Nanoironing van der Waals Heterostructures toward Electrically Controlled Quantum Dots.

Assembling two-dimensional van der Waals (vdW)-layered materials into heterostructures is an exciting development that sparked the discovery of rich correlated electronic phenomena. vdW heterostructures also offer possibilities for designer device applications in areas such as optoelectronics, valley- and spintronics, and quantum technology. However, realizing the full potential of these heterostructures requires interfaces with exceptionally low disorder which is challenging to engineer. Here, we show that thermal scanning probes can be used to create pristine interfaces in vdW heterostructures. Our approach is compatible at both the material- and device levels, and monolayer WS2 transistors show up to an order of magnitude improvement in electrical performance from this technique. We also demonstrate vdW heterostructures with low interface disorder enabling the electrical formation and control of quantum dots that can be tuned from macroscopic current flow to the single-electron tunneling regime.

Symmetry Breaking and Spin-Orbit Coupling for Individual Vacancy-Induced In-Gap States in MoS2 Monolayers.

Spins confined to point defects in atomically thin semiconductors constitute well-defined atomic-scale quantum systems that are being explored as single-photon emitters and spin qubits. Here, we investigate the in-gap electronic structure of individual sulfur vacancies in molybdenum disulfide (MoS2) monolayers using resonant tunneling scanning probe spectroscopy in the Coulomb blockade regime. Spectroscopic mapping of defect wave functions reveals an interplay of local symmetry breaking by a charge-state-dependent Jahn-Teller lattice distortion that, when combined with strong (≃100 meV) spin-orbit coupling, leads to a locking of an unpaired spin-1/2 magnetic moment to the lattice at low temperature, susceptible to lattice strain. Our results provide new insights into the spin and electronic structure of vacancy-induced in-gap states toward their application as electrically and optically addressable quantum systems.

Probing charge traps at the 2D semiconductor/dielectric interface.

The family of 2-dimensional (2D) semiconductors is a subject of intensive scientific research due to their potential in next-generation electronics. While offering many unique properties like atomic thickness and chemically inert surfaces, the integration of 2D semiconductors with conventional dielectric materials is challenging. The charge traps at the semiconductor/dielectric interface are among many issues to be addressed before these materials can be of industrial relevance. Conventional electrical characterization methods remain inadequate to quantify the traps at the 2D semiconductor/dielectric interface since the estimations of the density of interface traps, Dit, by different techniques may yield more than an order-of-magnitude discrepancy, even when extracted from the same device. Therefore, the challenge to quantify Dit at the 2D semiconductor/dielectric interface is about finding an accurate and reliable measurement method. In this review, we discuss characterization techniques which have been used to study the 2D semiconductor/dielectric interface. Specifically, we discuss the methods based on small-signal AC measurements, subthreshold slope measurements and low-frequency noise measurements. While these approaches were developed for silicon-based technology, 2D semiconductor devices possess a set of unique challenges requiring a careful re-evaluation when using these characterization techniques. We examine the conventional methods based on their efficacy and accuracy in differentiating various types of trap states and provide guidance to find an appropriate method for charge trap analysis and estimation of Dit at 2D semiconductor/dielectric interfaces.

Single Atomic Defect Conductivity for Selective Dilute Impurity Imaging in 2D Semiconductors.

Precisely controlled impurity doping is of fundamental significance in modern semiconductor technologies. Desired physical properties are often achieved at impurity concentrations well below parts per million level. For emergent two-dimensional semiconductors, development of reliable doping strategies is hindered by the inherent difficulty in identifying and quantifying impurities in such a dilute limit where the absolute number of atoms to be detected is insufficient for common analytical techniques. Here we report rapid high-contrast imaging of dilute single atomic impurities by using conductive atomic force microscopy. We show that the local conductivity is enhanced by more than 100-fold by a single impurity atom due to resonance-assisted tunneling. Unlike the closely related scanning tunneling microscopy, the local conductivity sensitively depends on the impurity energy level, allowing minority defects to be selectively imaged. We further demonstrate subsurface impurity detection with single monolayer depth resolution in multilayer materials.

Gate-Tunable Bound Exciton Manifolds in Monolayer MoSe2.

Two-dimensional (2D) semiconductors with point defects are predicted to host a variety of bound exciton complexes analogous to trions and biexcitons due to strong many-body effects. However, despite the common observation of defect-mediated subgap emission, the existence of such complexes remains elusive. Here, we report the observation of bound exciton (BX) complex manifolds in monolayer MoSe2 with intentionally created monoselenium vacancies (VSe) using proton beam irradiation. The emission intensity of different BX peaks is found to exhibit contrasting dependence on electrostatic doping near the onset of free electron injection. The observed trend is consistent with the model in which free excitons exist in equilibrium with excitons bound to neutral and charged VSe defects, which act as deep acceptors. These complexes are more strongly bound than trions and biexcitons, surviving up to around 180 K, and exhibit moderate valley polarization memory, indicating partial free exciton character.

Probing spin dynamics of ultra-thin van der Waals magnets via photon-magnon coupling.

Layered van der Waals (vdW) magnets can maintain a magnetic order even down to the single-layer regime and hold promise for integrated spintronic devices. While the magnetic ground state of vdW magnets was extensively studied, key parameters of spin dynamics, like the Gilbert damping, crucial for designing ultra-fast spintronic devices, remains largely unexplored. Despite recent studies by optical excitation and detection, achieving spin wave control with microwaves is highly desirable, as modern integrated information technologies predominantly are operated with these. The intrinsically small numbers of spins, however, poses a major challenge to this. Here, we present a hybrid approach to detect spin dynamics mediated by photon-magnon coupling between high-Q superconducting resonators and ultra-thin flakes of Cr2Ge2Te6 (CGT) as thin as 11 nm. We test and benchmark our technique with 23 individual CGT flakes and extract an upper limit for the Gilbert damping parameter. These results are crucial in designing on-chip integrated circuits using vdW magnets and offer prospects for probing spin dynamics of monolayer vdW magnets.

Dielectrics for Two-Dimensional Transition-Metal Dichalcogenide Applications.

Despite over a decade of intense research efforts, the full potential of two-dimensional transition-metal dichalcogenides continues to be limited by major challenges. The lack of compatible and scalable dielectric materials and integration techniques restrict device performances and their commercial applications. Conventional dielectric integration techniques for bulk semiconductors are difficult to adapt for atomically thin two-dimensional materials. This review provides a brief introduction into various common and emerging dielectric synthesis and integration techniques and discusses their applicability for 2D transition metal dichalcogenides. Dielectric integration for various applications is reviewed in subsequent sections including nanoelectronics, optoelectronics, flexible electronics, valleytronics, biosensing, quantum information processing, and quantum sensing. For each application, we introduce basic device working principles, discuss the specific dielectric requirements, review current progress, present key challenges, and offer insights into future prospects and opportunities.

Ferroelectricity in Niobium Oxide Dihalides NbOX2 (X = Cl, I): A Macroscopic- to Microscopic-Scale Study.

2D materials with ferroelectric and piezoelectric properties are of interest for energy harvesting, memory storage and electromechanical systems. Here, we present a systematic study of the ferroelectric properties in NbOX2 (X = Cl, I) across different spatial scales. The in-plane ferroelectricity in NbOX2 was investigated using transport and piezoresponse force microscopy (PFM) measurements, where it was observed that NbOCl2 has a stronger ferroelectric order than NbOI2. A high local field, exerted by both PFM and scanning tunneling microscopy (STM) tips, was found to induce 1D collinear ferroelectric strips in NbOCl2. STM imaging reveals the unreconstructed atomic structures of NbOX2 surfaces, and scanning tunneling spectroscopy was used to probe the electronic states induced at defect (vacancy) sites.

Liquid-Metal-Printed Ultrathin Oxides for Atomically Smooth 2D Material Heterostructures.

Two-dimensional (2D) semiconductors are promising channel materials for continued downscaling of complementary metal-oxide-semiconductor (CMOS) logic circuits. However, their full potential continues to be limited by a lack of scalable high-k dielectrics that can achieve atomically smooth interfaces, small equivalent oxide thicknesses (EOTs), excellent gate control, and low leakage currents. Here, large-area liquid-metal-printed ultrathin Ga2O3 dielectrics for 2D electronics and optoelectronics are reported. The atomically smooth Ga2O3/WS2 interfaces enabled by the conformal nature of liquid metal printing are directly visualized. Atomic layer deposition compatibility with high-k Ga2O3/HfO2 top-gate dielectric stacks on a chemical-vapor-deposition-grown monolayer WS2 is demonstrated, achieving EOTs of ∼1 nm and subthreshold swings down to 84.9 mV/dec. Gate leakage currents are well within requirements for ultrascaled low-power logic circuits. These results show that liquid-metal-printed oxides can bridge a crucial gap in dielectric integration of 2D materials for next-generation nanoelectronics.

Laser-induced topological spin switching in a 2D van der Waals magnet.

Two-dimensional (2D) van der Waals (vdW) magnets represent one of the most promising horizons for energy-efficient spintronic applications because their broad range of electronic, magnetic and topological properties. However, little is known about the interplay between light and spin properties in vdW layers. Here we show that ultrafast laser excitation can not only generate different type of spin textures in CrGeTe3 vdW magnets but also induce a reversible transformation between them in a topological toggle switch mechanism. Our atomistic spin dynamics simulations and wide-field Kerr microscopy measurements show that different textures can be generated via high-intense laser pulses within the picosecond regime. The phase transformation between the different topological spin textures is obtained as additional laser pulses are applied to the system where the polarisation and final state of the spins can be controlled by external magnetic fields. Our results indicate laser-driven spin textures on 2D magnets as a pathway towards reconfigurable topological architectures at the atomistic level.

Data-driven discovery of high performance layered van der Waals piezoelectric NbOI2.

Using high-throughput first-principles calculations to search for layered van der Waals materials with the largest piezoelectric stress coefficients, we discover NbOI2 to be the one among 2940 monolayers screened. The piezoelectric performance of NbOI2 is independent of thickness, and its electromechanical coupling factor of near unity is a hallmark of optimal interconversion between electrical and mechanical energy. Laser scanning vibrometer studies on bulk and few-layer NbOI2 crystals verify their huge piezoelectric responses, which exceed internal references such as In2Se3 and CuInP2S6. Furthermore, we provide insights into the atomic origins of anti-correlated piezoelectric and ferroelectric responses in NbOX2 (X = Cl, Br, I), based on bond covalency and structural distortions in these materials. Our discovery that NbOI2 has the largest piezoelectric stress coefficients among 2D materials calls for the development of NbOI2-based flexible nanoscale piezoelectric devices.

Electron tunneling at the molecularly thin 2D perovskite and graphene van der Waals interface.

Quasi-two-dimensional perovskites have emerged as a new material platform for optoelectronics on account of its intrinsic stability. A major bottleneck to device performance is the high charge injection barrier caused by organic molecular layers on its basal plane, thus the best performing device currently relies on edge contact. Herein, by leveraging on van der Waals coupling and energy level matching between two-dimensional Ruddlesden-Popper perovskite and graphene, we show that the plane-contacted perovskite and graphene interface presents a lower barrier than gold for charge injection. Electron tunneling across the interface occurs via a gate-tunable, direct tunneling-to-field emission mechanism with increasing bias, and photoinduced charge transfer occurs at femtosecond timescale (~50 fs). Field effect transistors fabricated on molecularly thin Ruddlesden-Popper perovskite using graphene contact exhibit electron mobilities ranging from 0.1 to 0.018 cm2V-1s-1 between 1.7 to 200 K. Scanning tunneling spectroscopy studies reveal layer-dependent tunneling barrier and domain size on few-layered Ruddlesden-Popper perovskite.

Harnessing Exciton-Exciton Annihilation in Two-Dimensional Semiconductors.

Strong many-body interactions in two-dimensional (2D) semiconductors give rise to efficient exciton-exciton annihilation (EEA). This process is expected to result in the generation of unbound high energy carriers. Here, we report an unconventional photoresponse of van der Waals heterostructure devices resulting from efficient EEA. Our heterostructures, which consist of monolayer transition metal dichalcogenide (TMD), hexagonal boron nitride (hBN), and few-layer graphene, exhibit photocurrent when photoexcited carriers possess sufficient energy to overcome the high energy barrier of hBN. Interestingly, we find that the device exhibits moderate photocurrent quantum efficiency even when the semiconducting TMD layer is excited at its ground exciton resonance despite the high exciton binding energy and large transport barrier. Using ab initio calculations, we show that EEA yields highly energetic electrons and holes with unevenly distributed energies depending on the scattering condition. Our findings highlight the dominant role of EEA in determining the photoresponse of 2D semiconductor optoelectronic devices.

Polarity Tunable Trionic Electroluminescence in Monolayer WSe2.

Monolayer WSe2 exhibits luminescence arising from various types of exciton complexes due to strong many-body effects. Here, we demonstrate selective electrical excitation of positive and negative trions in van der Waals metal-insulator-semiconductor (MIS) heterostructure consisting of few-layer graphene (FLG), hexagonal boron nitride (hBN), and monolayer WSe2. Intentional unbalanced injection of electrons and holes is achieved via field-emission tunneling and electrostatic accumulation. The device exhibits planar electroluminescence from either positive trion X+ or negative trion X- depending on the bias conditions. We show that hBN serves as a tunneling barrier material allowing selective injection of electron or holes into WSe2 from FLG layer. Our observation offers prospects for hot carrier injection, trion manipulation, and on-chip excitonic devices based on two-dimensional semiconductors.

Giant gate-tunable bandgap renormalization and excitonic effects in a 2D semiconductor.

Understanding the remarkable excitonic effects and controlling the exciton binding energies in two-dimensional (2D) semiconductors are crucial in unlocking their full potential for use in future photonic and optoelectronic devices. Here, we demonstrate large excitonic effects and gate-tunable exciton binding energies in single-layer rhenium diselenide (ReSe2) on a back-gated graphene device. We used scanning tunneling spectroscopy and differential reflectance spectroscopy to measure the quasiparticle electronic and optical bandgap of single-layer ReSe2, respectively, yielding a large exciton binding energy of 520 meV. Further, we achieved continuous tuning of the electronic bandgap and exciton binding energy of monolayer ReSe2 by hundreds of milli-electron volts through electrostatic gating, attributed to tunable Coulomb interactions arising from the gate-controlled free carriers in graphene. Our findings open a new avenue for controlling the bandgap renormalization and exciton binding energies in 2D semiconductors for a wide range of technological applications.

Effects Of Structural Phase Transition On Thermoelectric Performance in Lithium-Intercalated Molybdenum Disulfide (Li xMoS2).

Layered transition metal dichalcogenides (TMDCs) intercalated with alkali metals exhibit mixed metallic and semiconducting phases with variable fractions. Thermoelectric properties of such mixed-phase structure are of great interest because of the potential energy filtering effect, wherein interfacial energy barriers strongly scatter cold carriers rather than hot carriers, leading to enhanced Seebeck coefficient ( S). Here, we study the thermoelectric properties of mixed-phase Li xMoS2 as a function of its phase composition tuned by in situ thermally driven deintercalation. We find that the sign of Seebeck coefficient changes from positive to negative during initial reduction of the 1T/1T' phase fraction, indicating crossover from p- to n-type carrier conduction. These anomalous changes in Seebeck coefficient, which cannot be simply explained by the effect of deintercalation-induced reduction in carrier density, can be attributed to the hybrid electronic property of the mixed-phase Li xMoS2. Our work shows that careful phase engineering is a promising route toward achieving thermoelectric performance in TMDCs.

Suppressed Out-of-Plane Polarizability of Free Excitons in Monolayer WSe2.

Monolayer semiconductors are atomically thin quantum wells with strong confinement of electrons in a two-dimensional (2D) plane. Here, we experimentally study the out-of-plane polarizability of excitons in hBN-encapsulated monolayer WSe2 in strong electric fields of up to 1.6 V/nm (16 MV/cm). We monitor free exciton photoluminescence peaks with increasing electric fields at a constant carrier density, carefully compensating for unintentional photodoping in our double-gated device at 4 K. We show that the Stark shift is smaller than 0.4 meV despite the large electric fields applied, yielding an upper limit of polarizability α z to be ∼10-11 Dm/V. Such a small polarizability, which is nearly two orders of magnitude smaller than the previously reported value for MoS2, indicates strong atomic confinement of electrons in this 2D system and highlights the unusual robustness of free excitons against surface potential fluctuations.

Molecularly thin two-dimensional hybrid perovskites with tunable optoelectronic properties due to reversible surface relaxation.

Due to their layered structure, two-dimensional Ruddlesden-Popper perovskites (RPPs), composed of multiple organic/inorganic quantum wells, can in principle be exfoliated down to few and single layers. These molecularly thin layers are expected to present unique properties with respect to the bulk counterpart, due to increased lattice deformations caused by interface strain. Here, we have synthesized centimetre-sized, pure-phase single-crystal RPP perovskites (CH3(CH2)3NH3)2(CH3NH3)n-1PbnI3n+1 (n = 1-4) from which single quantum well layers have been exfoliated. We observed a reversible shift in excitonic energies induced by laser annealing on exfoliated layers encapsulated by hexagonal boron nitride. Moreover, a highly efficient photodetector was fabricated using a molecularly thin n = 4 RPP crystal, showing a photogain of 105 and an internal quantum efficiency of ~34%. Our results suggest that, thanks to their dynamic structure, atomically thin perovskites enable an additional degree of control for the bandgap engineering of these materials.

Electroluminescent Devices Based on 2D Semiconducting Transition Metal Dichalcogenides.

Ultrathin layers of van der Waals inorganic semiconductors represent a new class of excitonic materials with attractive light-emitting properties. Recent observation of valley polarization, optically pumped lasing, exciton-polaritons, and single-photon emission highlights the exciting prospects for two-dimensional (2D) semiconductors for applications in novel photonic devices. Development of efficient and reliable light sources based on excitonic electroluminescence in 2D semiconductors is of fundamental importance toward the practical implementation of photonic devices. Achieving electroluminescence in these atomically thin layers requires unconventional device designs and in-depth understanding of the carrier injection and transport mechanisms. Herein, various strategies for electrically generating excitons in 2D semiconducting transition metal dichalcogenides such as monolayer MoS2 are reviewed and challenges and opportunities are outlined. Furthermore, novel device concepts such as tunable chiral emission, electrically driven quantum emission, and high-frequency modulation are highlighted.

Characterization of the second- and third-harmonic optical susceptibilities of atomically thin tungsten diselenide.

We report the first detailed characterization of the sheet third-harmonic optical susceptibility, χ(3)s, of tungsten diselenide (WSe2). With a home-built multiphoton microscope setup developed to study harmonics generation, we map the second and third-harmonic intensities as a function of position in the sample, pump power and polarization angle, for single- and few-layers flakes of WSe2. We register a value of |χ(3)s| ≈ 0.9 × 10-28 m3 V-2 at a fundamental excitation frequency of ℏω = 0.8 eV, which is comparable in magnitude to the third-harmonic susceptibility of other group-VI transition metal dichalcogenides. The simultaneously recorded sheet second-harmonic susceptibility is found to be |χ(2)s| ≈ 0.7 × 10-19 m2 V-1 in very good agreement on the order of magnitude with recent reports for WSe2, which asserts the robustness of our values for |χ(3)s|.