Topological Antimonene.

Topological insulators are bulk insulators with metallic and fully spin-polarized surface states displaying Dirac-like band dispersion. Due to spin-momentum locking, these topological surface states (TSSs) have a predominant in-plane spin polarization in the bulk fundamental gap. Here, we show by spin-resolved photoemission spectroscopy that the TSS of a topological insulator interfaced with an antimonene bilayer exhibits nearly full out-of-plane spin polarization within the substrate gap. We connect this phenomenon to a symmetry-protected band crossing of the spin-polarized surface states. The nearly full out-of-plane spin polarization of the TSS occurs along a continuous path in the energy-momentum space, and the spin polarization within the gap can be reversibly tuned from nearly full out-of-plane to nearly full in-plane by electron doping. These findings pave the way to advanced spintronics applications that exploit the giant out-of-plane spin polarization of TSSs.

Interplay between Local Moment and Itinerant Magnetism in the Layered Metallic Antiferromagnet TaFe1.14Te3.

Two-dimensional antiferromagnets have garnered considerable interest for the next generation of functional spintronics. However, many bulk materials from which two-dimensional antiferromagnets are isolated are limited by their air sensitivity, low ordering temperatures, and insulating transport properties. TaFe1+yTe3 aims to address these challenges with increased air stability, metallic transport, and robust antiferromagnetism. Here, we synthesize TaFe1+yTe3 (y = 0.14), identify its structural, magnetic, and electronic properties, and elucidate the relationships between them. Axial-dependent high-field magnetization measurements on TaFe1.14Te3 reveal saturation magnetic fields ranging between 27 and 30 T with saturation magnetic moments of 2.05-2.12 µB. Magnetotransport measurements confirm that TaFe1.14Te3 is metallic with strong coupling between magnetic order and electronic transport. Angle-resolved photoemission spectroscopy measurements across the magnetic transition uncover a complex interplay between itinerant electrons and local magnetic moments that drives the magnetic transition. We demonstrate the ability to isolate few-layer sheets of TaFe1.14Te3, establishing TaFe1.14Te3 as a potential platform for two-dimensional spintronics.

Structural, magnetic, and dielectric properties of solution combustion synthesized LaFeO3, LaFe0.9Mn0.1O3, and LaMnO3 perovskites.

Nanocrystalline LaFeO3, LaFe0.9Mn0.1O3, and LaMnO3 perovskites have been synthesized by a novel solution combustion route, in which oxalyl dihydrazide (ODH) has been used as a fuel. These materials have been characterized using several physicochemical techniques. LaFeO3 and LaFe0.9Mn0.1O3 adopt an orthorhombic structure and LaMnO3 crystallizes in a rhombohedral structure as demonstrated by X-ray diffraction (XRD) patterns. The microporous character of the materials due to huge gas evolution during preparation has been revealed by field emission scanning electron microscopy (FESEM) images. Corresponding elements are present in stoichiometric amounts in all perovskites as revealed by energy dispersive X-ray spectroscopy (EDXS) analyses. X-ray photoelectron spectroscopy (XPS) studies demonstrate the presence of La3+, Fe2+, Fe3+, Mn3+, and Mn4+ species in the respective materials. Absorption bands in the frequency range of 500-600 cm-1 related to Fe-O/Mn-O bonds in FeO6/MnO6 octahedra are observed in Fourier transform infrared (FTIR) spectra. Raman spectroscopy depicts symmetric modes related to metal-oxygen bonds in orthorhombic and rhombohedral structures. Weak ferromagnetism has been observed in LaFeO3 and LaFe0.9Mn0.1O3 which is due to superexchange interaction between the magnetic cations. However, LaMnO3 shows paramagnetic behavior. The electrical characteristics exhibit the lowest dielectric loss for magnetic LaFeO3 among the LaFeO3, LaFe0.9Mn0.1O3, and LaMnO3 perovskites studied here.

Solution combustion synthesis, characterization, magnetic, and dielectric properties of CoFe2O4 and Co0.5M0.5Fe2O4 (M = Mn, Ni, and Zn).

Nanocrystalline CoFe2O4 and Co0.5M0.5Fe2O4 (M = Mn, Ni, and Zn) ferrites were prepared by the solution combustion method using oxalyl dihydrazide as a fuel. These materials were characterized by several physicochemical techniques. X-ray diffraction (XRD) patterns indicate the cubic spinel structure of these ferrites. Field emission scanning electron microscopy (FESEM) images demonstrate the microporous nature of the materials because of the large amount of gas production during their synthesis. High resolution transmission electron microscopy (HRTEM) images show lattice fringes corresponding to the {220} and {311} planes of the spinel structure. Fourier transform infrared (FTIR) spectra exhibit absorption bands around the 500-600 cm-1 wavenumber region which are related to metal-oxygen bonds with tetrahedral coordination. Symmetric and asymmetric stretching and symmetric bending modes associated with tetrahedral and octahedral cations present in the spinel structures have been assessed by Raman spectroscopy. X-ray photoelectron spectroscopy (XPS) studies demonstrate the presence of Co2+, Mn2+, Ni2+, Zn2+, and Fe3+ in tetrahedral and octahedral coordinations in these ferrites. Co0.5Zn0.5Fe2O4 is observed to show the highest saturation magnetization among all these materials. The dielectric measurements reveal that the dielectric constant and loss values decrease with an increase in frequency and the ac conductivity increases at higher frequencies due to mobilization of the charge carriers.

Low-energy electronic structure in the unconventional charge-ordered state of ScV6Sn6.

Kagome vanadates AV3Sb5 display unusual low-temperature electronic properties including charge density waves (CDW), whose microscopic origin remains unsettled. Recently, CDW order has been discovered in a new material ScV6Sn6, providing an opportunity to explore whether the onset of CDW leads to unusual electronic properties. Here, we study this question using angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling microscopy (STM). The ARPES measurements show minimal changes to the electronic structure after the onset of CDW. However, STM quasiparticle interference (QPI) measurements show strong dispersing features related to the CDW ordering vectors. A plausible explanation is the presence of a strong momentum-dependent scattering potential peaked at the CDW wavevector, associated with the existence of competing CDW instabilities. Our STM results further indicate that the bands most affected by the CDW are near vHS, analogous to the case of AV3Sb5 despite very different CDW wavevectors.

Visualizing the unusual spectral weight transfer in DyBa2Cu3O7-δ thin film.

We report a Spectroscopic Imaging Scanning Tunneling Microscopy (SI-STM) study of a DyBa2Cu3O7-δ (DBCO) thin film (Tc ~ 79 K) synthesized by the molecular beam epitaxy (MBE). We observed an unusual transfer of spectral weight in the local density of states (LDOS) spectra occurring only within the superconducting gap. By a systematic control of the tip-sample distance and the junction resistance, we demonstrate that the spectral weight transfer can be switched at a nano-meter length scale. These results suggest that an interaction between the STM tip and the sample alters the electronic configurations in the film. This probably originates from a combination of an intrinsic band bending at the interface between the surface and the bulk, and a tip-induced band bending. These results may open a new avenue for band engineering and applications of thin films of high-Tc cuprates.

Quantum Size Effects, Multiple Dirac Cones, and Edge States in Ultrathin Bi(110) Films.

The presence of inherently strong spin-orbit coupling in bismuth, its unique layer-dependent band topology and high carrier mobility make it an interesting system for both fundamental studies and applications. Theoretically, it has been suggested that strong quantum size effects should be present in the Bi(110) films, with the possibility of Dirac Fermion states in the odd-bilayer (BL) films, originating from dangling pz orbitals and quantum-spin hall (QSH) states in the even-bilayer films. However, the experimental verification of these claims has been lacking. Here, we study the electronic structure of Bi(110) films grown on a high-Tc superconductor, Bi2Sr2CaCu2O8+δ (Bi2212) using angle-resolved photoemission spectroscopy (ARPES). We observe an oscillatory behavior of electronic structure with the film thickness and identify the Dirac-states in the odd-bilayer films, consistent with the theoretical predictions. In the even-bilayer films, we find another Dirac state that was predicted to play a crucial role in the QSH effect. In the low thickness limit, we observe several extremely one-dimensional states, probably originating from the edge-states of Bi(110) islands. Our results provide a much needed experimental insight into the electronic and structural properties of Bi(110) films.

Role of Surface Termination in the Metal-Insulator Transition of V2O3(0001) Ultrathin Films.

Surface termination is known to play an important role in determining the physical properties of materials. It is crucial to know how surface termination affects the metal-insulator transition (MIT) of V2O3 films for both fundamental understanding and its applications. By changing growth parameters, we achieved a variety of surface terminations in V2O3 films that are characterized by low-energy electron diffraction (LEED) and photoemission spectroscopy techniques. Depending upon the terminations, our results show that MIT can be partially or fully suppressed near the surface region due to the different fillings of the electrons at the surface and subsurface layers and the change of screening length compared to the bulk. Across MIT, a strong redistribution of spectral weight and its transfer from a high-to-low-binding energy regime is observed in a wide energy scale. Our results show that the total spectral weight in the low-energy regime is not conserved across MIT, indicating a breakdown of the "sum rules of spectral weight", signature of a strongly correlated system. Such a change in spectral weight is possibly linked to the change in hybridization, lattice volume (i.e., effective carrier density), and the spin degree of freedom in the system that occurs across MIT. We find that MIT in this system is strongly correlation-driven, where the electron-electron interactions play a pivotal role. Moreover, our results provide better insight into the understanding of the electronic structure of strongly correlated systems and highlight the importance of accounting for surface effects during interpretation of the physical property data mainly using surface-sensitive probes, such as surface resistivity.

Correction: Influence of 4f filling on electronic and magnetic properties of rare earth-Au surface compounds.

Correction for 'Influence of 4f filling on electronic and magnetic properties of rare earth-Au surface compounds' by L. Fernandez et al., Nanoscale, 2020, 12, 22258-22267, DOI: 10.1039/D0NR04964F.

Valence band electronic structure of the van der Waals ferromagnetic insulators: VI[Formula: see text] and CrI[Formula: see text].

Ferromagnetic van der Waals (vdW) insulators are of great scientific interest for their promising applications in spintronics. It has been indicated that in the two materials within this class, CrI[Formula: see text] and VI[Formula: see text], the magnetic ground state, the band gap, and the Fermi level could be manipulated by varying the layer thickness, strain or doping. To understand how these factors impact the properties, a detailed understanding of the electronic structure would be required. However, the experimental studies of the electronic structure of these materials are still very sparse. Here, we present the detailed electronic structure of CrI[Formula: see text] and VI[Formula: see text] measured by angle-resolved photoemission spectroscopy (ARPES). Our results show a band-gap of the order of 1 eV, sharply contrasting some theoretical predictions such as Dirac half-metallicity and metallic phases, indicating that the intra-atomic interaction parameter (U) and spin-orbit coupling (SOC) were not properly accounted for in the calculations. We also find significant differences in the electronic properties of these two materials, in spite of similarities in their crystal structure. In CrI[Formula: see text], the valence band maximum is dominated by the I 5p, whereas in VI[Formula: see text] it is dominated by the V 3d derived states. Our results represent valuable input for further improvements in the theoretical modeling of these systems.

Bi-doped suppression of antisite disordering and associated magnetic properties of La2-x Bi x MnNiO6 (x = 0 and 1).

Here we report synthesis, structure, microstructure and magnetic properties of La2-x Bi x MnNiO6 (x = 0 and 1) double perovskites. Ricciardo et al (2009 Mater. Res. Bull. 44 239) have attempted to synthesize LaBiMnNiO6 (x = 1), but no further characterization was done due to large impurity content in the sample. We have been able to synthesize LaBiMnNiO6 phase at ambient pressure with traces of impurity at 750 °C using sol-gel method. This achievement leads us to compare the structural and magnetic properties of LaBiMnNiO6 with parent phase La2MnNiO6 to highlight the effect of Bi-doping in double perovskite. In contrast to the biphasic rhombohedral (R-3c) and monoclinic (P21/n) crystal structures of La2MnNiO6, LaBiMnNiO6 crystallized in single monoclinic (P21/n) phase. The EDX mapping confirmed the chemical homogeneity of the samples. The electron diffraction confirms the ordered structure of the sample. The microstructure analysis from HAADF-STEM revealed random distribution of misfit dislocations in the structure. Such defects are created to relax the strain due to unusual replacement of Mn/Ni atoms by La/Bi. We observed a decrease in TC with a large increase in magnetic moment of LaBiMnNiO6 compare to La2MnNiO6. There is also large suppression of low-temperature magnetic anomaly in Bi-substituted sample. The lowering of TC can be rationalized to the local structural distortion associated with the stereoactive 6s2-lone pair electron of Bi3+. On the other hand, the increase in magnetic moment and suppression of low-temperature magnetic anomaly for LaBiMnNiO6 can be ascribed to the suppression of antisite disorder in Bi-substituted sample.

Influence of 4f filling on electronic and magnetic properties of rare earth-Au surface compounds.

One-atom-thick rare-earth/noble metal (RE-NM) compounds are attractive materials to investigate two-dimensional magnetism, since they are easy to synthesize into a common RE-NM2 structure with high crystal perfection. Here we perform a comparative study of the GdAu2, HoAu2, and YbAu2 monolayer compounds grown on Au(111). We find the same atomic lattice quality and moiré superlattice periodicity in the three cases, but different electronic properties and magnetism. The YbAu2 monolayer reveals the characteristic electronic signatures of a mixed-valence configuration in the Yb atom. In contrast, GdAu2 and HoAu2 show the trivalent character of the rare-earth and ferromagnetic transitions below 22 K. Yet, the GdAu2 monolayer has an in-plane magnetic easy-axis, versus the out-of-plane one in HoAu2. The electronic bands of the two trivalent compounds are very similar, while the divalent YbAu2 monolayer exhibits different band features. In the latter, a strong 4f-5d hybridization is manifested in neatly resolved avoided crossings near the Fermi level. First principles theory points to a residual presence of empty 4f states, explaining the fluctuating valence of Yb in the YbAu2 monolayer.

Electron transport and thermoelectric properties of layered perovskite LaBaCo(2)O(5.5).

We have investigated systematically the physical transport properties of layered 112-type cobaltite by means of electrical resistivity, magnetoresistance and thermopower measurements. In order to understand the complex transport mechanism of LaBaCo(2)O(5.5), the data have been analysed using different theoretical models. The compound shows an electronic transition between two semiconducting states around 326 K, which coincides with the ferromagnetic transition. Interestingly, the system also depicts a significant magnetoresistance (MR) effect near the ferro/antiferromagnetic phase boundary and the highest value of MR is close to 5% at 245 K under ± 7 T. The temperature dependence of thermopower, S(T), exhibits p-type conductivity in the 60 K≤T≤320 K range and reaches a maximum value of around 303 µV K(-1) (at 120 K). In the low temperature antiferromagnetic region the unusual S(T) behaviour, generally observed for the cobaltite series LnBaCo(2)O(5.5) (Ln = rare earth), is explained by the electron magnon scattering mechanism.

A revisit to the effect of annealing temperature on magnetic properties of LaFe0.5Mn0.5O3.

We report an experimental study for the structural and magnetic properties of highly pure LaFe0.5Mn0.5O3 perovskite phase. The impurity free LaFe0.5Mn0.5O3 has been prepared by sol-gel technique at 500 °C and annealed at different temperatures up to 1000 °C. Previous works on LaFe0.5Mn0.5O3 revealed presence of secondary phases along with contradicting magnetic properties. Such as, Bhame et al (2005 Phys. Rev. B 72 054426-7) reported the superparamagnetic or spin-glass like behavior for 200 °C treated sample that persisted even at 700 °C sample. However, Wei et al (2012 Mater. Chem. Phys. 136 755-61) claimed room temperature ferromagnetism in all the samples annealed in the range of 600 °C-700 °C where the saturation magnetization decreases with the increase in temperature. These contradicting results lead us to revisit the effect of annealing temperature on the magnetic properties of LaFe0.5Mn0.5O3. We noticed a gradual increase in magnetization with increase in annealing temperatures without any signature of long range spin ordering for pure single phase samples. The increased magnetic moment with annealing temperatures has been attributed to the suppression of surface contribution of disordered spin. The low temperature magnetic behaviors can be explained by the interacting cluster glass behavior for the pristine as well as for 1000 °C annealed samples.

Indirect chiral magnetic exchange through Dzyaloshinskii-Moriya-enhanced RKKY interactions in manganese oxide chains on Ir(100).

Localized electron spins can couple magnetically via the Ruderman-Kittel-Kasuya-Yosida interaction even if their wave functions lack direct overlap. Theory predicts that spin-orbit scattering leads to a Dzyaloshinskii-Moriya type enhancement of this indirect exchange interaction, giving rise to chiral exchange terms. Here we present a combined spin-polarized scanning tunneling microscopy, angle-resolved photoemission, and density functional theory study of MnO2 chains on Ir(100). Whereas we find antiferromagnetic Mn-Mn coupling along the chain, the inter-chain coupling across the non-magnetic Ir substrate turns out to be chiral with a 120° rotation between adjacent MnO2 chains. Calculations reveal that the Dzyaloshinskii-Moriya interaction results in spin spirals with a periodicity in agreement with experiment. Our findings confirm the existence of indirect chiral magnetic exchange, potentially giving rise to exotic phenomena, such as chiral spin-liquid states in spin ice systems or the emergence of new quasiparticles.

Role of random magnetic anisotropy on the valence, magnetocaloric and resistivity properties in a hexagonal Sm2Ni0.87Si2.87 compound.

In this work, we report the effect of random magnetic anisotropy (RMA) on the valence, magnetocaloric and resistivity properties in a glassy intermetallic material Sm2Ni0.87Si2.87. On the basis of detailed studies on the valence band and core level electronic structure, we have established that both the Sm3+ and Sm2+ ions are present in the system, suggesting the compound to be of mixed valence in nature. The significant observation of positive magnetic entropy change in zero-field cooled measurement has been argued due to the presence of RMA that develops due to local electronic environmental variations between the rare-earth ions in the system. The quantum interference effect caused by the elastic electron-electron interaction is responsible for the resistivity upturn at low-temperature for this disordered metallic conductor.

Interplay between 3d-3d and 3d-4f interactions at the origin of the magnetic ordering in the Ba2LnFeO5 oxides.

A new family of oxides in which 3d-3d and 3d-4f interactions are of comparable strength has been synthesized and characterized both from structural and physical viewpoints. These compounds of formulation Ba2LnFeO5 (Ln = Sm, Eu, Gd, Dy, Ho, Er, Yb) are isotypic to the perovskite derivative Ba2YFeO5. They exhibit an original structure consisting of isolated FeO4 tetrahedra linked via LnO6 (or YO6) octahedra. Magnetic and calorimetric measurements show that all these compounds exhibit a unique, antiferromagnetic transition involving both the 3d and 4f ions. The antiferromagnetic properties of the Ln = Y phase (non-magnetic Y(3+)) and of the Ln = Eu (non-magnetic ground state multiplet of Eu(3+)) are ascribed to super-super exchange Fe-O-O-Fe interactions, leading to the lowest T(N) (5.5 K for Y and 4.6 K for Eu). The introduction of a magnetic lanthanide, i.e. Ln = Sm, Gd, Dy, Ho, Er, Yb, in the octahedral sites, leads to larger T(N) values (up to 9.8 K for Ln = Yb). It is found that several mechanisms must be taken into account to explain the complex evolution of the magnetic properties along the Ba2LnFeO5 series. In particular, the super-exchange Ln-O-Fe, as well as the on-site Ln(3+) magnetocrystalline anisotropy, are suggested to play crucial roles. This Ba2LnFeO5 series offers a rare opportunity to investigate experimentally a situation where the 3d-3d and 3d-4f interactions co-operate on an equal footing to trigger a unique long-range magnetic ordering in insulating oxides.

A comparative study of magnetic and dielectric behaviors for La(1-x)Bi(x)Mn(1-y)Fe(y)O3 series (with x = 0.5, 0.7 and y = 0.3, 0.7).

We have carried out an extensive investigation into the effect of doping on both the A- and B-sites for the multiferroic La(0.5)Bi(0.5)Mn(0.5)Fe(0.5)O(3) in relation to its physical properties. The temperature dependent magnetization and dielectric response are determined for different percentages of Bi- and Fe-substitutions. For La(0.5)Bi(0.5)Mn(0.7)Fe(0.3)O(3), there is a prominent ferromagnetic transition T(C) around 110 K, whereas the other La(0.5)Bi(0.5)Mn(0.3)Fe(0.7)O(3) and La(0.3)Bi(0.7)Mn(0.3)Fe(0.7)O(3) phases fail to exhibit any clear transition. On the other hand, for the Fe-rich phases, the coercive field increases to 2450 Oe compared to 1720 Oe (for the Mn-rich phase). All the compositions exhibit coexistence of ferromagnetic and antiferromagnetic phases at low temperatures. The temperature dependent dielectric constant of the investigated samples varies from 32,000 to 500 at room temperature and the data has been analyzed using the universal dielectric response model.

Electronic phase separation in transition metal oxide systems.

Electronic phase separation is increasingly getting recognized as a phenomenon of importance in understanding the magnetic and electron transport properties of transition metal oxides. The phenomenon dominates the rare-earth manganates of the formula Ln(1-x)A(x)MnO(3)(Ln = rare earth and A = alkaline earth) which exhibit ferromagnetism and metallicity as well as charge-ordering, depending on the composition, size of A-site cations and external factors such as magnetic and electric fields. We discuss typical phase separation scenarios in the manganates, with particular reference to Pr(1-x)Ca(x)MnO(3)(x= 0.3-0.4), (La(1-x)Ln(x))(0.7)Ca(0.3)MnO(3)(Ln = Pr, Nd, Gd and Y) and Nd(0.5)Sr(0.5)MnO(3). Besides discussing the magnetic and electron transport properties, we discuss electric field effects. Rare-earth cobaltates of the type Pr(0.7)Ca(0.3)CoO(3) and Gd(0.5)Ba(0.5)CoO(3) also exhibit interesting magnetic and electron transport properties which can be understood in terms of phase separation.