BACKGROUND Materials by design is an appealing idea that is very hard to realize in practice. Combining the best of different ingredients in one ultimate material is a task for which we currently have no general solution. However, we do have some successful examples to draw upon: Composite materials and III-V heterostructures have revolutionized many aspects of our lives. Still, we need a general strategy to solve the problem of mixing and matching crystals with different properties, creating combinations with predetermined attributes and functionalities. ADVANCES Two-dimensional (2D) materials offer a platform that allows creation of heterostructures with a variety of properties. One-atom-thick crystals now comprise a large family of these materials, collectively covering a very broad range of properties. The first material to be included was graphene, a zero-overlap semimetal. The family of 2D crystals has grown to includes metals (e.g., NbSe 2 ), semiconductors (e.g., MoS 2 ), and insulators [e.g., hexagonal boron nitride (hBN)]. Many of these materials are stable at ambient conditions, and we have come up with strategies for handling those that are not. Surprisingly, the properties of such 2D materials are often very different from those of their 3D counterparts. Furthermore, even the study of familiar phenomena (like superconductivity or ferromagnetism) in the 2D case, where there is no long-range order, raises many thought-provoking questions. A plethora of opportunities appear when we start to combine several 2D crystals in one vertical stack. Held together by van der Waals forces (the same forces that hold layered materials together), such heterostructures allow a far greater number of combinations than any traditional growth method. As the family of 2D crystals is expanding day by day, so too is the complexity of the heterostructures that could be created with atomic precision. When stacking different crystals together, the synergetic effects become very important. In the first-order approximation, charge redistribution might occur between the neighboring (and even more distant) crystals in the stack. Neighboring crystals can also induce structural changes in each other. Furthermore, such changes can be controlled by adjusting the relative orientation between the individual elements. Such heterostructures have already led to the observation of numerous exciting physical phenomena. Thus, spectrum reconstruction in graphene interacting with hBN allowed several groups to study the Hofstadter butterfly effect and topological currents in such a system. The possibility of positioning crystals in very close (but controlled) proximity to one another allows for the study of tunneling and drag effects. The use of semiconducting monolayers leads to the creation of optically active heterostructures. The extended range of functionalities of such heterostructures yields a range of possible applications. Now the highest-mobility graphene transistors are achieved by encapsulating graphene with hBN. Photovoltaic and light-emitting devices have been demonstrated by combining optically active semiconducting layers and graphene as transparent electrodes. OUTLOOK Currently, most 2D heterostructures are composed by direct stacking of individual monolayer flakes of different materials. Although this method allows ultimate flexibility, it is slow and cumbersome. Thus, techniques involving transfer of large-area crystals grown by chemical vapor deposition (CVD), direct growth of heterostructures by CVD or physical epitaxy, or one-step growth in solution are being developed. Currently, we are at the same level as we were with graphene 10 years ago: plenty of interesting science and unclear prospects for mass production. Given the fast progress of graphene technology over the past few years, we can expect similar advances in the production of the heterostructures, making the science and applications more achievable.

2D materials and van der Waals heterostructures

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 .

Reduced dimensionality and interlayer coupling in van der Waals materials gives rise to fundamentally different electronic
 1
 , optical
 2
 and many-body quantum3–5 properties in monolayers compared with the bulk. This layer-dependence permits the discovery of novel material properties in the monolayer regime. Ferromagnetic order in two-dimensional materials is a coveted property that would allow fundamental studies of spin behaviour in low dimensions and enable new spintronics applications6–8. Recent studies have shown that for the bulk-ferromagnetic layered materials CrI3 (ref. 9
 ) and Cr2Ge2Te6 (ref. 10
 ), ferromagnetic order is maintained down to the ultrathin limit at low temperatures. Contrary to these observations, we report the emergence of strong ferromagnetic ordering for monolayer VSe2, a material that is paramagnetic in the bulk11,12. Importantly, the ferromagnetic ordering with a large magnetic moment persists to above room temperature, making VSe2 an attractive material for van der Waals spintronics applications.

https://par.nsf.gov/servlets/purl/10090019

Strong room-temperature ferromagnetism in VSe2 monolayers on van der Waals substrates.

Magnetism, originating from the moving charges and spin of elementary particles, has revolutionized important technologies such as data storage and biomedical imaging, and continues to bring forth new phenomena in emergent materials and reduced dimensions. The recently discovered two-dimensional (2D) magnetic van der Waals crystals provide ideal platforms for understanding 2D magnetism, the control of which has been fueling opportunities for atomically thin, flexible magneto-optic and magnetoelectric devices (such as magnetoresistive memories and spin field-effect transistors). The seamless integration of 2D magnets with dissimilar electronic and photonic materials opens up exciting possibilities for unprecedented properties and functionalities. We review the progress in this area and identify the possible directions for device applications, which may lead to advances in spintronics, sensors, and computing.

Two-dimensional magnetic crystals and emergent heterostructure devices

The discovery of materials has often introduced new physical paradigms and enabled the development of novel devices. Two-dimensional magnetism, which is associated with strong intrinsic spin fluctuations, has long been the focus of fundamental questions in condensed matter physics regarding our understanding and control of new phases. Here we discuss magnetic van der Waals materials: two-dimensional atomic crystals that contain magnetic elements and thus exhibit intrinsic magnetic properties. These cleavable materials provide the ideal platform for exploring magnetism in the two-dimensional limit, where new physical phenomena are expected, and represent a substantial shift in our ability to control and investigate nanoscale phases. We present the theoretical background and motivation for investigating this class of crystals, describe the material landscape and the current experimental status of measurement techniques as well as devices, and discuss promising future directions for the study of magnetic van der Waals materials.

Magnetism in two-dimensional van der Waals materials.

Artificial heterostructures assembled from van der Waals materials promise to combine materials without the traditional restrictions in heterostructure-growth such as lattice matching conditions and atom interdiffusion. Simple stacking of van der Waals materials with diverse properties would thus enable the fabrication of novel materials or device structures with atomically precise interfaces. Because covalent bonding in these layered materials is limited to molecular planes and the interaction between planes are very weak, only small changes in the electronic structure are expected by stacking these materials on top of each other. Here we prepare interfaces between CVD-grown graphene and MoS2 and report the direct measurement of the electronic structure of such a van der Waals heterostructure by angle-resolved photoemission spectroscopy. While the Dirac cone of graphene remains intact and no significant charge transfer doping is detected, we observe formation of band gaps in the π-band of graphene, away ...

Direct Observation of Interlayer Hybridization and Dirac Relativistic Carriers in Graphene/MoS2 van der Waals Heterostructures

(Sub)monolayer MoTe2 is grown by molecular beam epitaxy on a bulk MoS2 substrate. The film morphology, the thermally induced transformation of structural and compositional phases, as well as the chemical stability upon exposure to atmosphere are investigated by scanning tunneling microscopy and photoemission spectroscopy. Predominantly, semiconducting α-MoTe2 islands are obtained under tellurium rich growth conditions and a substrate temperature of 200 °C. Under less tellurium-rich conditions, elongated and meandering MoTe2−x strands are formed rather than compact islands. Similarly, annealing of initial α-MoTe2 islands to above 500 °C causes the loss of tellurium and possibly transformation into the same MoTe2−x strands. Consequently, under vacuum conditions the the transformation of α-MoTe2 monolayers into the semimetallic β -MoTe2 high temperature phase is accompanied by a loss of Te and formation of MoTe2−x phase. The obtained tellurium deficient MoTe2−x phase is almost metallic but a small band gap of a few tens meV remains. The as-grown α-MoTe2 islands exhibit a moire structure with ~2.6 nm periodicity. This periodicity implies a rotation of ~56° between the MoTe2 and MoS2. We assign the observation of a specific rotation angle for the grown MoTe2 islands with respect to the MoS2 substrate to the lowest energy adsorption configuration for MoTe2 monolayers on MoS2 substrates. Exposure of the as grown films to atmosphere results in oxidation of the MoTe2 film. The oxidized film maintains the two-dimensional island morphology of the initial film and thus is a candidate for a 2D (amorphous) oxide layer on MoS2.

https://iopscience.iop.org/article/10.1088/2053-1583/2/4/044010/pdf

Molecular beam epitaxy of the van der Waals heterostructure MoTe 2 on MoS 2 : phase, thermal, and chemical stability

Heterostructures of dissimilar 2D materials are potential building blocks for novel materials and may enable the formation of new (photo)electronic device architectures. Previous work mainly focused on supporting graphene on insulating wide-band gap materials, such as hex-BN and mica. Here we investigate the interface between zero-band gap semiconductor graphene and band-gap semiconductor MoS2 as a potential building block for entirely 2D-material based semiconducting devices. We show that solution transfer results in water trapping at the interface which may be removed by annealing to ∼300 °C in a vacuum. After removal of the water, by high temperature annealing, ultraflat graphene is obtained on MoS2 with only a very weak moire pattern observable in scanning tunneling microscopy images due to lattice mismatch and random alignment of graphene with respect to the MoS2 substrate. Photoemission spectroscopy indicates interface dipole formation, p-type doping of graphene by ∼0.09 eV downward shift of the Fermi-level below the Dirac point, and a negative space charge region in bulk MoS2. Interestingly, valence band spectra of the graphene covered MoS2 surface indicate a band gap narrowing of the MoS2 surface by ∼0.1 eV. This band gap reduction at the surface is further evidence that interlayer van der Waals interactions critically influence the band structure of 2D-layered dichalcogenides and suggest that interfacing with dissimilar van der Waals materials allows tuning of their electronic properties.

Interface properties of CVD grown graphene transferred onto MoS2(0001)

The hydrogen evolution reaction (HER) is a fundamental process that impacts several important clean energy technologies. Great efforts have been taken to identify alternative materials that could replace Pt for this reaction or that may present additional functional properties such as optical activity and advanced electronic properties. Herein, it is reported a comparative study of the HER activity of MoTe2, MoSe2 and for the first time their solid solutions, obtained as two dimensional ultrathin films on highly oriented pyrolytic graphite. Combining advanced characterization techniques and density functional theory calculations 1 with electrochemical measurements, it is shown that the chemical activity of the scarcely reactive 2H phases can be boosted by the presence metallic twin boundaries. These defects, which are thermodynamically stable and naturally present on molecular beam epitaxy grown films, endow the basal plane of the 2H phase with a high chemical activity, such as in the case of the metastable 1T polymorph. The production of hydrogen from water splitting, using renewable energy sources, is one of the possible strategies to solve the current climate challenges, because hydrogen is a convenient energy carrier that can be used to chemically store the energy produced by other intermittent renewable sources. Electrolysis is the most efficient and industrially scalable method to split water. It comprises two separate reactions: the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). The former involves the adsorption and reduction of protons from the electrolyte to molecular hydrogen as a consequence of the application of a sufficiently high potential.[1] To reduce this potential and speed up the kinetics, efficient catalysts are needed. Currently, Pt group metals[2,3] show the highest activities, however their high cost and shortage of supply prevent a widespread industrial application. Among possible alternatives, transition metal carbides, chalcogenides, nitrides and phosphides are particularly promising, considering the good performance and low cost and natural abundance.[4,5]

Horacio Coy Diaz

Papers

Strong room-temperature ferromagnetism in VSe2 monolayers on van der Waals substrates.

Direct Observation of Interlayer Hybridization and Dirac Relativistic Carriers in Graphene/MoS2 van der Waals Heterostructures

Molecular beam epitaxy of the van der Waals heterostructure MoTe 2 on MoS 2 : phase, thermal, and chemical stability

Interface properties of CVD grown graphene transferred onto MoS2(0001)

Metallic Twin Boundaries Boost the Hydrogen Evolution Reaction on the Basal Plane of Molybdenum Selenotellurides