Dielectric disorder in two-dimensional materials

Understanding and controlling disorder is key to nanotechnology and materials science. Traditionally, disorder is attributed to local fluctuations of inherent material properties such as chemical and structural composition, doping or strain. Here, we present a fundamentally new source of disorder in nanoscale systems that is based entirely on the local changes of the Coulomb interaction due to fluctuations of the external dielectric environment. Using two-dimensional semiconductors as prototypes, we experimentally monitor dielectric disorder by probing the statistics and correlations of the exciton resonances, and theoretically analyse the influence of external screening and phonon scattering. Even moderate fluctuations of the dielectric environment are shown to induce large variations of the bandgap and exciton binding energies up to the 100 meV range, often making it a dominant source of inhomogeneities. As a consequence, dielectric disorder has strong implications for both the optical and transport properties of nanoscale materials and their heterostructures

Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy

Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules

Surface and grain boundary carbon heterogeneity in CH3NH3PbI3perovskites and its impact on optoelectronic properties

Rivaling state-of-the-art crystalline silicon, organic-inorganic hybrid perovskites have been intensely studied in recent years. Surface and interfacial engineering have been a focus for performance improvement. Even though significant progress has been made during the last decade in terms of the diversity and capability of perovskite-based devices, the structure-property relationship, particularly at the surface, which governs the real-world performance of these applications, is still unresolved. In the article, this issue was addressed by employing synchrotron-related experimental measurements, and a mechanism that correlates microstructure with surface chemistry was resolved. As a powerful and highly sensitive spectromicroscopy, soft x ray photoemission electron microscopy (X-PEEM) was used to probe the surface of perovskite films varying in post solvent annealing. Static and in situ grazing incidence hard x ray diffraction (GIXD) was used to track the grain growth dynamics during the film formation process. It was found that the nature of the surfaces was dictated by the local chemistry that varied due to mass flow during the development of the microstructure. Combining optical and electronic characterizations, it was confirmed that a more homogenous chemistry, i.e., uniform chemical components and properties, along with reduced strain and grain boundary energies, yielded more defect-tolerant films. Grain boundaries were more favorable for screening carriers than those in the control film. Our findings underscore the importance of the uniformity in the surface for developing a chemistry-structure-property relationship in perovskite materials, as well as engineering local chemistry toward high-performance and stable devices

Correlation-driven electron-hole asymmetry in graphene field effect devices

Electron-hole asymmetry is a fundamental property in solids that can determine the nature of quantum phase transitions and the regime of operation for devices. The observation of electron-hole asymmetry in graphene and recently in twisted graphene and moiré heterostructures has spurred interest into whether it stems from single-particle effects or from correlations, which are core to the emergence of intriguing phases in moiré systems. Here, we report an effective way to access electron-hole asymmetry in 2D materials by directly measuring the quasiparticle self-energy in graphene/Boron Nitride field-effect devices. As the chemical potential moves from the hole to the electron-doped side, we see an increased strength of electronic correlations manifested by an increase in the band velocity and inverse quasiparticle lifetime. These results suggest that electronic correlations intrinsically drive the electron-hole asymmetry in graphene and by leveraging this asymmetry can provide alternative avenues to generate exotic phases in twisted moiré heterostructures

A dielectric-defined lateral heterojunction in a monolayer semiconductor

Owing to their low dimensionality, two-dimensional semiconductors, such as monolayer molybdenum disulfide, have a range of properties that make them valuable in the development of nanoelectronics. For example, the electronic bandgap of these semiconductors is not an intrinsic physical parameter and can be engineered by manipulating the dielectric environment around the monolayer. Here we show that this dielectric-dependent electronic bandgap can be used to engineer a lateral heterojunction within a homogeneous MoS 2 monolayer. We visualize the heterostructure with Kelvin probe force microscopy and examine its influence on electrical transport experimentally and theoretically. We observe a lateral heterojunction with an approximately 90 meV band offset due to the differing degrees of bandgap renormalization of monolayer MoS 2 when it is placed on a substrate in which one segment is made from an amorphous fluoropolymer (Cytop) and another segment is made of hexagonal boron nitride. This heterostructure leads to a diode-like electrical transport with a strong asymmetric behaviour

Visualization of the flat electronic band in twisted bilayer graphene near the magic angle twist

Bilayer graphene has been predicted to host a moiré miniband with flat dispersion if the layers are stacked at specific twist angles known as the ’magic angles’1,2. Recently, twisted bilayer graphene (tBLG) with a magic angle twist was reported to exhibit a correlated insulating state and superconductivity3,4, where the presence of the flat miniband in the system is thought to be essential for the emergence of these ordered phases in the transport measurements. Although tunnelling spectroscopy5–9 and electronic compressibility measurements10 in tBLG have found a van Hove singularity that is consistent with the presence of the flat miniband, a direct observation of the flat dispersion in the momentum space of such a moiré miniband in tBLG is still lacking. Here, we report the visualization of this flat moiré miniband by using angle-resolved photoemission spectroscopy with nanoscale resolution. The high spatial resolution of this technique enabled the measurement of the local electronic structure of the tBLG. The measurements demonstrate the existence of the flat moiré band near the charge neutrality for tBLG close to the magic angle at room temperature