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The electronic properties of devices based on two-dimensional materials are significantly influenced by interactions with the substrate and electrode materials. Here, we use photoemission electron microscopy to investigate the real- and momentum-space electronic structures of electrically contacted single-layer WS2 stacked on hBN, SiO2, and TiO2 substrates. Using work function and X-ray absorption imaging, we single-out clean microscopic regions of each interface type and collect the valence band dispersion. We infer the alignments of the electronic bandgaps and electron affinities from the measured valence band offsets of WS2 and the three substrate materials using a simple electron affinity rule and discuss the implications for vertical band structure engineering using mixed three- and two-dimensional materials.

In two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs), new electronic phenomena such as tunable bandgaps 1-3 and strongly bound excitons and trions emerge from strong many-body effects 4-6 , beyond the spin and valley degrees of freedom induced by spin-orbit coupling and by lattice symmetry 7 . Combining single-layer TMDs with other 2D materials in van der Waals heterostructures offers an intriguing means of controlling the electronic properties through these many-body effects, by means of engineered interlayer interactions 8-10 . Here, we use micro-focused angle-resolved photoemission spectroscopy (microARPES) and in situ surface doping to manipulate the electronic structure of single-layer WS 2 on hexagonal boron nitride (WS 2 /h-BN). Upon electron doping, we observe an unexpected giant renormalization of the spin-orbit splitting of the single-layer WS 2 valence band, from 430 meV to 660 meV, together with a bandgap reduction of at least 325 meV, attributed to the formation of trionic quasiparticles. These findings suggest that the electronic, spintronic and excitonic properties are widely tunable in 2D TMD/h-BN heterostructures, as these are intimately linked to the quasiparticle dynamics of the materials 11-13 .

Quantum photonics promises significant advances in secure communications, metrology, sensing, and information processing/computation. Single-photon sources are fundamental to this endeavor. However, the lack of high-quality single photon sources remains a significant obstacle. We present here a paradigm for the control of single photon emitters (SPEs) and single photon purity by integrating monolayer WS 2 with the organic ferroelectric polymer poly(vinylidene fluoride- co -trifluoroethylene) (P(VDF-TrFE)). We demonstrate that the ferroelectric domains in the P(VDF-TrFE) film control the purity of single photon emission from the adjacent WS 2 . By switching the ferroelectric polarization, we reversibly tune the single photon purity between the semiclassical and quantum light regimes, with single photon purities as high as 94%. This demonstrates a method for modulating and encoding quantum photonic information, complementing more complex approaches. This multidimensional heterostructure introduces an approach for control of quantum emitters by combining the nonvolatile ferroic properties of a ferroelectric with the radiative properties of the zero-dimensional atomic-scale emitters embedded in the two-dimensional WS 2 semiconductor monolayer.

Quantum emitters are essential components of quantum photonic circuitry envisioned beyond the current optoelectronic state-of-the-art. Two dimensional materials are attractive hosts for such emitters. However, the high single photon purity required is rarely realized due to the presence of spectrally degenerate classical light originating from defects. Here, we show that design of a van der Waals heterostructure effectively eliminates this spurious light, resulting in purities suitable for a variety of quantum technological applications. Single photon purity from emitters in monolayer WSe 2 increases from 60% to 92% by incorporating this monolayer in a simple graphite/WSe 2 heterostructure. Fast interlayer charge transfer quenches a broad photoluminescence background by preventing radiative recombination through long-lived defect bound exciton states. This approach is generally applicable to other 2D emitter materials, circumvents issues of material quality, and offers a path forward to achieve the ultrahigh single photon purities ultimately required for photon-based quantum technologies.

Harnessing electronic excitations involving coherent coupling to bosonic modes is essential for the design and control of emergent phenomena in quantum materials. In situations where charge carriers induce a lattice distortion due to the electron-phonon interaction, the conducting states get "dressed", which leads to the formation of polaronic quasiparticles. The exploration of polaronic effects on low-energy excitations is in its infancy in two-dimensional materials. Here, we present the discovery of an interlayer plasmon polaron in heterostructures composed of graphene on top of single-layer WS 2 . By using micro-focused angle-resolved photoemission spectroscopy during in situ doping of the top graphene layer, we observe a strong quasiparticle peak accompanied by several carrier density-dependent shake-off replicas around the single-layer WS 2 conduction band minimum. Our results are explained by an effective many-body model in terms of a coupling between single-layer WS 2 conduction electrons and an interlayer plasmon mode. It is important to take into account the presence of such interlayer collective modes, as they have profound consequences for the electronic and optical properties of heterostructures that are routinely explored in many device architectures involving 2D transition metal dichalcogenides., (© 2024. The Author(s).)

Topological insulators (TIs) have shown promise as a spin-generating layer to switch the magnetization state of ferromagnets via spin-orbit torque (SOT) due to charge-to-spin conversion efficiency of the TI surface states that arises from spin-momentum locking. However, when TIs are interfaced with conventional bulk ferromagnetic metals, the combination of charge transfer and hybridization can potentially destroy the spin texture and hamper the possibility of accessing the TI surface states. Here, we fabricate an all van der Waals (vdW) heterostructure consisting of molecular beam epitaxy grown bulk-insulating Bi 2 Se 3 and exfoliated 2D metallic ferromagnet Fe 3 GeTe 2 (FGT) with perpendicular anisotropy. By detecting the magnetization state of the FGT via anomalous Hall effect and magneto-optical Kerr effect measurements, we determine the critical switching current density for magnetization switching to be J c ≈ 1.2 × 10 6 A/cm 2 , the lowest reported for the switching of a perpendicular anisotropy ferromagnet using Bi 2 Se 3 . From second harmonic Hall measurements, we further determine the SOT efficiency (ξ DL ) to be in the range of 1.8 ± 0.3 and 1.4 ± 0.08 between 5 and 150 K, comparable to the highest values reported for Bi 2 Se 3 . Our density functional theory calculations find that the weak interlayer interactions at the Bi 2 Se 3 /FGT interface lead to a weakened dipole at the interface and suppress the proximity induced magnetic moment on Bi 2 Se 3 . This enables direct access to the TI surface states contributed by the first quintuple layer, where the spins are singly degenerate with significant net in-plane spin polarization. Our results highlight the clear advantage of all-vdW heterostructures with weak interlayer interactions that can enhance SOT efficiency and minimize critical current density, an important step toward realizing next generation low-power nonvolatile memory and spintronic devices.

The ability to assemble layers of two-dimensional (2D) materials to form permutations of van der Waals heterostructures provides significant opportunities in materials design and synthesis. Interlayer interactions can enable desired properties and functionality, and understanding such interactions is essential to that end. Here we report formation of interlayer exciton-phonon bound states in Bi 2 Se 3 /WS 2 heterostructures, where the Bi 2 Se 3 A 1 (3) surface phonon, a mode particularly susceptible to electron-phonon coupling, is imprinted onto the excitonic emission of the WS 2 . The exciton-phonon bound state (or exciton-phonon quasiparticle) presents itself as evenly separated peaks superposed on the WS 2 excitonic photoluminescence spectrum, whose periodic spacing corresponds to the A 1 (3) surface phonon energy. Low-temperature polarized Raman spectroscopy of Bi 2 Se 3 reveals intense surface phonons and local symmetry breaking that allows the A 1 (3) surface phonon to manifest in otherwise forbidden scattering geometries. Our work advances knowledge of the complex interlayer van der Waals interactions and facilitates technologies that combine the distinctive transport and optical properties from separate materials into one device for possible spintronics, valleytronics, and quantum computing applications.

We present a method utilizing an applied electrostatic potential for suppressing the broad defect bound excitonic emission in two-dimensional materials (2DMs) which otherwise inhibits the purity of strain induced single photon emitters (SPEs). Our heterostructure consists of a WSe 2 monolayer on a polymer in which strain has been deterministically introduced via an atomic force microscope (AFM) tip. We show that by applying an electrostatic potential, the broad defect bound background is suppressed at cryogenic temperatures, resulting in a substantial improvement in single photon purity demonstrated by a 10-fold reduction of the correlation function g (2) (0) value from 0.73 to 0.07. In addition, we see a 2-fold increase in the intensity of the SPEs as well as the ability to activate/deactivate the emitters at certain wavelengths. Finally, we present an increase in the operating temperature of the SPE up to 110 K, a 50 K increase when compared with the results when no electrostatic potential is present.

Bilayers of 2D materials offer opportunities for creating devices with tunable electronic, optical, and mechanical properties. In van der Waals heterostructures (vdWHs) where the constituent monolayers have different lattice constants, a moiré superlattice forms with a length scale larger than the lattice constant of either constituent material regardless of twist angle. Here, we report the appearance of moiré Raman modes from nearly aligned WSe 2 -WS 2 vdWHs in the range of 240-260 cm -1 , which are absent in both monolayers and homobilayers of WSe 2 and WS 2 and in largely misaligned WSe 2 -WS 2 vdWHs. Using first-principles calculations and geometric arguments, we show that these moiré Raman modes are a consequence of the large moiré length scale, which results in zone-folded phonon modes that are Raman active. These modes are sensitive to changes in twist angle, but notably, they occur at identical frequencies for a given small twist angle away from either the 0-degree or 60-degree aligned heterostructure. Our measurements also show a strong Raman intensity modulation in the frequency range of interest, with near 0 and near 60-degree vdWHs exhibiting a markedly different dependence on excitation energy. In near 0-degree aligned WSe 2 -WS 2 vdWHs, a nearly complete suppression of both the moiré Raman modes and the WSe 2 A 1g Raman mode (∼250 cm -1 ) is observed when exciting with a 532 nm CW laser at room temperature. Temperature-dependent reflectance contrast measurements demonstrate the significant Raman intensity modulation arises from resonant Raman effects.

Oxygen conductors and transporters are important to several consequential renewable energy technologies, including fuel cells and syngas production. Separately, monolayer transition-metal dichalcogenides (TMDs) have demonstrated significant promise for a range of applications, including quantum computing, advanced sensors, valleytronics, and next-generation optoelectronics. Here, we synthesize a few-nanometer-thick Bi x O y Se z compound that strongly resembles a rare R 3 m bismuth oxide (Bi 2 O 3 ) phase and combine it with monolayer TMDs, which are highly sensitive to their environment. We use the resulting 2D heterostructure to study oxygen transport through Bi x O y Se z into the interlayer region, whereby the 2D material properties are modulated, finding extraordinarily fast diffusion near room temperature under laser exposure. The oxygen diffusion enables reversible and precise modification of the 2D material properties by controllably intercalating and deintercalating oxygen. Changes are spatially confined, enabling sub-micrometer features (e.g., pixels), and are long-term stable for more than 221 days. Our work suggests few-nanometer-thick Bi x O y Se z is a promising unexplored room-temperature oxygen transporter. Additionally, our findings suggest that the mechanism can be applied to other 2D materials as a generalized method to manipulate their properties with high precision and sub-micrometer spatial resolution.

Current-generated spin arising from spin-momentum locking in topological insulator (TI) surface states has been shown to switch the magnetization of an adjacent ferromagnet (FM) via spin-orbit torque (SOT) with a much higher efficiency than heavy metals. However, in such FM/TI heterostructures, most of the current is shunted through the FM metal due to its lower resistance, and recent calculations have also shown that topological surface states can be significantly impacted when interfaced with an FM metal such as Ni and Co. Hence, placing an insulating layer between the TI and FM will not only prevent current shunting, therefore minimizing overall power consumption, but may also help preserve the topological surface states at the interface. Here, we report the van der Waals epitaxial growth of β-phase In 2 Se 3 on Bi 2 Se 3 by molecular beam epitaxy and demonstrate its spin sensitivity by the electrical detection of current-generated spin in Bi 2 Se 3 surface states using a Fe/In 2 Se 3 detector contact. Our density functional calculations further confirm that the linear dispersion and spin texture of the Bi 2 Se 3 surface states are indeed preserved at the In 2 Se 3 /Bi 2 Se 3 interface. This demonstration of an epitaxial crystalline spin-sensitive barrier that can be grown directly on Bi 2 Se 3 , and verification that it preserves the topological surface state, is electrically insulating and spin-sensitive, is an important step toward minimizing overall power consumption in SOT switching in TI/FM heterostructures in fully epitaxial topological spintronic devices.

Characterizing and manipulating the circular polarization of light is central to numerous emerging technologies, including spintronics and quantum computing. Separately, monolayer tungsten disulfide (WS 2 ) is a versatile material that has demonstrated promise in a variety of applications, including single photon emitters and valleytronics. Here, we demonstrate a method to tune the photoluminescence (PL) intensity (factor of ×161), peak position (38.4 meV range), circular polarization (39.4% range), and valley polarization of a Bi 2 Se 3 -WS 2 2D heterostructure using a low-power laser (0.762 μW) in ambient conditions. Changes are spatially confined to the laser spot, enabling submicrometer (814 nm) features, and are long-term stable (>334 days). PL and valley polarization changes can be controllably reversed through laser exposure in a vacuum, allowing the material to be erased and reused. Atmospheric experiments and first-principles calculations indicate oxygen diffusion modulates the exciton radiative vs nonradiative recombination pathways, where oxygen absorption leads to brightening and desorption to darkening.

The twist angle between the monolayers in van der Waals heterostructures provides a new degree of freedom in tuning material properties. We compare the optical properties of WSe 2 homobilayers with 2H and 3R stacking using photoluminescence, Raman spectroscopy, and reflectance contrast measurements under ambient and cryogenic temperatures. Clear stacking-dependent differences are evident for all temperatures, with both photoluminescence and reflectance contrast spectra exhibiting a blue shift in spectral features in 2H compared to 3R bilayers. Density functional theory (DFT) calculations elucidate the source of the variations and the fundamental differences between 2H and 3R stackings. DFT finds larger energies for both A and B excitonic features in 2H than in 3R, consistent with experimental results. In both stacking geometries, the intensity of the dominant A 1g Raman mode exhibits significant changes as a function of laser excitation wavelength. These variations in intensity are intimately linked to the stacking- and temperature-dependent optical absorption through resonant enhancement effects. The strongest enhancement is achieved when the laser excitation coincides with the C excitonic feature, leading to the largest Raman intensity under 514 nm excitation in 2H stacking and at 520 nm in 3R stacked WSe 2 bilayers.

We have directly written nanoscale patterns of magnetic ordering in FeRh films using focused helium-ion beam irradiation. By varying the dose, we pattern arrays with metamagnetic transition temperatures that range from the as-grown film temperature to below room temperature. We employ transmission electron microscopy, X-ray diffraction, and temperature-dependent transport measurements to characterize the as-grown film, and magneto-optic Kerr effect imaging to quantify the He + irradiation-induced changes to the magnetic order. Moreover, we demonstrate temperature-dependent optical microscopy and conductive atomic force microscopy as indirect probes of the metamagnetic transition that are sensitive to the differences in dielectric properties and electrical conductivity, respectively, of FeRh in the antiferromagnetic (AF) and ferromagnetic (FM) states. Using density functional theory, we quantify strain- and defect-induced changes in spin-flip energy to understand their influence on the metamagnetic transition temperature. This work holds promise for in-plane AF-FM spintronic devices, by reducing the need for multiple patterning steps or different materials, and potentially eliminating interfacial polarization losses due to cross material interfacial spin scattering.

Van der Waals layered materials, such as transition metal dichalcogenides (TMDs), are an exciting class of materials with weak interlayer bonding, which enables one to create so-called van der Waals heterostructures (vdWH). One promising attribute of vdWH is the ability to rotate the layers at arbitrary azimuthal angles relative to one another. Recent work has shown that control of the twist angle between layers can have a dramatic effect on TMD vdWH properties, but the twist angle has been treated solely through the use of rigid-lattice moiré patterns. No atomic reconstruction, that is, any rearrangement of atoms within the individual layers, has been reported experimentally to date. Here, we demonstrate that vdWH of MoSe 2 /WSe 2 and MoS 2 /WS 2 at twist angles ≤1° undergo significant atomic level reconstruction leading to discrete commensurate domains divided by narrow domain walls, rather than a smoothly varying rigid-lattice moiré pattern as has been assumed in prior experimental work. Using conductive atomic force microscopy (CAFM), we show that TMD vdWH at small twist angles exhibit large domains of constant conductivity. The domains in samples with R-type stacking are triangular, whereas the domains in samples with H-type stacking are hexagonal. Transmission electron microscopy provides additional evidence of atomic reconstruction in MoSe 2 /WSe 2 structures and demonstrates the transition between a rigid-lattice moiré pattern for large angles and atomic reconstruction for small angles. We use density functional theory to calculate the band structures of the commensurate reconstructed domains and find that the modulation of the relative electronic band edges is consistent with the CAFM results and photoluminescence spectra. The presence of atomic reconstruction in TMD heterostructures and the observed impact on nanometer-scale electronic properties provide fundamental insight into the behavior of this important class of heterostructures.

Stacking two-dimensional (2D) van der Waals materials with different interlayer atomic registry in a heterobilayer causes the formation of a long-range periodic superlattice that may bestow the heterostructure with properties such as new quantum fractal states or superconductivity. Recent optical measurements of transition metal dichalcogenide (TMD) heterobilayers have revealed the presence of hybridized interlayer electron-hole pair excitations at energies defined by the superlattice potential. The corresponding quasiparticle band structures, so-called minibands, have remained elusive, and no such features have been reported for heterobilayers composed of a TMD and another type of 2D material. We introduce a new x-ray capillary technology for performing microfocused angle-resolved photoemission spectroscopy with a spatial resolution of ~1 μm, and directly observe minibands at certain twist angles in mini Brillouin zones (mBZs). We discuss their origin in terms of initial and final state effects by analyzing their dispersion in distinct mBZs., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

We report the synthesis of high-quality single monolayer MoS 2 samples using a novel technique that utilizes direct liquid injection (DLI) for the delivery of precursors. The DLI system vaporizes a liquid consisting of a selected precursor dissolved in a solvent into small, micron-sized droplets in an expansion chamber maintained at a selected temperature and pressure, before delivery to the deposition chamber. We demonstrate the synthesis of monolayer MoS 2 on SiO 2 /Si substrates using the DLI technique with film quality superior to exfoliated samples or those grown by traditional tube furnace chemical vapor deposition (CVD) methods. Photoluminescence measurements of DLI monolayers exhibit consistently brighter emission, narrower line width, and higher emission energy than their exfoliated and CVD counterparts. Conductive atomic force microscopy identifies a defect density of 8.3 × 10 11 /cm 2 in DLI MoS 2 , lower than the measured density in CVD material and nearly an order of magnitude improvement over the exfoliated MoS 2 investigated under the same conditions. The DLI method is directly applicable to many other van der Waals materials, which require the use of challenging low vapor pressure precursors, to the growth of alloys, and sequential growths of dissimilar materials leading to van der Waals heterostructures.

Electric fields can transform materials with respect to their structure and properties, enabling various applications ranging from batteries to spintronics. Recently electrolytic gating, which can generate large electric fields and voltage-driven ion transfer, has been identified as a powerful means to achieve electric-field-controlled phase transformations. The class of transition metal oxides provide many potential candidates that present a strong response under electrolytic gating. However, very few show a reversible structural transformation at room-temperature. Here, we report the realization of a digitally synthesized transition metal oxide that shows a reversible, electric-field-controlled transformation between distinct crystalline phases at room-temperature. In superlattices comprised of alternating one-unit-cell of SrIrO 3 and La 0.2 Sr 0.8 MnO 3 , we find a reversible phase transformation with a 7% lattice change and dramatic modulation in chemical, electronic, magnetic and optical properties, mediated by the reversible transfer of oxygen and hydrogen ions. Strikingly, this phase transformation is absent in the constituent oxides, solid solutions and larger period superlattices. Our findings open up this class of materials for voltage-controlled functionality.

We report continuous-wave second harmonic and sum frequency generation from two-dimensional transition metal dichalcogenide monolayers and their heterostructures with pump irradiances several orders of magnitude lower than those of conventional pulsed experiments. The high nonlinear efficiency originates from above-gap excitons in the band nesting regions, as revealed by wavelength-dependent second order optical susceptibilities quantified in four common monolayer transition metal dichalcogenides. Using sum frequency excitation spectroscopy and imaging, we identify and distinguish one- and two-photon resonances in both monolayers and heterobilayers. Data for heterostructures reveal responses from constituent layers accompanied by nonlinear signal correlated with interlayer transitions. We demonstrate spatial mapping of heterogeneous interlayer coupling by sum frequency and second harmonic confocal microscopy on heterobilayer MoSe 2 /WSe 2 .

Breaking the valley degeneracy in monolayer transition metal dichalcogenides through the valley-selective optical Stark effect (OSE) can be exploited for classical and quantum valleytronic operations such as coherent manipulation of valley superposition states. The strong light-matter interactions responsible for the OSE have historically been described by a two-level dressed-atom model, which assumes noninteracting particles. Here we experimentally show that this model, which works well in semiconductors far from resonance, does not apply for excitation near the exciton resonance in monolayer WS 2 . Instead, we show that an excitonic model of the OSE, which includes many-body Coulomb interactions, is required. We confirm the prediction from this theory that many-body effects between virtual excitons produce a dominant blue-shift for photoexcitation detuned from resonance by less than the exciton binding energy. As such, we suggest that our findings are general to low-dimensional semiconductors that support bound excitons and other many-body Coulomb interactions.

van der Waals heterostructures (vdWHs) leverage the characteristics of two-dimensional (2D) material building blocks to create a myriad of structures with unique and desirable properties. Several commonly employed fabrication strategies rely on polymeric stamps to assemble layers of 2D materials into vertical stacks. However, the properties of such heterostructures frequently are degraded by contaminants, typically of unknown composition, trapped between the constituent layers. Such contaminants, therefore, impede studies of the intrinsic properties of heterostructures and hinder their application. Here, we use the photothermal induced resonance (PTIR) technique to obtain infrared spectra and maps of the contaminants down to a few attomoles and with nanoscale resolution. Heterostructures comprised of WSe 2 , WS 2 , and hexagonal boron nitride layers were found to contain significant amounts of poly(dimethylsiloxane) (PDMS) and polycarbonate, corresponding to the stamp materials used in their construction. Additionally, we verify that an atomic force microscope-based "nanosqueegee" technique is an effective method for locally removing contaminants by comparing spectra within as-fabricated and cleaned regions. Having identified the source of the contaminants, we demonstrate that cleaning PDMS stamps with isopropyl alcohol or toluene prior to vdWH fabrication reduces PDMS contamination within the structures. The general applicability of the PTIR technique for identifying the sources corrupting vdWHs provides valuable guidance for devising mitigation strategies (e.g., stamp cleaning or pre-/post-treatments) and enhances capabilities for producing materials with precisely engineered properties.

Current generated spin polarization in topological insulator (TI) surface states due to spin-momentum locking has been detected recently using ferromagnet/tunnel barrier contacts, where the projection of the TI spin onto the magnetization of the ferromagnet is measured as a voltage. However, opposing signs of the spin voltage have been reported, which had been tentatively attributed to the coexistence of trivial two-dimensional electron gas states on the TI surface which may exhibit opposite current-induced polarization than that of the TI Dirac surface states. Models based on electrochemical potential have been presented to determine the sign of the spin voltage expected for the TI surface states. However, these models neglect critical experimental parameters which also affect the sign measured. Here we present a Mott two-spin current resistor model which takes into account these parameters such as spin-dependent interface resistances, and show that such inclusion can lead to a crossing of the voltage potential profiles for the spin-up and spin-down electrons within the channel, which can lead to measured spin voltages of either sign. These findings offer a resolution of the ongoing controversy regarding opposite signs of spin signal reported in the literature, and highlight the importance of including realistic experimental parameters in the model.

Monolayers of transition-metal dichalcogenides (TMDs) are promising components for flexible optoelectronic devices because of their direct band gap and atomically thin nature. The photoluminescence (PL) from these materials is often strongly suppressed by nonradiative recombination mediated by midgap defect states. Here, we demonstrate up to a 200-fold increase in PL intensity from monolayer MoS 2 synthesized by chemical vapor deposition (CVD) by controlled exposure to laser light in the ambient. This spatially resolved passivation treatment is stable in air and vacuum. Regions unexposed to laser light remain dark in fluorescence despite continuous impingement of ambient gas molecules. A wavelength-dependent study confirms that PL brightening is concomitant with exciton generation in the MoS 2 ; laser light below the optical band gap fails to produce any enhancement in the PL. We highlight the photosensitive nature of the process by successfully brightening with a low-power broadband white light source. We decouple changes in absorption from defect passivation by examining the degree of circularly polarized PL. This measurement, which is independent of exciton generation, confirms that laser brightening reduces the rate of nonradiative recombination in the MoS 2 . A series of gas exposure studies demonstrate a clear correlation between PL brightening and the presence of water. We propose that H 2 O molecules passivate sulfur vacancies in the CVD-grown MoS 2 but require photogenerated excitons to overcome a large adsorption barrier. This work represents an important step in understanding the passivation of CVD-synthesized TMDs and demonstrates the interplay between adsorption and exciton generation.

We present a paradigm for encoding strain into two-dimensional materials (2DMs) to create and deterministically place single-photon emitters (SPEs) in arbitrary locations with nanometer-scale precision. Our material platform consists of a 2DM placed on top of a deformable polymer film. Upon application of sufficient mechanical stress using an atomic force microscope tip, the 2DM/polymer composite deforms, resulting in formation of highly localized strain fields with excellent control and repeatability. We show that SPEs are created and localized at these nanoindents and exhibit single-photon emission up to 60 K, the highest temperature reported in these materials. This quantum calligraphy allows deterministic placement and real time design of arbitrary patterns of SPEs for facile coupling with photonic waveguides, cavities, and plasmonic structures. In addition to enabling versatile placement of SPEs, these results present a general methodology for imparting strain into 2DM with nanometer-scale precision, providing an invaluable tool for further investigations and future applications of strain engineering of 2DM and 2DM devices.

One of the most striking properties of three-dimensional topological insulators (TIs) is spin-momentum locking, where the spin is locked at right angles to momentum and hence an unpolarized charge current creates a net spin polarization. Alternatively, if a net spin is injected into the TI surface state system, it is distinctively associated with a unique carrier momentum and hence should generate a charge accumulation, as in the so-called inverse Edelstein effect. Here using a Fe/Al 2 O 3 /BN tunnel barrier, we demonstrate both effects in a single device in Bi 2 Te 3 : the electrical detection of the spin accumulation generated by an unpolarized current flowing through the surface states, and that of the charge accumulation generated by spins injected into the surface state system. This work is the first to utilize BN as part of a hybrid tunnel barrier on TI, where we observed a high spin polarization of 93% for the TI surfaces states. The reverse spin-to-charge measurement is an independent confirmation that spin and momentum are locked in the surface states of TI, and offers additional avenues for spin manipulation. It further demonstrates the robustness and versatility of electrical access to the spin system within TI surface states, an important step towards its utilization in TI-based spintronics devices.

An emerging class of semiconductor heterostructures involves stacking discrete monolayers such as transition metal dichalcogenides (TMDs) to form van der Waals heterostructures. In these structures, it is possible to create interlayer excitons (ILEs), spatially indirect, bound electron-hole pairs with the electron in one TMD layer and the hole in an adjacent layer. We are able to clearly resolve two distinct emission peaks separated by 24 meV from an ILE in a MoSe 2 /WSe 2 heterostructure fabricated using state-of-the-art preparation techniques. These peaks have nearly equal intensity, indicating they are of common character, and have opposite circular polarizations when excited with circularly polarized light. Ab initio calculations successfully account for these observations: they show that both emission features originate from excitonic transitions that are indirect in momentum space and are split by spin-orbit coupling. Also, the electron is strongly hybridized between both the MoSe 2 and WSe 2 layers, with significant weight in both layers, contrary to the commonly assumed model. Thus, the transitions are not purely interlayer in character. This work represents a significant advance in our understanding of the static and dynamic properties of TMD heterostructures.

Two-dimensional (2D) materials exhibit many exciting phenomena that make them promising as materials for future electronic, optoelectronic, and mechanical devices. Because of their atomic thinness, interfaces play a dominant role in determining material behavior. In order to observe and exploit the unique properties of these materials, it is therefore vital to obtain clean and repeatable interfaces. However, the conventional mechanical stacking of atomically thin layers typically leads to trapped contaminants and spatially inhomogeneous interfaces, which obscure the true intrinsic behavior. This work presents a simple and generic approach to create clean 2D material interfaces in mechanically stacked structures. The operating principle is to use an AFM tip to controllably squeeze contaminants out from between 2D layers and their substrates, similar to a "squeegee". This approach leads to drastically improved homogeneity and consistency of 2D material interfaces, as demonstrated by AFM topography and significant reduction of photoluminescence line widths. Also, this approach enables emission from interlayer excitons, demonstrating that the technique enhances interlayer coupling in van der Waals heterostructures. The technique enables repeatable observation of intrinsic 2D material properties, which is crucial for the continued development of these promising materials.

Transition-metal dichalcogenides (TMDs) are an exciting class of 2D materials that exhibit many promising electronic and optoelectronic properties with potential for future device applications. The properties of TMDs are expected to be strongly influenced by a variety of defects which result from growth procedures and/or fabrication. Despite the importance of understanding defect-related phenomena, there remains a need for quantitative nanometer-scale characterization of defects over large areas in order to understand the relationship between defects and observed properties, such as photoluminescence (PL) and electrical conductivity. In this work, we present conductive atomic force microscopy measurements which reveal nanometer-scale electronically active defects in chemical vapor deposition-grown WS 2 monolayers with defect density varying from 2.3 × 10 10 cm -2 to 4.5 × 10 11 cm -2 . Comparing these defect density measurements with PL measurements across large areas (>20 μm distances) reveals a strong inverse relationship between WS 2 PL intensity and defect density. We propose a model in which the observed electronically active defects serve as nonradiative recombination centers and obtain good agreement between the experiments and model.

Strong Coulomb attraction in monolayer transition metal dichalcogenides gives rise to tightly bound excitons and many-body interactions that dominate their optoelectronic properties. However, this Coulomb interaction can be screened through control of the surrounding dielectric environment as well as through applied voltage, which provides a potential means of tuning the bandgap, exciton binding energy, and emission wavelength. Here, we directly show that the bandgap and exciton binding energy can be optically tuned by means of the intensity of the incident light. Using transient absorption spectroscopy, we identify a sub-picosecond decay component in the excited-state dynamics of WS 2 that emerges for incident photon energies above the A-exciton resonance, which originates from a nonequilibrium population of charge carriers that form excitons as they cool. The generation of this charge-carrier population exhibits two distinct energy thresholds. The higher threshold is coincident with the onset of continuum states and therefore provides a direct optical means of determining both the bandgap and exciton binding energy. Using this technique, we observe a reduction in the exciton binding energy from 310 ± 30 to 220 ± 20 meV as the excitation density is increased from 3 × 10 11 to 1.2 × 10 12 photons/cm 2 . This reduction is due to dynamic dipolar screening of Coulomb interactions by excitons, which is the underlying physical process that initiates bandgap renormalization and leads to the insulator-metal transition in monolayer transition metal dichalcogenides.

The potential for valleytronic operation has stimulated much interest in studying polarized emission from transition metal dichalcogenides. In most studies, however, little regard is given to the character of laser excitation. We measure the circularly polarized photoluminescence of WSe 2 monolayers as a function of excitation energy for both continuous-wave (cw) and pulsed laser excitation sources. Using cw excitation, the temperature dependence of the depolarization of the trion follows the same trend as that of the neutral exciton and involves collisional broadening. However, the polarization of the trion is nearly twice the polarization of the neutral exciton at low temperatures. When a pulsed laser with the same average fluence is used as the excitation source, the degrees of polarization become very similar, in stark contrast to the cw results. The difference in polarization behaviors is linked to the different amounts of energy deposited in the system during these measurements for similar average fluences. At a moderate fluence, pulsed excitation also has the potential to fundamentally alter the emission characteristics of WSe 2 .

Monolayer transition metal dichalcogenides are promising materials for valleytronic operations. They exhibit two inequivalent valleys in the Brillouin zone, and the valley populations can be directly controlled and determined using circularly polarized optical excitation and emission. The photoluminescence polarization reflects the ratio of the two valley populations. A wide range of values for the degree of circularly polarized emission, P circ , has been reported for monolayer WS 2 , although the reasons for the disparity are unclear. Here, we optically populate one valley and measure P circ to explore the valley population dynamics at room temperature in a large number of monolayer WS 2 samples synthesized via chemical vapor deposition. Under resonant excitation, P circ ranges from 2 to 32%, and we observe a pronounced inverse relationship between photoluminescence (PL) intensity and P circ . High-quality samples exhibiting strong PL and long exciton relaxation time exhibit a low degree of valley polarization, and vice versa. This behavior is also demonstrated in monolayer WSe 2 samples and transferred WS 2 , indicating that this correlation may be more generally observed and account for the wide variations reported for P circ . Time-resolved PL provides insight into the role of radiative and nonradiative contributions to the observed polarization. Short nonradiative lifetimes result in a higher measured polarization by limiting opportunity for depolarizing scattering events.

Reduced dimensionality and strong Coulombic interactions in monolayer semiconductors lead to enhanced many-body interactions. Here, we report Auger recombination, i.e., exciton-exciton annihilation, in large-area chemical vapor deposition-grown monolayer WS 2 . Using ultrafast spectroscopy, we experimentally determine the Auger rate to be 0.089 ± 0.001 cm 2 /s at room temperature, which is an order of magnitude greater than the bulk value. This nonradiative recombination pathway dominates, regardless of excitation energy, for exciton densities greater than 8.0 ± 0.6 × 10 10 cm -2 and below the Mott density. Higher-energy excitation above the A exciton resonance may initially produce a hot electron-hole gas that precedes exciton formation. Therefore, we use resonant excitation of the A exciton to ensure accuracy and avoid artifacts associated with other photogenerated species.

Single-monolayer transition metal dichalcogenides exhibit exceptionally strong photoluminescence (PL), dominated by a combination of distinct neutral and charged exciton contributions. We show here that the surface charge associated with ferroelectric domains patterned into a lead zirconium titanate film with an atomic force microscope laterally controls the spatial distribution of neutral and charged exciton populations in an adjacent WS 2 monolayer. This is manifested by the intensity and spectral composition of the PL measured in air at room temperature from the areas of WS 2 over a ferroelectric domain with a polarization dipole pointed either out of the surface plane or into the surface plane. This approach enables spatial modulation of PL intensity and trion/neutral exciton populations and fabrication of lateral quantum dot arrays in any geometry, with potential applications in nonvolatile optically addressable memory or optical quantum computation., Competing Interests: The authors declare no competing financial interest.

There is a substantial interest in the heterostructures of semiconducting transition metal dichalcogenides (TMDCs) among each other or with arbitrary materials, through which the control of the chemical, structural, electronic, spintronic, and optical properties can lead to a change in device paradigms. A critical need is to understand the interface between TMDCs and insulating substrates, for example, high-κ dielectrics, which can strongly impact the electronic properties such as the optical gap. Here, we show that the chemical and electronic properties of the single-layer (SL) TMDC, WS 2 , can be transferred onto high-κ transition metal oxide substrates TiO 2 and SrTiO 3 . The resulting samples are much more suitable for measuring their electronic and chemical structures with angle-resolved photoemission than their native-grown SiO 2 substrates. We probe the WS 2 on the micron scale across 100 μm flakes and find that the occupied electronic structure is exactly as predicted for free-standing SL WS 2 with a strong spin-orbit splitting of 420 meV and a direct band gap at the valence band maximum. Our results suggest that TMDCs can be combined with arbitrary multifunctional oxides, which may introduce alternative means of controlling the optoelectronic properties of such materials.

We report room-temperature negative magnetoresistance in ferromagnet-graphene-ferromagnet (FM|Gr|FM) junctions with minority spin polarization exceeding 80%, consistent with predictions of strong minority spin filtering. We fabricated arrays of such junctions via chemical vapor deposition of multilayer graphene on lattice-matched single-crystal NiFe(111) films and standard photolithographic patterning and etching techniques. The junctions exhibit metallic transport behavior, low resistance, and the negative magnetoresistance characteristic of a minority spin filter interface throughout the temperature range 10 to 300 K. We develop a device model to incorporate the predicted spin filtering by explicitly treating a metallic minority spin channel with spin current conversion and a tunnel barrier majority spin channel and extract spin polarization of at least 80% in the graphene layer in our structures. The junctions also show antiferromagnetic coupling, consistent with several recent predictions. The methods and findings are relevant to fast-readout low-power magnetic random access memory technology, spin logic devices, and low-power magnetic field sensors.

Three-dimensional topological insulators (TIs) exhibit time-reversal symmetry protected, linearly dispersing Dirac surface states with spin-momentum locking. Band bending at the TI surface may also lead to coexisting trivial two-dimensional electron gas (2DEG) states with parabolic energy dispersion. A bias current is expected to generate spin polarization in both systems, although with different magnitude and sign. Here we compare spin potentiometric measurements of bias current-generated spin polarization in Bi 2 Se 3 (111) where Dirac surface states coexist with trivial 2DEG states, and in InAs(001) where only trivial 2DEG states are present. We observe spin polarization arising from spin-momentum locking in both cases, with opposite signs of the measured spin voltage. We present a model based on spin dependent electrochemical potentials to directly derive the sign expected for the Dirac surface states, and show that the dominant contribution to the current-generated spin polarization in the TI is from the Dirac surface states.

We report on preparation dependent properties observed in monolayer WS 2 samples synthesized via chemical vapor deposition (CVD) on a variety of common substrates (Si/SiO 2 , sapphire, fused silica) as well as samples that were transferred from the growth substrate onto a new substrate. The as-grown CVD materials (as-WS 2 ) exhibit distinctly different optical properties than transferred WS 2 (x-WS 2 ). In the case of CVD growth on Si/SiO 2 , following transfer to fresh Si/SiO 2 there is a ~50 meV shift of the ground state exciton to higher emission energy in both photoluminescence emission and optical reflection. This shift is indicative of a reduction in tensile strain by ~0.25%. Additionally, the excitonic state in x-WS 2 is easily modulated between neutral and charged exciton by exposure to moderate laser power, while such optical control is absent in as-WS 2 for all growth substrates investigated. Finally, we observe dramatically different laser power-dependent behavior for as-grown and transferred WS 2 . These results demonstrate a strong sensitivity to sample preparation that is important for both a fundamental understanding of these novel materials as well as reliable reproduction of device properties.

The surface states of 3D topological insulators (TIs) exhibit a helical spin texture with spin locked at right angles with momentum. The chirality of this spin texture is expected to invert crossing the Dirac point, a property that has been experimentally observed by optical probes. Here, we directly determine the chirality below the Dirac point by electrically detecting spin-momentum locking in surface states of a p-type TI, Sb2Te3. A current flowing in the Sb2Te3 surface states generates a net spin polarization due to spin-momentum locking, which is electrically detected as a voltage on an Fe/Al2O3 tunnel barrier detector. Measurements of this voltage as a function of current direction and detector magnetization indicate that hole spin-momentum locking follows the right-hand rule, opposite that of electron, providing direct confirmation that the chirality is indeed inverted below Dirac point. The spin signal is linear with current, and exhibits a temperature dependence consistent with the semiconducting nature of the TI film and freeze-out of bulk conduction below 100 K. Our results demonstrate that the chirality of the helical spin texture of TI surface states can be determined electrically, an enabling step in the electrical manipulation of spins in next generation TI-based quantum devices.

Single layers of MoS2 and MoSe2 were optically pumped with circularly polarized light and an appreciable polarization was initialized as the pump energy was varied. The circular polarization of the emitted photoluminescence was monitored as a function of the difference between the excitation energy and the A-exciton emission at the K-point of the Brillouin zone. Our results show a threshold of twice the LA phonon energy, specific to the material, above which phonon-assisted intervalley scattering causes depolarization. In both materials this leads to almost complete depolarization within ~100 meV above the threshold energy. We identify the extra kinetic energy of the exciton (independent of whether it is neutral or charged) as the key parameter for presenting a unifying picture of the depolarization process.

In bulk and quantum-confined semiconductors, magneto-optical studies have historically played an essential role in determining the fundamental parameters of excitons (size, binding energy, spin, dimensionality and so on). Here we report low-temperature polarized reflection spectroscopy of atomically thin WS2 and MoS2 in high magnetic fields to 65 T. Both the A and B excitons exhibit similar Zeeman splittings of approximately -230 μeV T(-1) (g-factor ≃-4), thereby quantifying the valley Zeeman effect in monolayer transition-metal disulphides. Crucially, these large fields also allow observation of the small quadratic diamagnetic shifts of both A and B excitons in monolayer WS2, from which radii of ∼1.53 and ∼1.16 nm are calculated. Further, when analysed within a model of non-local dielectric screening, these diamagnetic shifts also constrain estimates of the A and B exciton binding energies (410 and 470 meV, respectively, using a reduced A exciton mass of 0.16 times the free electron mass). These results highlight the utility of high magnetic fields for understanding new two-dimensional materials.

Monolayer WS2 offers great promise for use in optical devices due to its direct bandgap and high photoluminescence intensity. While fundamental investigations can be performed on exfoliated material, large-area and high quality materials are essential for implementation of technological applications. In this work, we synthesize monolayer WS2 under various controlled conditions and characterize the films using photoluminescence, Raman and x-ray photoelectron spectroscopies. We demonstrate that the introduction of hydrogen to the argon carrier gas dramatically improves the optical quality and increases the growth area of WS2, resulting in films exhibiting mm(2) coverage. The addition of hydrogen more effectively reduces the WO3 precursor and protects against oxidative etching of the synthesized monolayers. The stoichiometric WS2 monolayers synthesized using Ar + H2 carrier gas exhibit superior optical characteristics, with photoluminescence emission full width half maximum (FWHM) values below 40 meV and emission intensities nearly an order of magnitude higher than films synthesized in a pure Ar environment.

Single layers of transition metal dichalcogenides (TMDs) are direct gap semiconductors with nondegenerate valley indices. An intriguing possibility for these materials is the use of their valley index as an alternate state variable. Several limitations to such a utility include strong intervalley scattering, as well as multiparticle interactions leading to multiple emission channels. We prepare single-layer WS2 films such that the photoluminescence is from either the neutral or charged exciton (trion). After excitation with circularly polarized light, the neutral exciton emission has zero polarization. However, the trion emission has a large polarization (28%) at room temperature. The trion emission also has a unique, non-monotonic temperature dependence that is a consequence of the multiparticle nature of the trion. This temperature dependence enables us to determine that intervalley scattering, electron-hole radiative recombination, and Auger processes are the dominant mechanisms at work in this system. Because this dependence involves trion systems, one can use gate voltages to modulate the polarization (or intensity) emitted from TMD structures.

We report a systematic study of coherent spin precession and spin dephasing in electron-doped monolayer MoS2. Using time-resolved Kerr rotation spectroscopy and applied in-plane magnetic fields, a nanosecond time scale Larmor spin precession signal commensurate with g-factor |g0| ≃ 1.86 is observed in several different MoS2 samples grown by chemical vapor deposition. The dephasing rate of this oscillatory signal increases linearly with magnetic field, suggesting that the coherence arises from a subensemble of localized electron spins having an inhomogeneously broadened distribution of g-factors, g0 + Δg. In contrast to g0, Δg is sample-dependent and ranges from 0.042 to 0.115.

We demonstrate that hydrogenated graphene performs as a homoepitaxial tunnel barrier on a graphene charge/spin channel. We examine the tunneling behavior through measuring the IV curves and zero bias resistance. We also fabricate hydrogenated graphene/graphene nonlocal spin valves and measure the spin lifetimes using the Hanle effect, with spintronic nonlocal spin valve operation demonstrated up to room temperature. We show that while hydrogenated graphene indeed allows for spin transport in graphene and has many advantages over oxide tunnel barriers, it does not perform as well as similar fluorinated graphene/graphene devices, possibly due to the presence of magnetic moments in the hydrogenated graphene that act as spin scatterers.

Spin-based devices offer non-volatile, scalable, low power and reprogrammable functionality for emerging device technologies. Here we fabricate nanoscale spintronic devices with ferromagnetic metal/single-layer graphene tunnel barriers used to generate spin accumulation and spin currents in a silicon nanowire transport channel. We report the first observation of spin precession via the Hanle effect in both local three-terminal and non-local spin-valve geometries, providing a direct measure of spin lifetimes and confirmation of spin accumulation and pure spin transport. The use of graphene as the tunnel barrier provides a low-resistance area product contact and clean magnetic switching characteristics, because it smoothly bridges the nanowire and minimizes complicated magnetic domains that otherwise compromise the magnetic behaviour. Utilizing intrinsic two-dimensional layers such as graphene or hexagonal boron nitride as tunnel contacts on nanowires offers many advantages over conventional materials deposited by vapour deposition, enabling a path to highly scaled electronic and spintronic devices.

The interaction between surface plasmons (SP) and magnetic behavior has generated great research interest due to its potential for future magneto-optical devices with ultra-high sensitivity and ultra-fast switching. Here we combine two surface sensitive effects: magnetic second-harmonic generation (MSHG) and SP to enhance the detection sensitivity of the surface magnetization in a single-crystal iron film. We show that the MSHG signal can be significantly enhanced by SP in an attenuated total reflection (ATR) condition, and that the magnetic contrast can be varied over a wide range by the angle-of-incidence. Furthermore, the magnetic contrast of transverse and longitudinal MSHG display opposite trends, which originates from the change of relative phase between MSHG components. This new effect enhances the sensing of magnetic switching, which has potential usage in quaternary magnetic storage systems and bio-chemical sensors due to its very high surface sensitivity and simple structure.