The Effect of Nickel Substitution on Magnetism in the Layered van der Waals Ferromagnet Fe$_3$GeTe$_2$
Gil Drachuck, Zaher Salman, Morgan W. Masters, Valentin Taufour, Tej N. Lamichhane, Qisheng Lin, Warren E. Straszheim, Sergey L. Bud'ko, Paul C. Canfield
We have grown a series of nickel substituted single crystals of the layered ferromagnet (FM) Fe$_3$GeTe$_2$. The large single crystalline samples of (Fe$_{1-x}$Ni$_x$)$_3$GeTe$_2$ with $x = 0-0.84$ were characterized with single crystal X-ray diffraction, magnetic susceptibility, electrical resistance and muon spin spectroscopy. We find Fe can be continuously substituted with Ni with only minor structural variation. In addition, FM order is suppressed from $T_\mathrm{C}=212$~K for $x=0$ down to $T_\mathrm{C}=50$~K for $x=0.3$, which is accompanied with a strong suppression of saturated and effective moment, and Curie-Weiss temperature. Beyond $x=0.3$, the FM order is continuously smeared into a FM cluster glass phase, with a nearly full magnetic volume fraction. We attribute the observed change in the nature of magnetic order to the intrinsically disordered structure of Fe$_3$GeTe$_2$ and subsequent dilution effects from the Ni substitution.
The layered van der Waals ferromagnetic Fe$_3$GeTe$_2$ harbours an unconventional interplay between topology and magnetism, leading to a large anomalous Hall conductivity at low temperatures. Here, we investigate the temperature dependence of its charge dynamics and reveal that upon entering the ferromagnetic state at $T_C \sim 200$ K and further lowering the temperature there is the onset of a gradual spectral weight reshuffling from the mid-infrared range towards far- as well as near-infrared frequencies. This two-fold spectral weight transfer indicates the important role of the Hund's coupl…
We report anomalous Hall effect (AHE) in single crystals of quasi-two-dimensional Fe$_{3-x}$GeTe$_2$ ($x \approx 0.36$) ferromagnet grown by the flux method which induces defects on Fe site and bad metallic resistivity. Fe K-edge x-ray absorption spectroscopy was measured to provide information on local atomic environment in such crystals. The dc and ac magnetic susceptibility measurements indicate a second-stage transition below 119 K in addition to the paramagnetic to ferromagnetic transition at 153 K. A linear scaling behavior between the modified anomalous Hall resistivity $ρ_{xy}/μ_0H_{ef…
Ferromagnetic (FM) semimetals Fe$_n$GeTe$_2$(n=3, 4, 5), exhibit several symmetry-protected band-crossing points or lines near the Fermi energy (E$_F$) and these topological properties of energy bands lead to interesting transport properties. We study these materials employing the first-principle calculations and the tight-binding Hamiltonian constructed by fitting the parameters of the first principles calculation. In the presence of spin-orbit coupling (SOC) for n=3,5 a large Berry curvature (BC) concentrated on the nodal lines is observed. The consequence of the correlation of the topologic…
$μ$SR measurements of 3D Ising ferromagnetism in bulk Fe$_3$GeTe$_2$ crystals
Memorial University（纪念大学）；PSI Center for Neutron and Muon Sciences（瑞士保罗谢尔研究所中子与μ子科学中心）；Durham University（杜伦大学）；University of Warwick（华威大学）；Clarendon Laboratory, Department of Physics, University of Oxford（牛津大学物理系克拉伦登实验室）
To understand the magnetic properties of Fe$_3$GeTe$_2$, we performed the detailed first-principles study. Contrary to the conventional wisdom, it is unambiguously shown that Fe$_3$GeTe$_2$ is not ferromagnetic but antiferromagnetic carrying zero net moment in its stoichiometric phase. Fe defect and hole doping are the keys to make this material ferromagnetic, which are shown by the magnetic force response as well as the total energy calculation with the explicit Fe defects and the varied system charges. Further, we found that the electron doping also induces the antiferro- to ferromagnetic tr…
The critical properties of the single-crystalline van der Waals bonded ferromagnet Fe$_{3-x}$GeTe$_2$ were investigated by bulk dc magnetization around the paramagnetic (PM) to ferromagnetic (FM) phase transition. The Fe$_{3-x}$GeTe$_2$ single crystals grown by self-flux method with Fe deficiency $x \approx 0.36$ exhibit bulk FM ordering below $T_c = 152$ K. The Mössbauer spectroscopy was used to provide information on defects and local atomic environment in such crystals. Critical exponents $β= 0.372(4)$ with a critical temperature $T_c = 151.25(5)$ K and $γ= 1.265(15)$ with $T_c = 151.17(12)…
We have investigated the nature of ferromagnetic order and phase transitions in two dimensional (2D) van der Waals (vdW) layered material, Fe$_4$GeTe$_2$ through measurements of magnetization, magneto-caloric Effect (MCE), and heat capacity. Fe$_4$GeTe$_2$ hosts a complex magnetic phase with two distinct transitions: paramagnetic to ferromagnetic at around $T_\text{C}$ $\sim$ 266 K and another spin reorientation transition (SRT) at around $T_\text{SRT}$ $\sim $ 100 K. The magnetization measurements shows a prominent thermal hysteresis in proximity to $T_\text{SRT}$ at $H\parallel c$, which imp…
We present a comprehensive study on anisotropic magnetocaloric porperties of the van der Waals weak-itinerant ferromagnet Fe$_{3-x}$GeTe$_2$ that features gate-tunable room-temperature ferromagnetism in few-layer device. Intrinsic magnetocrystalline anisotropy is observed to be temperature-dependent and most likely favors the long-range magnetic order in thin Fe$_{3-x}$GeTe$_2$ crsytal. The magnetic entropy change $-ΔS_M$ also reveals an anisotropic characteristic between $H // ab$ and $H // c$, which could be well scaled into a universal curve. The peak value $-ΔS_M^{max}$ of 1.20 J kg$^{-1}$…
Magnetic anisotropy in the near-stoichiometric van der Waals ferromagnet Fe$_3$GeTe$_2$
Leibniz Institute for Solid State and Materials Research（莱布尼茨固体与材料研究所）；Institute for Solid State and Materials Physics, TU Dresden（德累斯顿工业大学固体与材料物理研究所）；Department of Condensed Matter and Materials Physics, S. N. Bose National Centre for Basic Sciences（S.N. 玻色基础科学国家中心凝聚态与材料物理系）；School of Physical Sciences, Indian Association for the Cultivation of Science（印度科学促进协会物理科学学院）
Contrasting anisotropic electron-phonon-spin coupling in Fe$_{3}$GeTe$_{2}$ and Fe$_{5}$GeTe$_{2}$: A helicity-resolved Raman study
Indian Institute of Technology Kharagpur（印度理工学院卡拉格普尔分校）；Jawaharlal Nehru University（贾瓦哈拉尔·尼赫鲁大学）；Institute of Nuclear Physics, Polish Academy of Sciences（波兰科学院核物理研究所）；Sungkyunkwan University（成均馆大学）
Thermal and Magnetoelastic Properties of the van der Waals Ferromagnet Fe$_{3-δ}$GeTe$_2$: Anisotropic Spontaneous Magnetostriction and Ferromagnetic Magnon Excitations
In the new van der Waals Kondo-lattice Fe$_3$GeTe$_2$, itinerant ferromagnetism and heavy fermionic behaviour coexist. Both the key properties of such a system namely a spin-polarized Fermi surface and a low Fermi momentum are expected to significantly alter Andreev reflection dominated transport at a contact with a superconducting electrode, and display unconventional proximity-induced superconductivity. We observed interplay between Andreev reflection and Kondo resonance at mesoscopic interfaces between superconducting Nb and Fe$_3$GeTe$_2$. Above the critical temperature ($T_c$) of Nb, the …
High-Temperature ferromagnetism from site-selective filling in (Fe,Ni)$_{6-δ}$GeTe$_2$
Yale University（耶鲁大学）；University of California, Berkeley（加州大学伯克利分校）；Lawrence Berkeley National Lab（劳伦斯伯克利国家实验室）；Cornell University（康奈尔大学）；University of Southern California（南加州大学）；Boston College（波士顿学院）
We measure the band structure of nickel along various high-symmetry lines of the bulk Brillouin zone with angle-resolved photoelectron spectroscopy. The Gutzwiller theory for a nine-band Hubbard model whose tight-binding parameters are obtained from non-magnetic density-functional theory resolves most of the long-standing discrepancies between experiment and theory on nickel. Thereby we support the view of itinerant ferromagnetism as induced by atomic correlations.
Dichotomy of flat bands in the van der Waals ferromagnet Fe$_5$GeTe$_2$
Rice University（莱斯大学）；University of Washington（华盛顿大学）；Oak Ridge National Laboratory（橡树岭国家实验室）；Los Alamos National Laboratory（洛斯阿拉莫斯国家实验室）；Kyung Hee University（庆熙大学）
We use the Gutzwiller variational theory to investigate the electronic and the magnetic properties of fcc-Nickel. Our particular focus is on the effects of the spin-orbit coupling. Unlike standard relativistic band-structure theories, we reproduce the experimental magnetic moment direction and we explain the change of the Fermi-surface topology that occurs when the magnetic moment direction is rotated by an external magnetic field. The Fermi surface in our calculation deviates from early de-Haas--van-Alphen (dHvA) results. We attribute these discrepancies to an incorrect interpretation of the …
In the local or itinerant extreme, magnetic excitations can be described by the Heisenberg model which treats electron spins as localized moments, or by the itinerant-electron model where the exchange interaction between electrons leads to unequal numbers of electrons with up and down spins. However, it has been elusive when both local moments and itinerant electrons are present in the intermediate range. Using inelastic neutron scattering, we provide direct spectroscopic evidence on the coexistence of and interplay between local moments and itinerant electrons in a van der Waals metallic ferr…
Ferromagnetic Nickel is the most celebrated iron group metal with pronounced discrepancies between the experimental electronic properties and predictions of density functional theories. In this work, we show in detail that the recently developed multi-band Gutzwiller theory provides a very good description of the quasi-particle band structure of nickel. We obtain the correct exchange splittings and we reproduce the experimental Fermi-surface topology. The correct (111)-direction of the magnetic easy axis and the right order of magnitude of the magnetic anisotropy are found. Our theory also rep…
Fe$_{3-x}$GeTe$_2$ is a layered van der Waals magnetic material with a relatively high ordering temperature and large anisotropy. While most studies have concluded the interlayer ordering to be ferromagnetic, there have also been reports of interlayer antiferromagnetism in Fe$_{3-x}$GeTe$_2$. Here, we investigate the interlayer magnetic ordering by neutron diffraction experiments, scanning tunneling microscopy (STM) and spin-polarized STM measurements, density functional theory plus U calculations and STM simulations. We conclude that the layers of Fe$_{3-x}$GeTe$_2$ are coupled ferromagnetica…
Fe$_5$GeTe$_2$ is a van der Waals (vdW)-coupled unconventional ferromagnetic metal with a high Curie temperature ($T_C$) exceeding 300 K. The formation of an anomalous ground state significantly below $T_C$ has received considerable attention, resulting in increased interest in understanding the spin-polarized electronic state evolution near the Fermi energy ($E_F$) as a function of temperature. Despite recent extensive studies, a microscopic understanding of the spin-polarized electronic structure around $E_F$ has not yet been established owing to the intrinsic complexity of both the crystal …
The magnetic structure and phase diagram of the layered ferromagnetic compound Fe$_3$GeTe$_2$ has been investigated by a combination of synthesis, x-ray and neutron diffraction, high resolution microscopy, and magnetization measurements. Single crystals were synthesized by self-flux reactions, and single crystal neutron diffraction finds ferromagnetic order with moments of 1.11(5)$μ_B$/Fe aligned along the $c$-axis at 4K. These flux-grown crystals have a lower Curie temperature $T_{\textrm{c}}\approx$150K compared to crystals previously grown by vapor transport ($T_{\textrm{c}}$=220K). The dif…
We calculate the spin- and temperature-dependent local density of states for ferromagnetic Ni in the presence of a core hole at a distinguished site in the lattice. Correlations among the valence electrons and between valence and core electrons are described within a multi-band Hubbard model which is treated by means of second-order perturbation theory around the Hartree-Fock solution. The core-hole potential causes strong screening effects in the Ni valence band. The local magnetic moment is found to be decreased by a factor 5-6. The consequences for the spin polarisation of CVV Auger electro…
We report a giant magnetic moment enhancement of ferromagnetic nickel nanoparticles (11 nm) embedded in multi-walled carbon nanotubes. High-energy synchrotron x-ray diffraction experiment and chemical analysis are used to accurately determine the ferromagnetic nickel concentration. Magnetic measurements up to 900 K show an intriguing result-the saturation magnetization of the nickel nanoparticles embedded in the multi-walled carbon nanotubes is about 3.4 times as much as the value expected from the measured nickel concentration while the Curie temperature is the same as that of bulk nickel. Th…
In order to tune the magnetic properties of the cleavable high-Curie temperature ferromagnet Fe$_{5-x}$GeTe$_2$, the effect of increasing the electron count through arsenic substitution has been investigated. Small additions of arsenic (2.5 and 5%) seemingly enhance ferromagnetic order in polycrystalline samples by quenching fluctuations on one of the three magnetic sublattices, whereas larger As concentrations decrease the ferromagnetic Curie temperature ($T_{\rm C}$) and saturation magnetization. This work also describes the growth and characterization of Fe$_{4.8}$AsTe$_2$ single crystals t…
Among two-dimensional materials, Fe$_3$GeTe$_2$ has come to occupy a very important place owing to its ferromagnetic nature with one of the highest Curie temperatures among known van der Waals materials and the potential for hosting skyrmions. In this combined experimental and theoretical work, we investigate the magnetic bubble domains as well as the microscopic domain wall profile using spin-polarized scanning tunneling microscopy in combination with atomistic spin-dynamics simulations performed with parameters from density functional theory calculations. We find a weak magneto-electric effe…
We have studied the magnetic properties of quasi two-dimensional itinerant ferromagnet Fe$_4$GeTe$_2$ as functions of temperature and magnetic field ($B$) with field parallel to the $ab$-plane ($B\|ab$) and $c$-axis ($B\|c$) of the crystal. This van der Waals compound undergoes a continuous paramagnetic to ferromagnetic phase transition below $T_C$ = 270.0 K and a pronounced spin reorientation transition at around $T_{SR}$ $\sim$ 115 K where the easy axis of magnetization changes its direction from in-plane to out-of-plane. The temperature evolution of magnetization in the FM state is highly a…
Fe$_{3}$GeTe$_{2}$ is a two-dimensional van der Waals material with a ferromagnetic ground state and a maximum transition temperature $T_{\mathrm{c}}\sim225$ K. However, when Fe$_{3}$GeTe$_{2}$ is synthesized lower values of $T_{\mathrm{c}}$ are often reported. This is attributed to a deficiency in the Fe at the 2c site in the crystal structure. Here we investigate the effect of Fe deficiency and the substitution of Co for Fe on the magnetic properties of this system. We have synthesized both polycrystalline material and single crystals by chemical vapor transport and the flux method, with the…
We report the doping effects of cobalt on van der Waals (vdW) magnet Fe$_5$GeTe$_2$. A series of (Fe$_{1-x}$Co$_x$)$_5$GeTe$_2$ (0$\leq$x$\leq$0.44) single crystals have been successfully grown, their structural, magnetic and transport properties are investigated. For x=0.20, The Curie temperature $T_C$ increases from 276~K to 337~K. Moreover, the magnetic easy-axis is reoriented to the $ab$-plane from the $c$-axis in undoped Fe$_5$GeTe$_2$ with largely enhanced magnetic anisotropy. These magnetic properties would make (Fe$_{0.8}$Co$_{0.2}$)$_5$GeTe$_2$ more effective in stabilizing magnetic o…
The quasi-two-dimensional van der Waals magnet Fe$_{5-δ}$GeTe$_2$ has emerged as a promising platform for electronic and spintronic functionalities at room temperature, owing to its large ferromagnetic ordering temperature $T_{\text{C}}$ $\sim$ 315 K. Interestingly, by cobalt (Co) substitution of iron in F5GT, $i.e.$ $({\text{Fe}}_{1-x}{\text{Co}}_x)_{5-δ}{\text{GeTe}}_2$ (Co-F5GT), not only can its magnetic transition temperature be further enhanced, but the magnetic and structural ground states can also be tuned. Specifically, an antiferromagnetic (AFM) order is induced beyond the Co doping …
Fe$_{5-x}$GeTe$_2$ is a centrosymmetric, layered van der Waals (vdW) ferromagnet that displays Curie temperatures $T_c$ (270-330 K) that are within the useful range for spintronic applications. However, little is known about the interplay between its topological spin textures (e.g., merons, skyrmions) with technologically relevant transport properties such as the topological Hall effect (THE), or topological thermal transport. Here, we show via high-resolution Lorentz transmission electron microscopy that merons and anti-meron pairs coexist with Néel skyrmions in Fe$_{5-x}$GeTe$_2$ over a wide…
Suppression of local magnetic moment formation and paramagnetic exchange interactions in monolayer Fe$_3$GeTe$_2$
Moscow Institute of Physics and Technology（莫斯科物理技术学院）；M. N. Mikheev Institute of Metal Physics of Ural Branch of Russian Academy of Sciences（俄罗斯科学院乌拉尔分校 M.N. 米凯耶夫金属物理研究所）；Radboud University, Institute for Molecules and Materials（拉德堡德大学分子与材料研究所）
Spin Reorientation Driven Renormalization of Spin-Phonon Coupling in Fe$_4$GeTe$_2$
S. N. Bose National Centre for Basic Sciences（S.N. 玻色基础科学国家中心）；Uppsala University（乌普萨拉大学）；Bose Institute（玻色研究所）；Indian Institute of Technology Madras（马德拉斯印度理工学院）；Saha Institute of Nuclear Physics（萨哈核物理研究所）
Neutron scattering measurements on powder NaNiO2 reveal magnetic Bragg peaks and spin waves characteristic of strongly correlated s=1/2 magnetic moments arranged in ferromagnetic layers which are stacked antiferromagnetically. This structure lends itself to stacking sequence frustration in the presence of mixing between nickel and alkali metal sites, possibly providing a natural explanation for the enigmatic spin glass state of the isostructural compound, LiNiO2.
The electronic structure and magnetism in the sodium nickelate NaNiO_2 in the low-temperature phase is studied from density-functional calculations using the linear muffin-tin orbitals method. An antiferromagnetic solution with a magnetic moment of 0.7 m_B per Ni ion is found. A ferrodistorsive orbital ordering is shown to occur due to the Jahn-Teller distortion around the Ni^{3+} ion in agreement with the orbital ordering inferred from neutron diffraction. While the intralayer exchange is ferromagnetic, the interlayer exchange is weakly antiferromagnetic, mediated by a long Ni-O-Na-O-Ni super…
We present a systematic density functional theory (DFT) plus Hubbard $U$ study of structural trends and the stability of different magnetically ordered states across the rare-earth nickelate series, $R$NiO$_3$, with $R$ from Lu to La. In particular, we investigate how the magnetic order, the change of the rare-earth ion, and the Hubbard interaction $U$ are affecting the bond-length disproportionation between the nickel sites. Our results show that structural parameters can be obtained that are in very good agreement with present experimental data, and that DFT+$U$ is in principle able to captu…
Some Bravais lattices have a particular geometry that can slow down the motion of Bloch electrons by pre-localization due to the band-structure properties. Another known source of electronic localization in solids is the Coulomb repulsion in partially filled d- or f-orbitals, which leads to the formation of local magnetic moments. The combination of these two effects is usually considered of little relevance to strongly correlated materials. Here we show that it represents, instead, the underlying physical mechanism in two of the most important ferromagnets: nickel and iron. In nickel, the van…
Iron, cobalt and nickel are archetypal ferromagnetic metals. In bulk, electronic conduction in these materials takes place mainly through the $s$ and $p$ electrons, whereas the magnetic moments are mostly in the narrow $d$-electron bands, where they tend to align. This general picture may change at the nanoscale because electrons at the surfaces of materials experience interactions that differ from those in the bulk. Here we show direct evidence for such changes: electronic transport in atomic-scale contacts of pure ferromagnets (iron, cobalt and nickel), despite their strong bulk ferromagneti…
We investigate the unusual temperature dependence of the anomalous Hall effect in Ni. By varying the thickness of the MBE-grown Ni films, the longitudinal resistivity is uniquely tuned without resorting to doping impurities; consequently, the intrinsic and extrinsic contributions are cleanly separated out. In stark contrast to other ferromagnets such as Fe, the intrinsic contribution in Ni is found to be strongly temperature dependent with a value of 1100 (ohm*cm)^(-1) at low temperatures and 500 (ohm*cm)^(-1) at high temperatures. This pronounced temperature dependence, a cause of long-standi…
The recent observation of superconductivity in infinite-layer nickelates has brought intense debate on the established knowledge of unconventional superconductivity based on the cuprates. Despite many similarities, the nickelates differ from the cuprates in many characteristics, the most notable one among which is the magnetism. Instead of a canonical antiferromagnetic Mott insulator as the undoped cuprates, from which the superconductivity is generally believed to arise upon doping, the undoped nickelates show no sign of magnetic ordering in experiments. Through a combined density functional …
