Materials research has driven the development of modern nano-electronic devices. In particular, research in magnetic thin films has revolutionized the development of spintronic devices1,2 because identifying new magnetic materials is key to better device performance and design. Van der Waals crystals retain their chemical stability and structural integrity down to the monolayer and, being atomically thin, are readily tuned by various kinds of gate modulation3,4. Recent experiments have demonstrated that it is possible to obtain two-dimensional ferromagnetic order in insulating Cr2Ge2Te6 (ref. 5) and CrI3 (ref. 6) at low temperatures. Here we develop a device fabrication technique and isolate monolayers from the layered metallic magnet Fe3GeTe2 to study magnetotransport. We find that the itinerant ferromagnetism persists in Fe3GeTe2 down to the monolayer with an out-of-plane magnetocrystalline anisotropy. The ferromagnetic transition temperature, Tc, is suppressed relative to the bulk Tc of 205 kelvin in pristine Fe3GeTe2 thin flakes. An ionic gate, however, raises Tc to room temperature, much higher than the bulk Tc. The gate-tunable room-temperature ferromagnetism in two-dimensional Fe3GeTe2 opens up opportunities for potential voltage-controlled magnetoelectronics7-11 based on atomically thin van der Waals crystals.

Gate-tunable Room-temperature Ferromagnetism in Two-dimensional Fe 3 GeTe 2

Stacking order can influence the physical properties of two-dimensional van der Waals materials1,2. Here we applied hydrostatic pressure up to 2 GPa to modify the stacking order in the van der Waals magnetic insulator CrI3. We observed an irreversible interlayer antiferromagnetic-to-ferromagnetic transition in atomically thin CrI3 by magnetic circular dichroism and electron tunnelling measurements. The effect was accompanied by a monoclinic-to-rhombohedral stacking-order change characterized by polarized Raman spectroscopy. Before the structural change, the interlayer antiferromagnetic coupling energy can be tuned up by nearly 100% with pressure. Our experiment reveals the interlayer ferromagnetic ground state, which is established in bulk CrI3 but not observed in native exfoliated thin films. The observed correlation between the magnetic ground state and the stacking order is in good agreement with first principles calculations3–8 and suggests a route towards nanoscale magnetic textures by moire engineering3,9. Pressure-induced changes in the magnetic order of atomically thin van der Waals crystals are revealed and attributed to changes in the stacking arrangement.

Pressure-controlled interlayer magnetism in atomically thin CrI3.

Two-dimensional layered materials, such as graphene and transition metal dichalcogenides (TMDs), have been under intensive investigation. The rapid progress of research on graphene and TMDs is now stimulating the exploration of different types of layered materials (LMs). Raman spectroscopy has shown its great potential in the characterization of layer numbers, interlayer coupling and layer-stacking configurations and will benefit the future explorations of other LMs. Lattice vibrations or Raman spectra of many LMs in bulk have been discussed since the 1960s. However, different results were obtained because of differences or limitations in the Raman instruments at early stages. The developments of modern Raman spectroscopy now allow us to revisit the Raman spectra of these LMs under the same experimental conditions. Moreover, to the best of our knowledge, there were limitations in detailed reviews on the Raman spectra of these different LMs. Here, we provide a review on Raman spectra of various LMs, including semiconductors, topological insulators, insulators, semi-metals and superconductors. We firstly introduce a unified method based on symmetry analysis and polarization measurements to assign the observed Raman modes and characterize the crystal structure of different types of LMs. Then, we revisit and update the positions and assignments of vibration modes by re-measuring the Raman spectra of different types of LMs and by comparing our results to those reported in previous papers. We apply the recent advances on the interlayer vibrations of graphene and TMDs to these various LMs and obtain their shear modulus. The observation of the shear modes of LMs in bulk facilitates an accurate and fast characterization of layer numbers during preparation processes in the future by a robust layer-number dependency on the frequencies of the shear modes. We also summarize the recent advances on the layer-stacking dependence on the intensities of interlayer shear vibrations. Finally, we review the recent advances on Raman spectroscopy in the characterization of anisotropic LMs, such as black phosphorus and rhenium diselenide. We believe that this review will benefit the future research studies on the fundamental physics and potential applications of these various LMs, particularly when they are reduced down to monolayers or multilayers.

Review on the Raman spectroscopy of different types of layered materials

2D van der Waals (vdW) magnets, which present intrinsic ferromagnetic/antiferromagnetic ground states at finite temperatures down to atomic-layer thicknesses, open a new horizon in materials science and enable the potential development of new spin-related applications. The layered structure of vdW magnets facilitates their atomic-layer cleavability and magnetic anisotropy, which counteracts spin fluctuations, thereby providing an ideal platform for theoretically and experimentally exploring magnetic phase transitions in the 2D limit. With reduced dimensions, the susceptibility of 2D magnets to a large variety of external stimuli also makes them more promising than their bulk counterpart in various device applications. Here, the current status of characterization and tuning of the magnetic properties of 2D vdW magnets, particularly the atomic-layer thickness, is presented. Various state-of-the-art optical and electrical techniques have been applied to reveal the magnetic states of 2D vdW magnets. Other emerging 2D vdW magnets and future perspectives on the stacking strategy are also given; it is believed that they will excite more intensive research and provide unprecedented opportunities in the field of spintronics.

Intrinsic Van Der Waals Magnetic Materials from Bulk to the 2D Limit: New Frontiers of Spintronics.

Silicene, the ultimate scaling of a silicon atomic sheet in a buckled honeycomb lattice, represents a monoelemental class of two-dimensional (2D) materials similar to graphene but with unique potential for a host of exotic electronic properties. Nonetheless, there is a lack of experimental studies largely due to the interplay between material degradation and process portability issues. This review highlights the state-of-the-art experimental progress and future opportunities in the synthesis, characterization, stabilization, processing and experimental device examples of monolayer silicene and its derivatives. The electrostatic characteristics of the Ag-removal silicene field-effect transistor exhibit ambipolar charge transport, corroborating with theoretical predictions on Dirac fermions and Dirac cone in the band structure. The electronic structure of silicene is expected to be sensitive to substrate interaction, surface chemistry, and spin-orbit coupling, holding great promise for a variety of novel applications, such as topological bits, quantum sensing, and energy devices. Moreover, the unique allotropic affinity of silicene with single-crystalline bulk silicon suggests a more direct path for the integration with or revolution to ubiquitous semiconductor technology. Both the materials and process aspects of silicene research also provide transferable knowledge to other Xenes like stanene, germanene, phosphorene, and so forth.

Silicene, silicene derivatives, and their device applications.

How a certain ground state of complex physical systems emerges, especially in two-dimensional materials, is a fundamental question in condensed-matter physics. A particularly interesting case is systems belonging to the class of XY Hamiltonian where the magnetic order parameter of conventional nature is unstable in two-dimensional materials leading to a Berezinskii−Kosterlitz−Thouless transition. Here, we report how the XXZ-type antiferromagnetic order of a magnetic van der Waals material, NiPS3, behaves upon reducing the thickness and ultimately becomes unstable in the monolayer limit. Our experimental data are consistent with the findings based on renormalization-group theory that at low temperatures a two-dimensional XXZ system behaves like a two-dimensional XY one, which cannot have a long-range order at finite temperatures. This work provides the experimental examination of the XY magnetism in the atomically thin limit and opens opportunities of exploiting these fundamental theorems of magnetism using magnetic van der Waals materials. Exploring the ground state of two-dimensional (2D) magnetic systems enriches the fundamental understanding of magnetism and boosts the applications. The authors here show the suppression of magnetic order and 2D XY behavior in XXZ-type antiferromagnet NiPS3 when approaching the monolayer limit by Raman spectroscopy.

https://pr.ibs.re.kr/bitstream/8788114/5746/1/2019-267_Suppression%20of%20magnetic%20ordering%20in%20XXZ-type%20antiferromagnetic%20monolayer%20NiPS3.pdf

Suppression of magnetic ordering in XXZ-type antiferromagnetic monolayer NiPS 3

How a certain ground state of complex physical systems emerges, especially in two-dimensional materials, is a fundamental question in condensed-matter physics. A particularly interesting case is systems belonging to the class of XY Hamiltonian where the magnetic order parameter of conventional nature is unstable in two-dimensional materials leading to a Berezinskii-Kosterlitz-Thouless transition. Here, we report how the XXZ-type antiferromagnetic order of a magnetic van der Waals material, NiPS3, behaves upon reducing the thickness and ultimately becomes unstable in the monolayer limit. Our experimental data are consistent with the findings based on renormalization group theory that at low temperatures a two-dimensional XXZ system behaves like a two-dimensional XY one, which cannot have a long-range order at finite temperatures. This work provides experimental examination of the XY magnetism in the atomically thin limit and opens new opportunities of exploiting these fundamental theorems of magnetism using magnetic van der Waals materials.

/pdf/suppression-of-magnetic-ordering-in-xxz-type-2orz6nv8n9.pdf

Suppression of magnetic ordering in XXZ-type antiferromagnetic monolayer NiPS3

Magnetic ordering in the two-dimensional limit has been one of the most important issues in condensed matter physics for the past several decades. The recent discovery of new magnetic van der Waals materials heralds a much-needed easy route for the studies of two-dimensional magnetism: the thickness dependence of the magnetic ordering has been examined by using Ising- and XXZ-type magnetic van der Waals materials. Here, we investigated the magnetic ordering of MnPS3, a two-dimensional antiferromagnetic material of Heisenberg-type, by Raman spectroscopy from bulk all the way down to bilayer. The phonon modes that involve the vibrations of Mn ions exhibit characteristic changes as the temperature gets lowered through the Neel temperature. In bulk MnPS3, the Raman peak at ~155 cm-1 becomes considerably broadened near the Neel temperature and upon further cooling is subsequently red-shifted. The measured peak positions and polarization dependences of the Raman spectra are in excellent agreement with our first-principles calculations. In few-layer MnPS3, the peak at ~155 cm-1 exhibits the characteristic red-shift at low temperatures down to the bilayer, indicating that the magnetic ordering is surprisingly stable at such a thin limit. Our work sheds light on the hitherto unexplored magnetic ordering in the Heisenberg-type antiferromagnetic systems in the atomic-layer limit.

https://iopscience.iop.org/article/10.1088/2053-1583/ab27d5/pdf

Antiferromagnetic ordering in van der Waals 2D magnetic material MnPS 3 probed by Raman spectroscopy

An exciton is the bosonic quasiparticle of electron–hole pairs bound by the Coulomb interaction1. Bose–Einstein condensation of this exciton state has long been the subject of speculation in various model systems2,3, and examples have been found more recently in optical lattices and two-dimensional materials4–9. Unlike these conventional excitons formed from extended Bloch states4–9, excitonic bound states from intrinsically many-body localized states are rare. Here we show that a spin–orbit-entangled exciton state appears below the Neel temperature of 150 kelvin in NiPS3, an antiferromagnetic van der Waals material. It arises intrinsically from the archetypal many-body states of the Zhang–Rice singlet10,11, and reaches a coherent state assisted by the antiferromagnetic order. Using configuration-interaction theory, we determine the origin of the coherent excitonic excitation to be a transition from a Zhang–Rice triplet to a Zhang–Rice singlet. We combine three spectroscopic tools—resonant inelastic X-ray scattering, photoluminescence and optical absorption—to characterize the exciton and to demonstrate an extremely narrow excitonic linewidth below 50 kelvin. The discovery of the spin–orbit-entangled exciton in antiferromagnetic NiPS3 introduces van der Waals magnets as a platform to study coherent many-body excitons. A spin–orbit-entangled exciton state in the van der Waals material NiPS3 is observed, and found to arise from many-body states of a Zhang–Rice singlet.

Coherent many-body exciton in van der Waals antiferromagnet NiPS3.

Raman spectra of few-layer MoSe2 were measured with eight excitation energies. New peaks that appear only near resonance with various exciton states are analyzed, and the modes are assigned. The resonance profiles of the Raman peaks reflect the joint density of states for optical transitions, but the symmetry of the exciton wave functions leads to selective enhancement of the A1g mode at the A exciton energy and the shear mode at the C exciton energy. We also find Davydov splitting of intralayer A1g, E1g, and A2u modes due to interlayer interaction for some excitation energies near resonances. Furthermore, by fitting the spectral positions of interlayer shear and breathing modes and Davydov splitting of intralayer modes to a linear chain model, we extract the strength of the interlayer interaction. We find that the second-nearest-neighbor interlayer interaction amounts to about 30% of the nearest-neighbor interaction for both in-plane and out-of-plane vibrations.

Kangwon Kim

Papers

Suppression of magnetic ordering in XXZ-type antiferromagnetic monolayer NiPS 3

Suppression of magnetic ordering in XXZ-type antiferromagnetic monolayer NiPS3

Antiferromagnetic ordering in van der Waals 2D magnetic material MnPS 3 probed by Raman spectroscopy

Coherent many-body exciton in van der Waals antiferromagnet NiPS3.

Davydov Splitting and Excitonic Resonance Effects in Raman Spectra of Few-Layer MoSe2