Magneto-optical Kerr effect microscopy is used to show that monolayer chromium triiodide is an Ising ferromagnet with out-of-plane spin orientation. The question of what happens to the properties of a material when it is thinned down to atomic-scale thickness has for a long time been a largely hypothetical one. In the past decade, new experimental methods have made it possible to isolate and measure a range of two-dimensional structures, enabling many theoretical predictions to be tested. But it has been a particular challenge to observe intrinsic magnetic effects, which could shed light on the longstanding fundamental question of whether intrinsic long-range magnetic order can robustly exist in two dimensions. In this issue of Nature, two groups address this challenge and report ferromagnetism in atomically thin crystals. Xiang Zhang and colleagues measured atomic layers of Cr2Ge2Te6 and observed ferromagnetic ordering with a transition temperature that, unusually, can be controlled using small magnetic fields. Xiaodong Xu and colleagues measured atomic layers of CrI3 and observed ferromagnetic ordering that, remarkably, was suppressed in double layers of CrI3, but restored in triple layers. The two studies demonstrate a platform with which to test fundamental properties of purely two-dimensional magnets. Since the discovery of graphene1, the family of two-dimensional materials has grown, displaying a broad range of electronic properties. Recent additions include semiconductors with spin–valley coupling2, Ising superconductors3,4,5 that can be tuned into a quantum metal6, possible Mott insulators with tunable charge-density waves7, and topological semimetals with edge transport8,9. However, no two-dimensional crystal with intrinsic magnetism has yet been discovered10,11,12,13,14; such a crystal would be useful in many technologies from sensing to data storage15. Theoretically, magnetic order is prohibited in the two-dimensional isotropic Heisenberg model at finite temperatures by the Mermin–Wagner theorem16. Magnetic anisotropy removes this restriction, however, and enables, for instance, the occurrence of two-dimensional Ising ferromagnetism. Here we use magneto-optical Kerr effect microscopy to demonstrate that monolayer chromium triiodide (CrI3) is an Ising ferromagnet with out-of-plane spin orientation. Its Curie temperature of 45 kelvin is only slightly lower than that of the bulk crystal, 61 kelvin, which is consistent with a weak interlayer coupling. Moreover, our studies suggest a layer-dependent magnetic phase, highlighting thickness-dependent physical properties typical of van der Waals crystals17,18,19. Remarkably, bilayer CrI3 displays suppressed magnetization with a metamagnetic effect20, whereas in trilayer CrI3 the interlayer ferromagnetism observed in the bulk crystal is restored. This work creates opportunities for studying magnetism by harnessing the unusual features of atomically thin materials, such as electrical control for realizing magnetoelectronics12, and van der Waals engineering to produce interface phenomena15.

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Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit

Graphene is very popular because of its many fascinating properties, but its lack of an electronic bandgap has stimulated the search for 2D materials with semiconducting character. Transition metal dichalcogenides (TMDCs), which are semiconductors of the type MX2, where M is a transition metal atom (such as Mo or W) and X is a chalcogen atom (such as S, Se or Te), provide a promising alternative. Because of its robustness, MoS2 is the most studied material in this family. TMDCs exhibit a unique combination of atomic-scale thickness, direct bandgap, strong spin–orbit coupling and favourable electronic and mechanical properties, which make them interesting for fundamental studies and for applications in high-end electronics, spintronics, optoelectronics, energy harvesting, flexible electronics, DNA sequencing and personalized medicine. In this Review, the methods used to synthesize TMDCs are examined and their properties are discussed, with particular attention to their charge density wave, superconductive and topological phases. The use of TMCDs in nanoelectronic devices is also explored, along with strategies to improve charge carrier mobility, high frequency operation and the use of strain engineering to tailor their properties. Two-dimensional transition metal dichalcogenides (TMDCs) exhibit attractive electronic and mechanical properties. In this Review, the charge density wave, superconductive and topological phases of TMCDs are discussed, along with their synthesis and applications in devices with enhanced mobility and with the use of strain engineering to improve their properties.

2D transition metal dichalcogenides

Investigations of two-dimensional transition-metal chalcogenides (TMCs) have recently revealed interesting physical phenomena, including the quantum spin Hall effect1,2, valley polarization3,4 and two-dimensional superconductivity
 5
 , suggesting potential applications for functional devices6–10. However, of the numerous compounds available, only a handful, such as Mo- and W-based TMCs, have been synthesized, typically via sulfurization11–15, selenization16,17 and tellurization
 18
 of metals and metal compounds. Many TMCs are difficult to produce because of the high melting points of their metal and metal oxide precursors. Molten-salt-assisted methods have been used to produce ceramic powders at relatively low temperature
 19
 and this approach
 20
 was recently employed to facilitate the growth of monolayer WS2 and WSe2. Here we demonstrate that molten-salt-assisted chemical vapour deposition can be broadly applied for the synthesis of a wide variety of two-dimensional (atomically thin) TMCs. We synthesized 47 compounds, including 32 binary compounds (based on the transition metals Ti, Zr, Hf, V, Nb, Ta, Mo, W, Re, Pt, Pd and Fe), 13 alloys (including 11 ternary, one quaternary and one quinary), and two heterostructured compounds. We elaborate how the salt decreases the melting point of the reactants and facilitates the formation of intermediate products, increasing the overall reaction rate. Most of the synthesized materials in our library are useful, as supported by evidence of superconductivity in our monolayer NbSe2 and MoTe2 samples21,22 and of high mobilities in MoS2 and ReS2. Although the quality of some of the materials still requires development, our work opens up opportunities for studying the properties and potential application of a wide variety of two-dimensional TMCs.

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A library of atomically thin metal chalcogenides

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

Material research has been a major driving force in the development of modern nano-electronic devices. In particular, research in magnetic thin films has revolutionized the development of spintronic devices; identifying new magnetic materials is key to better device performance and new device paradigm. The advent of two-dimensional van der Waals crystals creates new possibilities. This family of materials retain their chemical stability and structural integrity down to monolayers and, being atomically thin, are readily tuned by various kinds of gate modulation. Recent experiments have demonstrated that it is possible to obtain two-dimensional ferromagnetic order in insulating Cr$_2$Ge$_2$Te$_6$ and CrI$_3$ at low temperatures. Here, we developed a new device fabrication technique, and successfully isolated monolayers from layered metallic magnet Fe$_3$GeTe$_2$ for magnetotransport study. We found that the itinerant ferromagnetism persists in Fe$_3$GeTe$_2$ down to monolayer with an out-of-plane magnetocrystalline anisotropy. The ferromagnetic transition temperature, $T_c$, is suppressed in pristine Fe$_3$GeTe$_2$ thin flakes. An ionic gate, however, dramatically raises the $T_c$ up to room temperature, significantly higher than the bulk $T_c$ of 205 Kelvin. The gate-tunable room-temperature ferromagnetism in two-dimensional Fe$_3$GeTe$_2$ opens up opportunities for potential voltage-controlled magnetoelectronics based on atomically thin van der Waals crystals.

Gate-tunable Room-temperature Ferromagnetism in Two-dimensional Fe$_3$GeTe$_2$

The superconducting properties of NbSe2 as it approaches the monolayer limit are investigated by means of magnetotransport measurements, uncovering evidence of spin–momentum locking.

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Ising pairing in superconducting NbSe2 atomic layers

Time reversal and spatial inversion are two key symmetries for conventional Bardeen–Cooper–Schrieffer (BCS) superconductivity
 1
 . Breaking inversion symmetry can lead to mixed-parity Cooper pairing and unconventional superconducting properties1–5. Two-dimensional (2D) NbSe2 has emerged as a new non-centrosymmetric superconductor with the unique out-of-plane or Ising spin–orbit coupling (SOC)6–9. Here we report the observation of an unusual continuous paramagnetic-limited superconductor–normal metal transition in 2D NbSe2. Using tunelling spectroscopy under high in-plane magnetic fields, we observe a continuous closing of the superconducting gap at the upper critical field at low temperatures, in stark contrast to the abrupt first-order transition observed in BCS thin-film superconductors10–12. The paramagnetic-limited continuous transition arises from a large spin susceptibility of the superconducting phase due to the Ising SOC. The result is further supported by self-consistent mean-field calculations based on the ab initio band structure of 2D NbSe2. Our findings establish 2D NbSe2 as a promising platform to explore novel spin-dependent superconducting phenomena and device concepts
 1
 , such as equal-spin Andreev reflection
 13
 and topological superconductivity14–16. Tunnelling spectroscopy reveals a continuous closing of the superconducting gap at low temperature and high in-plane magnetic field in few-layer NbSe2, due to the Ising spin–orbit coupling of these materials.

An unusual continuous paramagnetic-limited superconducting phase transition in 2D NbSe 2

Time reversal and spatial inversion are two key symmetries for conventional Bardeen-Cooper-Schrieffer (BCS) superconductivity. Breaking inversion symmetry can lead to mixed-parity Cooper pairing and unconventional superconducting properties. Two-dimensional (2D) NbSe$_2$ has emerged as a new non-centrosymmetric superconductor with the unique out-of-plane or Ising spin-orbit coupling (SOC). Here, we report the observation of an unusual continuous paramagnetic-limited superconductor-normal metal transition in 2D NbSe$_2$. Using tunneling spectroscopy under high in-plane magnetic fields, we observe a continuous closing of the superconducting gap at the upper critical field at low temperatures, in stark contrast to the abrupt first-order transition observed in BCS thin film superconductors. The paramagnetic-limited continuous transition arises from a large spin susceptibility of the superconducting phase due to the Ising SOC. The result is further supported by self-consistent mean-field calculations based on the ab initio band structure of 2D NbSe$_2$. Our findings establish 2D NbSe$_2$ as a promising platform for exploring novel spin-dependent superconducting phenomena and device concepts, such as equal-spin Andreev reflection and topological superconductivity.

Ju-Hyun Park

Papers

Ising pairing in superconducting NbSe2 atomic layers

An unusual continuous paramagnetic-limited superconducting phase transition in 2D NbSe 2

An unusual continuous paramagnetic-limited superconducting phase transition in 2D NbSe$_2$