Intralayer charge-transfer moiré excitons in van der Waals superlattices.

Moiré patterns of transition metal dichalcogenide heterobilayers have proved to be an ideal platform on which to host unusual correlated electronic phases, emerging magnetism and correlated exciton physics. Whereas the existence of new moiré excitonic states is established1-4 through optical measurements, the microscopic nature of these states is still poorly understood, often relying on empirically fit models. Here, combining large-scale first-principles GW (where G and W denote the one-particle Green's function and the screened Coulomb interaction, respectively) plus Bethe-Salpeter calculations and micro-reflection spectroscopy, we identify the nature of the exciton resonances in WSe2/WS2 moiré superlattices, discovering a rich set of moiré excitons that cannot be captured by prevailing continuum models. Our calculations show moiré excitons with distinct characters, including modulated Wannier excitons and previously unidentified intralayer charge-transfer excitons. Signatures of these distinct excitonic characters are confirmed experimentally by the unique carrier-density and magnetic-field dependences of different moiré exciton resonances. Our study highlights the highly non-trivial exciton states that can emerge in transition metal dichalcogenide moiré superlattices, and suggests new ways of tuning many-body physics in moiré systems by engineering excited-states with specific spatial characters.

Imaging two-dimensional generalized Wigner crystals.

The Wigner crystal1 has fascinated condensed matter physicists for nearly 90 years2-14. Signatures of two-dimensional (2D) Wigner crystals were first observed in 2D electron gases under high magnetic field2-4, and recently reported in transition metal dichalcogenide moiré superlattices6-9. Direct observation of the 2D Wigner crystal lattice in real space, however, has remained an outstanding challenge. Conventional scanning tunnelling microscopy (STM) has sufficient spatial resolution but induces perturbations that can potentially alter this fragile state. Here we demonstrate real-space imaging of 2D Wigner crystals in WSe2/WS2 moiré heterostructures using a specially designed non-invasive STM spectroscopy technique. This employs a graphene sensing layer held close to the WSe2/WS2 moiré superlattice. Local STM tunnel current into the graphene layer is modulated by the underlying Wigner crystal electron lattice in the WSe2/WS2 heterostructure. Different Wigner crystal lattice configurations at fractional electron fillings of n = 1/3, 1/2 and 2/3, where n is the electron number per site, are directly visualized. The n = 1/3 and n = 2/3 Wigner crystals exhibit triangular and honeycomb lattices, respectively, to minimize nearest-neighbour occupations. The n = 1/2 state spontaneously breaks the original C3 symmetry and forms a stripe phase. Our study lays a solid foundation for understanding Wigner crystal states in WSe2/WS2 moiré heterostructures and provides an approach that is generally applicable for imaging novel correlated electron lattices in other systems.

Mott and generalized Wigner crystal states in WSe2/WS2 moiré superlattices.

Moiré superlattices can be used to engineer strongly correlated electronic states in two-dimensional van der Waals heterostructures, as recently demonstrated in the correlated insulating and superconducting states observed in magic-angle twisted-bilayer graphene and ABC trilayer graphene/boron nitride moiré superlattices1-4. Transition metal dichalcogenide moiré heterostructures provide another model system for the study of correlated quantum phenomena5 because of their strong light-matter interactions and large spin-orbit coupling. However, experimental observation of correlated insulating states in this system is challenging with traditional transport techniques. Here we report the optical detection of strongly correlated phases in semiconducting WSe2/WS2 moiré superlattices. We use a sensitive optical detection technique and reveal a Mott insulator state at one hole per superlattice site and surprising insulating phases at 1/3 and 2/3 filling of the superlattice, which we assign to generalized Wigner crystallization on the underlying lattice6-11. Furthermore, the spin-valley optical selection rules12-14 of transition metal dichalcogenide heterostructures allow us to optically create and investigate low-energy excited spin states in the Mott insulator. We measure a very long spin relaxation lifetime of many microseconds in the Mott insulating state, orders of magnitude longer than that of charge excitations. Our studies highlight the value of using moiré superlattices beyond graphene to explore correlated physics.

Second-Order Temporal Coherence of Polariton Lasers Based on an Atomically Thin Crystal in a Microcavity.

Bosonic condensation and lasing of exciton polaritons in microcavities is a fascinating solid-state phenomenon. It provides a versatile platform to study out-of-equilibrium many-body physics and has recently appeared at the forefront of quantum technologies. Here, we study the photon statistics via the second-order temporal correlation function of polariton lasing emerging from an optical microcavity with an embedded atomically thin MoSe_{2} crystal. Furthermore, we investigate the macroscopic polariton phase transition for varying excitation powers and temperatures. The lower-polariton exhibits photon bunching below the threshold, implying a dominant thermal distribution of the emission, while above the threshold, the second-order correlation transits towards unity, which evidences the formation of a coherent state. Our findings are in agreement with a microscopic numerical model, which explicitly includes scattering with phonons on the quantum level.

Imaging moiré flat bands in three-dimensional reconstructed WSe2/WS2 superlattices.

Moiré superlattices in transition metal dichalcogenide (TMD) heterostructures can host novel correlated quantum phenomena due to the interplay of narrow moiré flat bands and strong, long-range Coulomb interactions1-9. However, microscopic knowledge of the atomically reconstructed moiré superlattice and resulting flat bands is still lacking, which is critical for fundamental understanding and control of the correlated moiré phenomena. Here we quantitatively study the moiré flat bands in three-dimensional (3D) reconstructed WSe2/WS2 moiré superlattices by comparing scanning tunnelling spectroscopy (STS) of high-quality exfoliated TMD heterostructure devices with ab initio simulations of TMD moiré superlattices. A strong 3D buckling reconstruction accompanied by large in-plane strain redistribution is identified in our WSe2/WS2 moiré heterostructures. STS imaging demonstrates that this results in a remarkably narrow and highly localized K-point moiré flat band at the valence band edge of the heterostructure. A series of moiré flat bands are observed at different energies that exhibit varying degrees of localization. Our observations contradict previous simplified theoretical models but agree quantitatively with ab initio simulations that fully capture the 3D structural reconstruction. Our results reveal that the strain redistribution and 3D buckling in TMD heterostructures dominate the effective moiré potential and the corresponding moiré flat bands at the Brillouin zone K points.

Dynamic Tuning of Moiré Excitons in a WSe2/WS2 Heterostructure via Mechanical Deformation.

Moiré superlattices in van der Waals (vdW) heterostructures form by stacking atomically thin layers on top of one another with a twist angle or lattice mismatch. The resulting moiré potential leads to a strong modification of the band structure, which can give rise to exotic quantum phenomena ranging from correlated insulators and superconductors to moiré excitons and Wigner crystals. Here, we demonstrate the dynamic tuning of moiré potential in a WSe2/WS2 heterostructure at cryogenic temperature. We utilize the optical fiber tip of a cryogenic scanning near-field optical microscope (SNOM) to locally deform the heterostructure and measure its near-field optical response simultaneously. The deformation of the heterostructure increases the moiré potential, which leads to a red shift of the moiré exciton resonances. We observe the interlayer exciton resonance shifts up to 20 meV, while the intralayer exciton resonances shift up to 17 meV.

Excitons in Bilayer MoS_{2} Displaying a Colossal Electric Field Splitting and Tunable Magnetic Response.

van der Waals heterostructures composed of transition metal dichalcogenide monolayers (TMDCs) are characterized by their truly rich excitonic properties which are determined by their structural, geometric, and electronic properties: In contrast to pure monolayers, electrons and holes can be hosted in different materials, resulting in highly tunable dipolar many-particle complexes. However, for genuine spatially indirect excitons, the dipolar nature is usually accompanied by a notable quenching of the exciton oscillator strength. Via electric and magnetic field dependent measurements, we demonstrate that a slightly biased pristine bilayer MoS_{2} hosts strongly dipolar excitons, which preserve a strong oscillator strength. We scrutinize their giant dipole moment, and shed further light on their orbital and valley physics via bias-dependent magnetic field measurements.

Nanoscale Conductivity Imaging of Correlated Electronic States in WSe_{2}/WS_{2} Moiré Superlattices.

We report the nanoscale conductivity imaging of correlated electronic states in angle-aligned WSe_{2}/WS_{2} heterostructures using microwave impedance microscopy. The noncontact microwave probe allows us to observe the Mott insulating state with one hole per moiré unit cell that persists for temperatures up to 150 K, consistent with other characterization techniques. In addition, we identify for the first time a Mott insulating state at one electron per moiré unit cell. Appreciable inhomogeneity of the correlated states is directly visualized in the heterobilayer region, indicative of local disorders in the moiré superlattice potential or electrostatic doping. Our work provides important insights on 2D moiré systems down to the microscopic level.

Strain-Tunable Single Photon Sources in WSe2 Monolayers.

The appearance of single photon sources in atomically thin semiconductors holds great promises for the development of a flexible and ultracompact quantum technology in which elastic strain engineering can be used to tailor their emission properties. Here, we show a compact and hybrid two-dimensional semiconductor-piezoelectric device that allows for controlling the energy of single photons emitted by quantum emitters localized in wrinkled WSe2 monolayers. We demonstrate that strain fields exerted by the piezoelectric device can be used to tune the energy of localized excitons in WSe2 up to 18 meV in a reversible manner while leaving the single photon purity unaffected over a wide range. Interestingly, we find that the magnitude and, in particular, the sign of the energy shift as a function of stress is emitter dependent. With the help of finite element simulations we suggest a simple model that explains our experimental observations and, furthermore, discloses that the type of strain (tensile or compressive) experienced by the quantum emitters strongly depends on their localization across the wrinkles. Our findings are of strong relevance for the practical implementation of single photon devices based on two-dimensional materials as well as for understanding the effects of strain on their emission properties.

Brightening of a dark monolayer semiconductor via strong light-matter coupling in a cavity.

Engineering the properties of quantum materials via strong light-matter coupling is a compelling research direction with a multiplicity of modern applications. Those range from modifying charge transport in organic molecules, steering particle correlation and interactions, and even controlling chemical reactions. Here, we study the modification of the material properties via strong coupling and demonstrate an effective inversion of the excitonic band-ordering in a monolayer of WSe2 with spin-forbidden, optically dark ground state. In our experiments, we harness the strong light-matter coupling between cavity photon and the high energy, spin-allowed bright exciton, and thus creating two bright polaritonic modes in the optical bandgap with the lower polariton mode pushed below the WSe2 dark state. We demonstrate that in this regime the commonly observed luminescence quenching stemming from the fast relaxation to the dark ground state is prevented, which results in the brightening of this intrinsically dark material. We probe this effective brightening by temperature-dependent photoluminescence, and we find an excellent agreement with a theoretical model accounting for the inversion of the band ordering and phonon-assisted polariton relaxation.

Advances in Rare-Earth Tritelluride Quantum Materials: Structure, Properties, and Synthesis.

A distinct class of 2D layered quantum materials with the chemical formula of RTe3 (R = lanthanide) has gained significant attention owing to the occurrence of collective quantum states, superconductivity, charge density waves (CDW), spin density waves, and other advanced quantum properties. To study the Fermi surface nesting driven CDW formation, the layered RTe3 family stages an excellent low dimensional genre system. In addition to the primary energy gap feature observed at higher energy, optical spectroscopy study on some RTe3 evidence a second CDW energy gap structure indicating the occurrence of multiple CDW ordering even with light and intermediate RTe3 compounds. Here, a comprehensive review of the fundamentals of RTe3 layered tritelluride materials is presented with a special focus on the recent advances made in electronic structure, CDW transition, superconductivity, magnetic properties of these unique quantum materials. A detailed description of successful synthesis routes including the flux method, self-flux method, and CVT along with potential applications is summarized.

Abnormal Phase Transition and Band Renormalization of Guanidinium-Based Organic-Inorganic Hybrid Perovskite.

Low-dimensional organic-inorganic hybrid perovskites have attracted much interest owing to their superior solar conversion performance, environmental stability, and excitonic properties compared to their three-dimensional (3D) counterparts. Among reduced-dimensional perovskites, guanidinium-based perovskites crystallize in layered one-dimensional (1D) and two-dimensional (2D). Here, our studies demonstrate how the dimensionality of the hybrid perovskite influences the chemical and physical properties under different pressures (i.e., bond distance, angle, vdW distance). Comprehensive studies show that 1D GuaPbI3 does not undergo a phase transition even up to high pressures (∼13 GPa) and its band gap monotonically reduces with pressure. In contrast, 2D Gua2PbI4 exhibits an early phase transition at 5.5 GPa and its band gap follow nonmonotonic pressure response associated with phase transition as well as other bond angle changes. Computational simulations reveal that the phase transition is related to the structural deformation and rotation of PbI6 octahedra in 2D Gua2PbI4 owing to a larger degree of freedom of deformation. The soft lattice allows them to uptake large pressures, which renders structural phase transitions possible. Overall the results offer the first insights into how layered perovskites with different dimensionality respond to structural changes driven by pressure.

Spatial coherence of room-temperature monolayer WSe2 exciton-polaritons in a trap.

The emergence of spatial and temporal coherence of light emitted from solid-state systems is a fundamental phenomenon intrinsically aligned with the control of light-matter coupling. It is canonical for laser oscillation, emerges in the superradiance of collective emitters, and has been investigated in bosonic condensates of thermalized light, as well as exciton-polaritons. Our room temperature experiments show the strong light-matter coupling between microcavity photons and excitons in atomically thin WSe2. We evidence the density-dependent expansion of spatial and temporal coherence of the emitted light from the spatially confined system ground-state, which is accompanied by a threshold-like response of the emitted light intensity. Additionally, valley-physics is manifested in the presence of an external magnetic field, which allows us to manipulate K and K' polaritons via the valley-Zeeman-effect. Our findings validate the potential of atomically thin crystals as versatile components of coherent light-sources, and in valleytronic applications at room temperature.

Epitaxial Synthesis of Highly Oriented 2D Janus Rashba Semiconductor BiTeCl and BiTeBr Layers.

The family of layered BiTeX (X = Cl, Br, I) compounds are intrinsic Janus semiconductors with giant Rashba-splitting and many exotic surface and bulk physical properties. To date, studies on these materials required mechanical exfoliation from bulk crystals which yielded thick sheets in nonscalable sizes. Here, we report epitaxial synthesis of Janus BiTeCl and BiTeBr sheets through a nanoconversion technique that can produce few triple layers of Rashba semiconductors (<10 nm) on sapphire substrates. The process starts with van der Waals epitaxy of Bi2Te3 sheets on sapphire and converts these sheets to BiTeCl or BiTeBr layers at high temperatures in the presence of chemically reactive BiCl3/BiBr3 inorganic vapor. Systematic Raman, XRD, SEM, EDX, and other studies show that highly crystalline BiTeCl and BiTeBr sheets can be produced on demand. Atomic level growth mechanism is also proposed and discussed to offer further insights into growth process steps. Overall, this work marks the direct deposition of 2D Janus Rashba materials and offers pathways to synthesize other Janus compounds belonging to MXY family members.

The synthesis of competing phase GeSe and GeSe2 2D layered materials.

We demonstrate the synthesis of layered anisotropic semiconductor GeSe and GeSe2 nanomaterials through low temperature (∼400 °C) and atmospheric pressure chemical vapor deposition using halide based precursors. Results show that GeI2 and H2Se precursors successfully react in the gas-phase and nucleate on a variety of target substrates including sapphire, Ge, GaAs, or HOPG. Layer-by-layer growth takes place after nucleation to form layered anisotropic materials. Detailed SEM, EDS, XRD, and Raman spectroscopy measurements together with systematic CVD studies reveal that the substrate temperature, selenium partial pressure, and the substrate type ultimately dictate the resulting stoichiometry and phase of these materials. Results from this work introduce the phase control of Ge and Se based nanomaterials (GeSe and GeSe2) using halide based CVD precursors at ATM pressures and low temperatures. Overall findings also extend our fundamental understanding of their growth by making the first attempt to correlate growth parameters to resulting competing phases of Ge-Se based materials.

Low-temperature synthesis of 2D anisotropic MoTe2 using a high-pressure soft sputtering technique.

We demonstrate a high-pressure soft sputtering technique that can grow large area 1T' phase MoTe2 sheets on HOPG and Al2O3 substrates at temperatures as low as 300 °C. The results show that a single Mo/Te co-sputtering step on heated substrates produces highly defected films as a result of the low Te sticking coefficient. The stoichiometry is significantly improved when a 2-step technique is used, which first co-sputters Mo and Te onto an unheated substrate and then anneals the deposited material to crystalize it into 1T' phase MoTe2. A MoTe2-x 1T' film with the lowest Te vacancy content (x = 0.14) was synthesized using a 300 °C annealing step, but a higher processing temperature was prohibited due to MoTe2 decomposition with an activation energy of 80.7 kJ mol-1. However, additional ex situ thermal processing at ∼1 torr tellurium pressure can further reduce the Te-vacancy (VTe) concentration, resulting in an improvement in the composition from MoTe1.86 to MoTe1.9. Hall measurements indicate that the films produced with the 2-step in situ process are n-type with a carrier concentration of 4.6 × 1014 cm-2 per layer, presumably from the large VTe concentration stabilizing the 1T' over the 2H phase. Our findings (a) demonstrate that large scale synthesis of tellurium based vdW materials is possible using industrial growth and processing techniques and (b) accentuate the challenges in producing stoichiometric MoTe2 thin films.