A few-layer covalent network of fullerenes.

The two natural allotropes of carbon, diamond and graphite, are extended networks of sp3-hybridized and sp2-hybridized atoms, respectively1. By mixing different hybridizations and geometries of carbon, one could conceptually construct countless synthetic allotropes. Here we introduce graphullerene, a two-dimensional crystalline polymer of C60 that bridges the gulf between molecular and extended carbon materials. Its constituent fullerene subunits arrange hexagonally in a covalently interconnected molecular sheet. We report charge-neutral, purely carbon-based macroscopic crystals that are large enough to be mechanically exfoliated to produce molecularly thin flakes with clean interfaces-a critical requirement for the creation of heterostructures and optoelectronic devices2. The synthesis entails growing single crystals of layered polymeric (Mg4C60)∞ by chemical vapour transport and subsequently removing the magnesium with dilute acid. We explore the thermal conductivity of this material and find it to be much higher than that of molecular C60, which is a consequence of the in-plane covalent bonding. Furthermore, imaging few-layer graphullerene flakes using transmission electron microscopy and near-field nano-photoluminescence spectroscopy reveals the existence of moiré-like superlattices3. More broadly, the synthesis of extended carbon structures by polymerization of molecular precursors charts a clear path to the systematic design of materials for the construction of two-dimensional heterostructures with tunable optoelectronic properties.

Quenched Excitons in WSe2/α-RuCl3 Heterostructures Revealed by Multimessenger Nanoscopy.

We investigate heterostructures composed of monolayer WSe2 stacked on α-RuCl3 using a combination of Terahertz (THz) and infrared (IR) nanospectroscopy and imaging, scanning tunneling spectroscopy (STS), and photoluminescence (PL). Our observations reveal itinerant carriers in the heterostructure prompted by charge transfer across the WSe2/α-RuCl3 interface. Local STS measurements show the Fermi level is shifted to the valence band edge of WSe2 which is consistent with p-type doping and verified by density functional theory (DFT) calculations. We observe prominent resonances in near-IR nano-optical and PL spectra, which are associated with the A-exciton of WSe2. We identify a concomitant, near total, quenching of the A-exciton resonance in the WSe2/α-RuCl3 heterostructure. Our nano-optical measurements show that the charge-transfer doping vanishes while excitonic resonances exhibit near-total recovery in "nanobubbles", where WSe2 and α-RuCl3 are separated by nanometer distances. Our broadband nanoinfrared inquiry elucidates local electrodynamics of excitons and an electron-hole plasma in the WSe2/α-RuCl3 system.

Ultralocalized Optoelectronic Properties of Nanobubbles in 2D Semiconductors.

The optical properties of transition-metal dichalcogenides have previously been modified at the nanoscale by using mechanical and electrical nanostructuring. However, a clear experimental picture relating the local electronic structure with emission properties in such structures has so far been lacking. Here, we use a combination of scanning tunneling microscopy (STM) and near-field photoluminescence (nano-PL) to probe the electronic and optical properties of single nanobubbles in bilayer heterostructures of WSe2 on MoSe2. We show from tunneling spectroscopy that there are electronic states deeply localized in the gap at the edge of such bubbles, which are independent of the presence of chemical defects in the layers. We also show a significant change in the local band gap on the bubble, with a continuous evolution to the edge of the bubble over a length scale of ∼20 nm. Nano-PL measurements observe a continuous redshift of the interlayer exciton on entering the bubble, in agreement with the band-to-band transitions measured by STM. We use self-consistent Schrödinger-Poisson simulations to capture the essence of the experimental results and find that strong doping in the bubble region is a key ingredient to achieving the observed localized states, together with mechanical strain.

Facile and quantitative estimation of strain in nanobubbles with arbitrary symmetry in 2D semiconductors verified using hyperspectral nano-optical imaging.

When layers of van der Waals materials are deposited via exfoliation or viscoelastic stamping, nanobubbles are sometimes created from aggregated trapped fluids. Though they can be considered a nuisance, nanobubbles have attracted scientific interest in their own right owing to their ability to generate large in-plane strain gradients that lead to rich optoelectronic phenomena, especially in the semiconducting transition metal dichalcogenides. Determination of the strain within the nanobubbles, which is crucial to understanding these effects, can be approximated using elasticity theory. However, the Föppl-von Kármán equations that describe strain in a distorted thin plate are highly nonlinear and often necessitate assuming circular symmetry to achieve an analytical solution. Here, we present an easily implemented numerical method to solve for strain tensors of nanobubbles with arbitrary symmetry in 2D crystals. The method only requires topographic information from atomic force microscopy and the Poisson ratio of the 2D material. We verify that this method reproduces the strain for circularly symmetric nanobubbles that have known analytical solutions. Finally, we use the method to reproduce the Grüneisen parameter of the E' mode for 1L-WS2 nanobubbles on template-stripped Au by comparing the derived strain with measured Raman shifts from tip-enhanced Raman spectroscopy, demonstrating the utility of our method for estimating localized strain in 2D crystals.

Programmable nanowrinkle-induced room-temperature exciton localization in monolayer WSe2.

Localized states in two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been the subject of intense study, driven by potential applications in quantum information science. Despite the rapidly growing knowledge surrounding these emitters, their microscopic nature is still not fully understood, limiting their production and application. Motivated by this challenge, and by recent theoretical and experimental evidence showing that nanowrinkles generate strain-localized room-temperature emitters, we demonstrate a method to intentionally induce wrinkles with collections of stressors, showing that long-range wrinkle direction and position are controllable with patterned array design. Nano-photoluminescence (nano-PL) imaging combined with detailed strain modeling based on measured wrinkle topography establishes a correlation between wrinkle properties, particularly shear strain, and localized exciton emission. Beyond the array-induced wrinkles, nano-PL spatial maps further reveal that the strain environment around individual stressors is heterogeneous due to the presence of fine wrinkles that are less deterministic. At cryogenic temperatures, antibunched emission is observed, confirming that the nanocone-induced strain is sufficiently large for the formation of quantum emitters. At 300 K, detailed nanoscale hyperspectral images uncover a wide range of low-energy emission peaks originating from the fine wrinkles, and show that the states can be tightly confined to regions <10 nm, even in ambient conditions. These results establish a promising potential route towards realizing room temperature quantum emission in 2D TMDC systems.

Direct nano-imaging of light-matter interactions in nanoscale excitonic emitters.

Strong light-matter interactions in localized nano-emitters placed near metallic mirrors have been widely reported via spectroscopic studies in the optical far-field. Here, we report a near-field nano-spectroscopic study of localized nanoscale emitters on a flat Au substrate. Using quasi 2-dimensional CdSe/CdxZn1-xS nanoplatelets, we observe directional propagation on the Au substrate of surface plasmon polaritons launched from the excitons of the nanoplatelets as wave-like fringe patterns in the near-field photoluminescence maps. These fringe patterns were confirmed via extensive electromagnetic wave simulations to be standing-waves formed between the tip and the edge-up assembled nano-emitters on the substrate plane. We further report that both light confinement and in-plane emission can be engineered by tuning the surrounding dielectric environment of the nanoplatelets. Our results lead to renewed understanding of in-plane, near-field electromagnetic signal transduction from the localized nano-emitters with profound implications in nano and quantum photonics as well as resonant optoelectronics.

Programming twist angle and strain profiles in 2D materials.

Moiré superlattices in twisted two-dimensional materials have generated tremendous excitement as a platform for achieving quantum properties on demand. However, the moiré pattern is highly sensitive to the interlayer atomic registry, and current assembly techniques suffer from imprecise control of the average twist angle, spatial inhomogeneity in the local twist angle, and distortions caused by random strain. We manipulated the moiré patterns in hetero- and homobilayers through in-plane bending of monolayer ribbons, using the tip of an atomic force microscope. This technique achieves continuous variation of twist angles with improved twist-angle homogeneity and reduced random strain, resulting in moiré patterns with tunable wavelength and ultralow disorder. Our results may enable detailed studies of ultralow-disorder moiré systems and the realization of precise strain-engineered devices.

Imaging strain-localized excitons in nanoscale bubbles of monolayer WSe2 at room temperature.

In monolayer transition-metal dichalcogenides, localized strain can be used to design nanoarrays of single photon sources. Despite strong empirical correlation, the nanoscale interplay between excitons and local crystalline structure that gives rise to these quantum emitters is poorly understood. Here, we combine room-temperature nano-optical imaging and spectroscopic analysis of excitons in nanobubbles of monolayer WSe2 with atomistic models to study how strain induces nanoscale confinement potentials and localized exciton states. The imaging of nanobubbles in monolayers with low defect concentrations reveals localized excitons on length scales of around 10 nm at multiple sites around the periphery of individual nanobubbles, in stark contrast to predictions of continuum models of strain. These results agree with theoretical confinement potentials atomistically derived from the measured topographies of nanobubbles. Our results provide experimental and theoretical insights into strain-induced exciton localization on length scales commensurate with exciton size, realizing key nanoscale structure-property information on quantum emitters in monolayer WSe2.

Campanile Near-Field Probes Fabricated by Nanoimprint Lithography on the Facet of an Optical Fiber.

One of the major challenges to the widespread adoption of plasmonic and nano-optical devices in real-life applications is the difficulty to mass-fabricate nano-optical antennas in parallel and reproducible fashion, and the capability to precisely place nanoantennas into devices with nanometer-scale precision. In this study, we present a solution to this challenge using the state-of-the-art ultraviolet nanoimprint lithography (UV-NIL) to fabricate functional optical transformers onto the core of an optical fiber in a single step, mimicking the 'campanile' near-field probes. Imprinted probes were fabricated using a custom-built imprinter tool with co-axial alignment capability with sub <100 nm position accuracy, followed by a metallization step. Scanning electron micrographs confirm high imprint fidelity and precision with a thin residual layer to facilitate efficient optical coupling between the fiber and the imprinted optical transformer. The imprinted optical transformer probe was used in an actual NSOM measurement performing hyperspectral photoluminescence mapping of standard fluorescent beads. The calibration scans confirmed that imprinted probes enable sub-diffraction limited imaging with a spatial resolution consistent with the gap size. This novel nano-fabrication approach promises a low-cost, high-throughput, and reproducible manufacturing of advanced nano-optical devices.