Kyle Seyler

Highly anisotropic and robust excitons in monolayer black phosphorus

Semi-metallic graphene and semiconducting monolayer transition-metal dichalcogenides are the most intensively studied two-dimensional materials of recent years. Lately, black phosphorus has emerged as a promising new two-dimensional material due to its widely tunable and direct bandgap, high carrier mobility and remarkable in-plane anisotropic electrical, optical and phonon properties. However, current progress is primarily limited to its thin-film form. Here, we reveal highly anisotropic and strongly bound excitons in monolayer black phosphorus using polarization-resolved photoluminescence measurements at room temperature. We show that, regardless of the excitation laser polarization, the emitted light from the monolayer is linearly polarized along the light effective mass direction and centres around 1.3 eV, a clear signature of emission from highly anisotropic bright excitons. Moreover, photoluminescence excitation spectroscopy suggests a quasiparticle bandgap of 2.2 eV, from which we estimate an exciton binding energy of ∼0.9 eV, consistent with theoretical results based on first principles. The experimental observation of highly anisotropic, bright excitons with large binding energy not only opens avenues for the future explorations of many-electron physics in this unusual two-dimensional material, but also suggests its promising future in optoelectronic devices.

Observation of Long-Lived Interlayer Excitons in Monolayer MoSe2-WSe2 Heterostructures

Van der Waals bound heterostructures constructed with two-dimensional materials, such as graphene, boron nitride and transition metal dichalcogenides, have sparked wide interest in device physics and technologies at the two-dimensional limit. One highly coveted heterostructure is that of differing monolayer transition metal dichalcogenides with type-II band alignment, with bound electrons and holes localized in individual monolayers, that is, interlayer excitons. Here, we report the observation of interlayer excitons in monolayer MoSe2-WSe2 heterostructures by photoluminescence and photoluminescence excitation spectroscopy. We find that their energy and luminescence intensity are highly tunable by an applied vertical gate voltage. Moreover, we measure an interlayer exciton lifetime of ~1.8 ns, an order of magnitude longer than intralayer excitons in monolayers. Our work demonstrates optical pumping of interlayer electric polarization, which may provoke further exploration of interlayer exciton condensation, as well as new applications in two-dimensional lasers, light-emitting diodes and photovoltaic devices.

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

Since the discovery of graphene, the family of two-dimensional materials has grown, displaying a broad range of electronic properties. Recent additions include semiconductors with spin–valley coupling, Ising superconductors that can be tuned into a quantum metal, possible Mott insulators with tunable charge-density waves, and topological semimetals with edge transport. However, no two-dimensional crystal with intrinsic magnetism has yet been discovered; such a crystal would be useful in many technologies from sensing to data storage. Theoretically, magnetic order is prohibited in the two-dimensional isotropic Heisenberg model at finite temperatures by the Mermin–Wagner theorem. 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 crystals. Remarkably, bilayer CrI3 displays suppressed magnetization with a metamagnetic effect, 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 magnetoelectronics, and van der Waals engineering to produce interface phenomena.

Valley-polarized exciton dynamics in a 2D semiconductor heterostructure

Stacking to prolong valley lifetime In the material MoSe2, which, like graphene, has a two-dimensional honeycomb crystal lattice, the electronic structure has two “valleys.” Electrons can be distinguished by the valley they reside in, making them act as potential information carriers. However, electrons easily lose this information by scattering into the other valley. Rivera et al. placed single layers of MoSe2 and WSe2 on top of each other and shone circularly polarized light on the structure. The light caused excitons—pairs of electrons and holes—to form so that the hole and electron came from the same valley but different layers. The valley-specific character of such excitons persisted far longer than would be possible in a single layer of either material. Science, this issue p. 688 Photoluminescence measurements are used to deduce a valley lifetime of 40 nanoseconds in heterostructures of MoSe2 and WSe2. Heterostructures comprising different monolayer semiconductors provide an attractive setting for fundamental science and device technologies, such as in the emerging field of valleytronics. We realized valley-specific interlayer excitons in monolayer WSe2-MoSe2 vertical heterostructures. We created interlayer exciton spin-valley polarization by means of circularly polarized optical pumping and determined a valley lifetime of 40 nanoseconds. This long-lived polarization enables the visualization of the expansion of a valley-polarized exciton cloud over several micrometers. The spatial pattern of the polarization evolves into a ring with increasing exciton density, a manifestation of valley exciton exchange interactions. Our work introduces van der Waals heterostructures as a promising platform from which to study valley exciton physics.

Electrical control of second-harmonic generation in a WSe2 monolayer transistor

Nonlinear optical frequency conversion, in which optical fields interact with a nonlinear medium to produce new field frequencies, is ubiquitous in modern photonic systems. However, the nonlinear electric susceptibilities that give rise to such phenomena are often challenging to tune in a given material and, so far, dynamical control of optical nonlinearities remains confined to research laboratories as a spectroscopic tool. Here, we report a mechanism to electrically control second-order optical nonlinearities in monolayer WSe₂, an atomically thin semiconductor. We show that the intensity of second-harmonic generation at the A-exciton resonance is tunable by over an order of magnitude at low temperature and nearly a factor of four at room temperature through electrostatic doping in a field-effect transistor. Such tunability arises from the strong exciton charging effects in monolayer semiconductors, which allow for exceptional control over the oscillator strengths at the exciton and trion resonances. The exciton-enhanced second-harmonic generation is counter-circularly polarized to the excitation laser due to the combination of the two-photon and one-photon valley selection rules, which have opposite helicity in the monolayer. Our study paves the way towards a new platform for chip-scale, electrically tunable nonlinear optical devices based on two-dimensional semiconductors.

Van der Waals engineering of ferromagnetic semiconductor heterostructures for spin and valleytronics

A van der Waals heterostructure of monolayer WSe2 and ferromagnetic CrI3 enables exceptional control of valley pseudospin. The integration of magnetic material with semiconductors has been fertile ground for fundamental science as well as of great practical interest toward the seamless integration of information processing and storage. We create van der Waals heterostructures formed by an ultrathin ferromagnetic semiconductor CrI3 and a monolayer of WSe2. We observe unprecedented control of the spin and valley pseudospin in WSe2, where we detect a large magnetic exchange field of nearly 13 T and rapid switching of the WSe2 valley splitting and polarization via flipping of the CrI3 magnetization. The WSe2 photoluminescence intensity strongly depends on the relative alignment between photoexcited spins in WSe2 and the CrI3 magnetization, because of ultrafast spin-dependent charge hopping across the heterostructure interface. The photoluminescence detection of valley pseudospin provides a simple and sensitive method to probe the intriguing domain dynamics in the ultrathin magnet, as well as the rich spin interactions within the heterostructure.

Determination of band offsets, hybridization, and exciton binding in 2D semiconductor heterostructures

Photoemission measurements on exfoliated 2D heterostructures reveal detailed electronic structure and hybridization effects. Combining monolayers of different two-dimensional semiconductors into heterostructures creates new phenomena and device possibilities. Understanding and exploiting these phenomena hinge on knowing the electronic structure and the properties of interlayer excitations. We determine the key unknown parameters in MoSe2/WSe2 heterobilayers by using rational device design and submicrometer angle-resolved photoemission spectroscopy (μ-ARPES) in combination with photoluminescence. We find that the bands in the K-point valleys are weakly hybridized, with a valence band offset of 300 meV, implying type II band alignment. We deduce that the binding energy of interlayer excitons is more than 200 meV, an order of magnitude higher than that in analogous GaAs structures. Hybridization strongly modifies the bands at Γ, but the valence band edge remains at the K points. We also find that the spectrum of a rotationally aligned heterobilayer reflects a mixture of commensurate and incommensurate domains. These results directly answer many outstanding questions about the electronic nature of MoSe2/WSe2 heterobilayers and demonstrate a practical approach for high spectral resolution in ARPES of device-scale structures.

Room-temperature ferroelectricity in CuInP2S6 ultrathin flakes

Two-dimensional (2D) materials have emerged as promising candidates for various optoelectronic applications based on their diverse electronic properties, ranging from insulating to superconducting. However, cooperative phenomena such as ferroelectricity in the 2D limit have not been well explored. Here, we report room-temperature ferroelectricity in 2D CuInP2S6 (CIPS) with a transition temperature of ∼320 K. Switchable polarization is observed in thin CIPS of ∼4 nm. To demonstrate the potential of this 2D ferroelectric material, we prepare a van der Waals (vdW) ferroelectric diode formed by CIPS/Si heterostructure, which shows good memory behaviour with on/off ratio of ∼100. The addition of ferroelectricity to the 2D family opens up possibilities for numerous novel applications, including sensors, actuators, non-volatile memory devices, and various vdW heterostructures based on 2D ferroelectricity.

Directional interlayer spin-valley transfer in two-dimensional heterostructures

Van der Waals heterostructures formed by two different monolayer semiconductors have emerged as a promising platform for new optoelectronic and spin/valleytronic applications. In addition to its atomically thin nature, a two-dimensional semiconductor heterostructure is distinct from its three-dimensional counterparts due to the unique coupled spin-valley physics of its constituent monolayers. Here, we report the direct observation that an optically generated spin-valley polarization in one monolayer can be transferred between layers of a two-dimensional MoSe2–WSe2 heterostructure. Using non-degenerate optical circular dichroism spectroscopy, we show that charge transfer between two monolayers conserves spin-valley polarization and is only weakly dependent on the twist angle between layers. Our work points to a new spin-valley pumping scheme in nanoscale devices, provides a fundamental understanding of spin-valley transfer across the two-dimensional interface, and shows the potential use of two-dimensional semiconductors as a spin-valley generator in two-dimensional spin/valleytronic devices for storing and processing information.

Giant tunneling magnetoresistance in spin-filter van der Waals heterostructures

An intrinsic magnetic tunnel junction An electrical current running through two stacked magnetic layers is larger if their magnetizations point in the same direction than if they point in opposite directions. These so-called magnetic tunnel junctions, used in electronics, must be carefully engineered. Two groups now show that high magnetoresistance intrinsically occurs in samples of the layered material CrI3 sandwiched between graphite contacts. By varying the number of layers in the samples, Klein et al. and Song et al. found that the electrical current running perpendicular to the layers was largest in high magnetic fields and smallest near zero field. This observation is consistent with adjacent layers naturally having opposite magnetizations, which align parallel to each other in high magnetic fields. Science, this issue p. 1218, p. 1214 The atomic layers of the material CrI3 act as spin filters in graphite/CrI3/graphite junctions. Magnetic multilayer devices that exploit magnetoresistance are the backbone of magnetic sensing and data storage technologies. Here, we report multiple-spin-filter magnetic tunnel junctions (sf-MTJs) based on van der Waals (vdW) heterostructures in which atomically thin chromium triiodide (CrI3) acts as a spin-filter tunnel barrier sandwiched between graphene contacts. We demonstrate tunneling magnetoresistance that is drastically enhanced with increasing CrI3 layer thickness, reaching a record 19,000% for magnetic multilayer structures using four-layer sf-MTJs at low temperatures. Using magnetic circular dichroism measurements, we attribute these effects to the intrinsic layer-by-layer antiferromagnetic ordering of the atomically thin CrI3. Our work reveals the possibility to push magnetic information storage to the atomically thin limit and highlights CrI3 as a superlative magnetic tunnel barrier for vdW heterostructure spintronic devices.