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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.

Understanding plasmon-mediated electron emission and energy transfer on the nanometer length scale is critical to controlling light-matter interactions at nanoscale dimensions. In a high-resolution lithographic material, electron emission and energy transfer lead to chemical transformations. In this work, we employ such chemical transformations in two different high-resolution electron-beam lithography resists, poly(methyl methacrylate) (PMMA) and hydrogen silsesquioxane (HSQ), to map local electron emission and energy transfer with nanometer resolution from plasmonic nanoantennas excited by femtosecond laser pulses. We observe exposure of the electron-beam resists (both PMMA and HSQ) in regions on the surface of nanoantennas where the local field is significantly enhanced. Exposure in these regions is consistent with previously reported optical-field-controlled electron emission from plasmonic hotspots as well as earlier work on low-electron-energy scanning probe lithography. For HSQ, in addition to exposure in hotspots, we observe resist exposure at the centers of rod-shaped nanoantennas in addition to exposure in plasmonic hotspots. Optical field enhancement is minimized at the center of nanorods suggesting that exposure in these regions involves a different mechanism to that in plasmonic hotspots. Our simulations suggest that exposure at the center of nanorods results from the emission of hot electrons produced via plasmon decay in the nanorods. Overall, the results presented in this work provide a means to map both optical-field-controlled electron emission and hot-electron transfer from nanoparticles via chemical transformations produced locally in lithographic materials.

In this work, we use electron energy-loss spectroscopy to map the complete plasmonic spectrum of aluminum nanodisks with diameters ranging from 3 to 120 nm fabricated by high-resolution electron-beam lithography. Our nanopatterning approach allows us to produce localized surface plasmon resonances across a wide spectral range spanning 2-8 eV. Electromagnetic simulations using the finite element method support the existence of dipolar, quadrupolar, and hexapolar surface plasmon modes as well as centrosymmetric breathing modes depending on the location of the electron-beam excitation. In addition, we have developed an approach using nanolithography that is capable of meV control over the energy and attosecond control over the lifetime of volume plasmons in these nanodisks. The precise measurement of volume plasmon lifetime may also provide an opportunity to probe and control the DC electrical conductivity of highly confined metallic nanostructures. Lastly, we show the strong influence of the nanodisk boundary in determining both the energy and lifetime of surface plasmons and volume plasmons locally across individual aluminum nanodisks, and we have compared these observations to similar effects produced by scaling the nanodisk diameter.

Here we demonstrate the design, fabrication, and characterization of ultrafast, surface-plasmon enhanced Au nanorod optical field emitter arrays. We present a quantitative study of electron emission from Au nanorod arrays fabricated by high-resolution electron-beam lithography and excited by 35 fs pulses of 800 nm light. We present accurate models for both the optical field enhancement of Au nanorods within high-density arrays, and electron emission from those nanorods. We have also studied the effects of surface plasmon damping induced by metallic interface layers at the substrate/nanorod interface on near-field enhancement and electron emission. We have identified the peak optical field at which the electron emission mechanism transitions from a 3-photon absorption mechanism to strong-field tunneling emission. Moreover, we have investigated the effects of nanorod array density on nanorod charge yield, including measurement of space-charge effects. The Au nanorod photocathodes presented in this work display 100-1000 times higher conversion efficiency relative to previously reported UV triggered emission from planar Au photocathodes. Consequently, the Au nanorod arrays triggered by ultrafast pulses of 800 nm light in this work may outperform equivalent UV-triggered Au photocathodes, while also offering nanostructuring of the electron pulse produced from such a cathode, which is of interest for X-ray free-electron laser (XFEL) development where nanostructured electron pulses may facilitate more efficient and brighter XFEL radiation.

One challenge existing since the invention of electron-beam lithography (EBL) is understanding the exposure mechanisms that limit the resolution of EBL. To overcome this challenge, we need to understand the spatial distribution of energy density deposited in the resist, that is, the point-spread function (PSF). During EBL exposure, the processes of electron scattering, phonon, photon, plasmon, and electron emission in the resist are combined, which complicates the analysis of the EBL PSF. Here, we show the measurement of delocalized energy transfer in EBL exposure by using chromatic aberration-corrected energy-filtered transmission electron microscopy (EFTEM) at the sub-10 nm scale. We have defined the role of spot size, electron scattering, secondary electrons, and volume plasmons in the lithographic PSF by performing EFTEM, momentum-resolved electron energy loss spectroscopy (EELS), sub-10 nm EBL, and Monte Carlo simulations. We expect that these results will enable alternative ways to improve the resolution limit of EBL. Furthermore, our approach to study the resolution limits of EBL may be applied to other lithographic techniques where electrons also play a key role in resist exposure, such as ion-beam-, X-ray-, and extreme-ultraviolet lithography.

We investigated electron-beam lithography with an aberration-corrected scanning transmission electron microscope. We achieved 2 nm isolated feature size and 5 nm half-pitch in hydrogen silsesquioxane resist. We also analyzed the resolution limits of this technique by measuring the point-spread function at 200 keV. Furthermore, we measured the energy loss in the resist using electron-energy-loss spectroscopy.

We show the importance of sidewall chemistry for the graphoepitaxial alignment of PS-b-PDMS using prepatterns fabricated by electron beam lithography of hydrogen silsesquioxane (HSQ) and by deep ultraviolet (DUV) lithography on SiO(2) thin films. Density multiplication of polystyrene-block-polydimethylsiloxane (PS-b-PDMS) within both prepatterns was achieved by using a room temperature dynamic solvent annealing environment. Selective tuning of PS and PDMS wetting on the HSQ template sidewalls was also achieved through careful functionalization of the template and substrate surface using either brush or a self-assembled trimethylsilyl monolayer. PDMS selectively wets HSQ sidewalls treated with a brush layer of PDMS, whiereas PS is found to selectively wet HSQ sidewalls treated with hexamethyldisilazane (HMDS) to produce a trimethylsilyl-terminated surface. The etch resistance of the aligned polymer was also evaluated to understand the implications of using block copolymer patterns which have high etch resistance, self-forming (PDMS) wetting layers at both interfaces. The results outlined in this work may have direct applications in nanolithography for continued device scaling toward the end-of-roadmap era.

We report the self-seeded growth of highly crystalline Ge nanowires, with a mean diameter as small as 6 nm without the need for a metal catalyst. The nanowires, synthesized using the purpose-built precursor hexakis(trimethylsilyl)digermane, exhibit high aspect ratios (>1000) while maintaining a uniform core diameter along their length. Additionally, the nanowires are encased in an amorphous shell of material derived from the precursor, which acts to passivate their surfaces and isolates the Ge seed particles from which the nanowires grow. The diameter of the nanowires was found to depend on the synthesis temperature employed. Specifically, there is a linear relationship between the inverse radius of the nanowires and the synthesis temperature, which can be explained by a model for the size-dependent melting of simple metals.