Electron Beam Induced Circularly Polarized Light Emission of Chiral Gold Nanohelices.

Chiral plasmonic nanostructures possess a chiroptical response orders of magnitude stronger than that of natural biomolecular systems, making them highly promising for a wide range of biochemical, medical, and physical applications. Despite extensive efforts to artificially create and tune the chiroptical properties of chiral nanostructures through compositional and geometrical modifications, a fundamental understanding of their underlying mechanisms remains limited. In this study, we present a comprehensive investigation of individual gold nanohelices by using advanced analytical electron microscopy techniques. Our results, as determined by angle-resolved cathodoluminescence polarimetry measurements, reveal a strong correlation between the circular polarization state of the emitted far-field radiation and the handedness of the chiral nanostructure in terms of both its dominant circularity and directional intensity distribution. Further analyses, including electron energy-loss measurements and numerical simulations, demonstrate that this correlation is driven by longitudinal plasmonic modes that oscillate along the helical windings, much like straight nanorods of equal strength and length. However, due to the three-dimensional shape of the structures, these longitudinal modes induce dipolar transverse modes with charge oscillations along the short axis of the helices for certain resonance energies. Their radiative decay leads to observed emission in the visible range. Our findings provide insight into the radiative properties and underlying mechanisms of chiral plasmonic nanostructures and enable their future development and application in a wide range of fields, such as nano-optics, metamaterials, molecular physics, biochemistry, and, most promising, chiral sensing via plasmonically enhanced chiral optical spectroscopy techniques.

Linear indium atom chains at graphene edges.

The presence of metal atoms at the edges of graphene nanoribbons (GNRs) opens new possibilities toward tailoring their physical properties. We present here formation and high-resolution characterization of indium (In) chains on the edges of graphene-supported GNRs. The GNRs are formed when adsorbed hydrocarbon contamination crystallizes via laser heating into small ribbon-like patches of a second graphitic layer on a continuous graphene monolayer and onto which In is subsequently physical vapor deposited. Using aberration-corrected scanning transmission electron microscopy (STEM), we find that this leads to the preferential decoration of the edges of the overlying GNRs with multiple In atoms along their graphitic edges. Electron-beam irradiation during STEM induces migration of In atoms along the edges of the GNRs and triggers the formation of longer In atom chains during imaging. Density functional theory (DFT) calculations of GNRs similar to our experimentally observed structures indicate that both bare zigzag (ZZ) GNRs as well as In-terminated ZZ-GNRs have metallic character, whereas in contrast, In termination induces metallicity for otherwise semiconducting armchair (AC) GNRs. Our findings provide insights into the creation and properties of long linear metal atom chains at graphitic edges.

Nanoscale mapping of shifts in dark plasmon modes in sub 10 nm aluminum nanoantennas.

In this work, we report the fabrication and spectroscopic characterization of subwavelength aluminum nanocavities-consisting of hexamer or tetramer clusters of sub 10 nm width Al nanorods-with tunable localized surface plasmon resonance (LSPR) energies on suspended SiNxmembranes. Here the volume plasmon (VP) and LSPR modes of lithographically-fabricated Al nanocavities are revealed by low-loss electron energy-loss spectroscopy (EELS) in an aberration corrected scanning transmission electron microscope (STEM). We show that the existence of grain boundaries (GBs) in these nanocavities results in shifts in the VP energy and a reduction in the VP lifetime. We map the VP energy and lifetime across GBs and we observe a decrease in VP energy and lifetime at GBs that is consistent with a reduction in free carrier density and increased plasmon scattering at these locations. Dipolar LSPR modes resonant in the UV and blue regions of the electromagnetic spectrum as well as higher-energy optically dark quadrupolar and hexapolar LSPR modes are also observed and mapped by STEM and EELS. All LSPR modes are confirmed via electromagnetic simulations based on the boundary element method. Both tetramer and hexamer structures support the excitation of dipolar bright and dipolar dark modes. Finally, we find that asymmetries in fabricated nanorod hexamer and tetramer nanocavities result in a mode mixing leading to a shift in dipolar dark LSPR modes.

Hybrid Graphene-Supported Aluminum Plasmonics.

Controlled fabrication of devices for plasmonics on suspended graphene enables obtaining tunable localized surface plasmon resonances (LSPRs), reducing the red-shift of LSPRs, and creating hybrid 3D-2D systems promising for adjustable dipole-dipole coupling and plasmon-mediated catalysis. Here, we apply a low-cost fabrication methodology to produce patterned aluminum nanostructures (bowties and tetramers) on graphene monolayers via electron-beam lithography and trap platinum (Pt) nanoclusters (NCs) within their hotspots by thermal annealing. We reveal the LSPRs of aluminum plasmonics on graphene using electron energy-loss spectroscopy (EELS) and energy-filtered transmission electron microscopy (EFTEM) in a monochromated scanning transmission electron microscope (STEM). The LSPRs of these nanostructures are measured to be between visible and ultraviolet regions of the spectrum and are confirmed by electromagnetic simulations. The antibonding dipole and bonding dipole modes of both structures are tuned by controlling their gap size. The tetramers enable the simultaneous excitation of both antibonding and bonding dipole modes at the poles of nanoprisms, while bowties allow us to excite these modes separately either at the poles or within the hotspot. We further show that the hybrid nanocavity-NC systems are in the intermediate coupling regime providing an enhanced plasmon absorption in the Pt NCs via the energy transfer from the antibonding dipole mode to the Pt NCs. The dipole LSPR of Pt NCs also couples to the bonding-type breathing mode in bowties. Our findings suggest that these hybrid nanocavity-graphene systems are of high application potential for plasmon-mediated catalysis, surface-enhanced fluorescence, and quantum technologies.

Uncovering the Evolution of Low-Energy Plasmons in Nanopatterned Aluminum Plasmonics on Graphene.

We report adjusting the charge-transfer-plasmon (CTP) resonances of aluminum (Al) bowties on suspended monolayer graphene via controlled nanofabrication and focused electron-beam irradiation. CTP resonances of bowties with a conductive junction blue-shift with an increase in junction width, whereas their 3λ/2 and λ resonances barely red-shift. These plasmon modes are derived and confirmed by an LC circuit model and electromagnetic simulations performed with boundary-element and frequency-domain methods. A monotonic decay of the CTP lifetime is observed, while the junction width is extended. Instead, the lifetimes of 3λ/2 and λ resonances are nearly independent of junction width. When the junction is shrunk by electron-beam irradiation, all antenna resonances red-shift. Having created an electron-beam-induced sub 5 nm gap in bowties, we monitor the unambiguous transition of a CTP into a bonding-type gap mode, which is highly sensitive to the separation distance. Meanwhile, the 3λ/2 and λ resonances evolve into dipolar bright and dipolar dark modes.

Aerosol Jet Printing of Graphene and Carbon Nanotube Patterns on Realistically Rugged Substrates.

Direct-write additive manufacturing of graphene and carbon nanotube (CNT) patterns by aerosol jet printing (AJP) is promising for the creation of thermal and electrical interconnects in (opto)electronics. In realistic application scenarios, this however often requires deposition of graphene and CNT patterns on rugged substrates such as, for example, roughly machined and surface-oxidized metal block heat sinks. Most AJP of graphene/CNT patterns has thus far however concentrated on flat wafer- or foil-type substrates. Here, we demonstrate AJP of graphene and single walled CNT (SWCNT) patterns on realistically rugged plasma-electrolytic-oxidized (PEO) Al blocks, which are promising heat sink materials. We show that AJP on the rugged substrates offers line resolution of down to ∼40 µm width for single AJP passes, however, at the cost of noncomplete substrate coverage including noncovered µm-sized pores in the PEO Al blocks. With multiple AJP passes, full coverage including coverage of the pores is, however, readily achieved. Comparing archetypical aqueous and organic graphene and SWCNT inks, we show that the choice of the ink system drastically influences the nanocarbon AJP parameter window, deposit microstructure including crystalline quality, compactness of deposit, and inter/intrapass layer adhesion for multiple passes. Simple electrical characterization indicates aqueous graphene inks as the most promising choice for AJP-deposited electrical interconnect applications. Our parameter space screening thereby forms a framework for rational process development for graphene and SWCNT AJP on application-relevant, rugged substrates.

Single Indium Atoms and Few-Atom Indium Clusters Anchored onto Graphene via Silicon Heteroatoms.

Single atoms and few-atom nanoclusters are of high interest in catalysis and plasmonics, but pathways for their fabrication and placement remain scarce. We report here the self-assembly of room-temperature-stable single indium (In) atoms and few-atom In clusters (2-6 atoms) that are anchored to substitutional silicon (Si) impurity atoms in suspended monolayer graphene membranes. Using atomically resolved scanning transmission electron microscopy (STEM), we find that the symmetry of the In structures is critically determined by the three- or fourfold coordination of the Si "anchors". All structures are produced without electron-beam induced materials modification. In turn, when activated by electron beam irradiation in the STEM, we observe in situ the formation, restructuring, and translation of the Si-anchored In structures. Our results on In-Si-graphene provide a materials system for controlled self-assembly and heteroatomic anchoring of single atoms and few-atom nanoclusters on graphene.

Towards chirality control of graphene nanoribbons embedded in hexagonal boron nitride.

The integrated in-plane growth of graphene nanoribbons (GNRs) and hexagonal boron nitride (h-BN) could provide a promising route to achieve integrated circuitry of atomic thickness. However, fabrication of edge-specific GNRs in the lattice of h-BN still remains a significant challenge. Here we developed a two-step growth method and successfully achieved sub-5-nm-wide zigzag and armchair GNRs embedded in h-BN. Further transport measurements reveal that the sub-7-nm-wide zigzag GNRs exhibit openings of the bandgap inversely proportional to their width, while narrow armchair GNRs exhibit some fluctuation in the bandgap-width relationship. An obvious conductance peak is observed in the transfer curves of 8- to 10-nm-wide zigzag GNRs, while it is absent in most armchair GNRs. Zigzag GNRs exhibit a small magnetic conductance, while armchair GNRs have much higher magnetic conductance values. This integrated lateral growth of edge-specific GNRs in h-BN provides a promising route to achieve intricate nanoscale circuits.

New imaging modes for analyzing suspended ultra-thin membranes by double-tip scanning probe microscopy.

Scanning probe microscopy (SPM) techniques are amongst the most important and versatile experimental methods in surface- and nanoscience. Although their measurement principles on rigid surfaces are well understood and steady progress on the instrumentation has been made, SPM imaging on suspended, flexible membranes remains difficult to interpret. Due to the interaction between the SPM tip and the flexible membrane, morphological changes caused by the tip can lead to deformations of the membrane during scanning and hence significantly influence measurement results. On the other hand, gaining control over such modifications can allow to explore unknown physical properties and functionalities of such membranes. Here, we demonstrate new types of measurements that become possible with two SPM instruments (atomic force microscopy, AFM, and scanning tunneling microscopy, STM) that are situated on opposite sides of a suspended two-dimensional (2D) material membrane and thus allow to bring both SPM tips arbitrarily close to each other. One of the probes is held stationary on one point of the membrane, within the scan area of the other probe, while the other probe is scanned. This way new imaging modes can be obtained by recording a signal on the stationary probe as a function of the position of the other tip. The first example, which we term electrical cross-talk imaging (ECT), shows the possibility of performing electrical measurements across the membrane, potentially in combination with control over the forces applied to the membrane. Using ECT, we measure the deformation of the 2D membrane around the indentation from the AFM tip. In the second example, which we term mechanical cross-talk imaging (MCT), we disentangle the mechanical influence of a scanning probe tip (e.g. AFM) on a freestanding membrane by means of independently recording the response of the opposing tip. In this way we are able to separate the tip-induced membrane deformation topography from the (material-dependent) force between the tip and the membrane. Overall, the results indicate that probing simultaneously both surfaces of ultra-thin membranes, such as suspended 2D materials, could provide novel insights into the electronic properties of the materials.

Isolating hydrogen in hexagonal boron nitride bubbles by a plasma treatment.

Atomically thin hexagonal boron nitride (h-BN) is often regarded as an elastic film that is impermeable to gases. The high stabilities in thermal and chemical properties allow h-BN to serve as a gas barrier under extreme conditions. Here, we demonstrate the isolation of hydrogen in bubbles of h-BN via plasma treatment. Detailed characterizations reveal that the substrates do not show chemical change after treatment. The bubbles are found to withstand thermal treatment in air, even at 800 °C. Scanning transmission electron microscopy investigation shows that the h-BN multilayer has a unique aligned porous stacking nature, which is essential for the character of being transparent to atomic hydrogen but impermeable to hydrogen molecules. In addition, we successfully demonstrated the extraction of hydrogen gases from gaseous compounds or mixtures containing hydrogen element. The successful production of hydrogen bubbles on h-BN flakes has potential for further application in nano/micro-electromechanical systems and hydrogen storage.

Atomic-Scale Deformations at the Interface of a Mixed-Dimensional van der Waals Heterostructure.

Molecular self-assembly due to chemical interactions is the basis of bottom-up nanofabrication, whereas weaker intermolecular forces dominate on the scale of macromolecules. Recent advances in synthesis and characterization have brought increasing attention to two- and mixed-dimensional heterostructures, and it has been recognized that van der Waals (vdW) forces within the structure may have a significant impact on their morphology. Here, we suspend single-walled carbon nanotubes (SWCNTs) on graphene to create a model system for the study of a 1D-2D molecular interface through atomic-resolution scanning transmission electron microscopy observations. When brought into contact, the radial deformation of SWCNTs and the emergence of long-range linear grooves in graphene revealed by the three-dimensional reconstruction of the heterostructure are observed. These topographic features are strain-correlated but show no sensitivity to carbon nanotube helicity, electronic structure, or stacking order. Finally, despite the random deposition of the nanotubes, we show that the competition between strain and vdW forces results in aligned carbon-carbon interfaces spanning hundreds of nanometers.

Atomic Structure of Intrinsic and Electron-Irradiation-Induced Defects in MoTe2.

Studying the atomic structure of intrinsic defects in two-dimensional transition-metal dichalcogenides is difficult since they damage quickly under the intense electron irradiation in transmission electron microscopy (TEM). However, this can also lead to insights into the creation of defects and their atom-scale dynamics. We first show that MoTe2 monolayers without protection indeed quickly degrade during scanning TEM (STEM) imaging, and discuss the observed atomic-level dynamics, including a transformation from the 1H phase into 1T', 3-fold rotationally symmetric defects, and the migration of line defects between two 1H grains with a 60° misorientation. We then analyze the atomic structure of MoTe2 encapsulated between two graphene sheets to mitigate damage, finding the as-prepared material to contain an unexpectedly large concentration of defects. These include similar point defects (or quantum dots, QDs) as those created in the nonencapsulated material and two different types of line defects (or quantum wires, QWs) that can be transformed from one to the other under electron irradiation. Our density functional theory simulations indicate that the QDs and QWs embedded in MoTe2 introduce new midgap states into the semiconducting material and may thus be used to control its electronic and optical properties. Finally, the edge of the encapsulated material appears amorphous, possibly due to the pressure caused by the encapsulation.

Grain boundary-mediated nanopores in molybdenum disulfide grown by chemical vapor deposition.

Molybdenum disulfide (MoS2) is a particularly interesting member of the family of two-dimensional (2D) materials due to its semiconducting and tunable electronic properties. Currently, the most reliable method for obtaining high-quality industrial scale amounts of 2D materials is chemical vapor deposition (CVD), which results in polycrystalline samples. As grain boundaries (GBs) are intrinsic defect lines within CVD-grown 2D materials, their atomic structure is of paramount importance. Here, through atomic-scale analysis of micrometer-long GBs, we show that covalently bound boundaries in 2D MoS2 tend to be decorated by nanopores. Such boundaries occur when differently oriented MoS2 grains merge during growth, whereas the overlap of grains leads to boundaries with bilayer areas. Our results suggest that the nanopore formation is related to stress release in areas with a high concentration of dislocation cores at the grain boundaries, and that the interlayer interaction leads to intrinsic rippling at the overlap regions. This provides insights for the controlled fabrication of large-scale MoS2 samples with desired structural properties for applications.

Visualising the strain distribution in suspended two-dimensional materials under local deformation.

We demonstrate the use of combined simultaneous atomic force microscopy (AFM) and laterally resolved Raman spectroscopy to study the strain distribution around highly localised deformations in suspended two-dimensional materials. Using the AFM tip as a nanoindentation probe, we induce localised strain in suspended few-layer graphene, which we adopt as a two-dimensional membrane model system. Concurrently, we visualise the strain distribution under and around the AFM tip in situ using hyperspectral Raman mapping via the strain-dependent frequency shifts of the few-layer graphene's G and 2D Raman bands. Thereby we show how the contact of the nm-sized scanning probe tip results in a two-dimensional strain field with µm dimensions in the suspended membrane. Our combined AFM/Raman approach thus adds to the critically required instrumental toolbox towards nanoscale strain engineering of two-dimensional materials.