Yohannes Abate

Nanoscale Infrared Absorption Spectroscopy of Individual Nanoparticles Enabled by Scattering-Type Near-Field Microscopy

Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption.

Real-space mapping of nanoplasmonic hotspots via optical antenna-gap loading

Plasmonic hotspots located in the nanogaps of infrared optical antennas are mapped in the near-field. The enhanced evanescent field resonance is shown to depend strongly on excitation wavelength, the excitation and detection laser polarization, and gap size. In addition, we demonstrate that in nanogap hotspot imaging using scattering probes, the probe tip can be considered as a load in the gap of the antenna, and the impedance of the load can then be tuned from inductive to capacitive or vice versa by changing the dielectric value of the tip load. Experimental results are in agreement with finite-difference time-domain simulations.

Nanoscale subsurface- and material-specific identification of single nanoparticles

We report on high resolution subsurface and material specific differentiation of silica, Au and silica-capped Au nanoparticles using scattering-type scanning near-field optical microscopy (s-SNOM) in the visible (λ=633 nm) and mid-infrared (λ=10.7 μm) frequencies. Strong optical contrast is observed in the visible wavelength, mainly because of the dipolar plasmon resonance of the embedded Au nanoparticles which is absent in the infrared. We show that the use of small tapping amplitude improves the apparent image contrast in nanoparticles by causing increased tip-particle and reduced tip-substrate interactions. Experimental results are in excellent agreement with extended dipole model calculations modified to include the capping layer characterized by its refractive index.

Optimization and enhancement of H− ions in a magnetized sheet plasma

Several schemes to improve the efficiency of extraction of H− ions from a magnetized sheet plasma source are reported. Parameters that affect the optimization of the extraction process such as plasma electrode position relative to the core plasma, plasma electrode bias, extraction electrode bias, neutral gas pressure, and discharge current were investigated. The negative hydrogen ion current density extracted from pure hydrogen plasma under optimum conditions was 0.15 A/m2. Enhancement of the H− current density has been observed by as much as 73.3% when argon was mixed with hydrogen at a 10%/90% ratio. The addition of argon raised the electron density by ten times and increased the electron temperature by 40% at the center of the sheet plasma. These plasma parameters were of comparable value with and without argon at the periphery of the sheet. The existence of high-energy electrons at the core and the presence of cold electrons at the periphery of the sheet plasma conform to ideal conditions of H−product...

Photodissociation spectroscopy of Zn+(H2O) and Zn+(D2O)

We report on a study of the photodissociation spectroscopy of weakly bound Zn+(H2O) and Zn+(D2O) complexes. The work is supported by ab initio electronic structure calculations of the ground and low-lying excited energy surfaces. We assign two molecular absorption bands in the near UV correlating to Zn+ (4s-4p)-based transitions, and identify vibrational progressions associated with both intermolecular and intramolecular vibrational modes of the cluster. Partially resolved rotational structure is consistent with a C(2V) equilibrium complex geometry. Experimental spectroscopic constants are in very good agreement with ab initio theoretical predictions. Results are compared with previous work on main group and transition metal ion-H2O clusters.

Nanoscopy reveals surface-metallic black phosphorus

Black phosphorus (BP) is an emerging two-dimensional material with intriguing physical properties. It is highly anisotropic and highly tunable by means of both the number of monolayers and surface doping. Here, we experimentally investigate and theoretically interpret the near-field properties of a-few-atomic-monolayer nanoflakes of BP. We discover near-field patterns of bright outside fringes and a high surface polarizability of nanofilm BP consistent with its surface-metallic, plasmonic behavior at mid-infrared frequencies <1176 cm−1. We conclude that these fringes are caused by the formation of a highly polarizable layer at the BP surface. This layer has a thickness of ~1 nm and exhibits plasmonic behavior. We estimate that it contains free carriers in a concentration of n≈1.1 × 1020 cm−3. Surface plasmonic behavior is observed for 10–40 nm BP thicknesses but absent for a 4-nm BP thickness. This discovery opens up a new field of research and potential applications in nanoelectronics, plasmonics and optoelectronics.

Nanometer-scale dielectric constant of Ge quantum dots using apertureless near-field scanning optical microscopy

Tip-enhanced near-field scattering images of Ge quantum dots (QDs) with 20–40 nm height and 220–270 nm diameter grown on a Si substrate have been observed with a spatial resolution of 15 nm. Changing the wavelength of the incident light, the contrast of the images is reversed. It is found that the scattering intensity is caused by the dielectric constants of the materials under the probe. By changing the wavelength of the incident light, we have obtained information about the dielectric constant dispersion of single Ge QDs.

Control of Plasmonic Nanoantennas by Reversible Metal-insulator Transition

We demonstrate dynamic reversible switching of VO2 insulator-to-metal transition (IMT) locally on the scale of 15 nm or less and control of nanoantennas, observed for the first time in the near-field. Using polarization-selective near-field imaging techniques, we simultaneously monitor the IMT in VO2 and the change of plasmons on gold infrared nanoantennas. Structured nanodomains of the metallic VO2 locally and reversibly transform infrared plasmonic dipole nanoantennas to monopole nanoantennas. Fundamentally, the IMT in VO2 can be triggered on femtosecond timescale to allow ultrafast nanoscale control of optical phenomena. These unique features open up promising novel applications in active nanophotonics.

Near-field edge fringes at sharp material boundaries

We have studied the formation of near-field fringes when sharp edges of materials are imaged using scattering-type scanning near-field optical microscope (s-SNOM). The materials we have investigated include dielectrics, metals, a near-perfect conductor, and those that possess anisotropic permittivity and hyperbolic dispersion. For our theoretical analysis, we use a technique that combines full-wave numerical simulations of tip-sample near-field interaction and signal demodulation at higher orders akin to what is done in typical s-SNOM experiments. Unlike previous tip-sample interaction near-field models, our advanced technique allows simulation of the realistic tip and sample structure. Our analysis clarifies edge imaging of recently emerged layered materials such as hexagonal boron nitride and transition metal dichalcogenides (in particular, molybdenum disulfide), as well as traditional plasmonic materials such as gold. Hexagonal boron nitride is studied at several wavelengths, including the wavelength where it possesses excitation of phonon-polaritons and hyperbolic dispersion. Based on our results of s-SNOM imaging in different demodulation orders, we specify resonant and non-resonant types of edges and describe the edge fringes for each case. We clarify near-field edge-fringe formation at material sharp boundaries, both outside bright fringes and the low-contrast region at the edge, and elaborate on the necessity of separating them from propagating waves on the surface of polaritonic materials.

Geometric constraints on phase coexistence in vanadium dioxide single crystals

The appearance of stripe phases is a characteristic signature of strongly correlated quantum materials, and its origin in phase-changing materials has only recently been recognized as the result of the delicate balance between atomic and mesoscopic materials properties. A vanadium dioxide (VO2) single crystal is one such strongly correlated material with stripe phases. Infrared nano-imaging on low-aspect-ratio, single-crystal VO2 microbeams decorated with resonant plasmonic nanoantennas reveals a novel herringbone pattern of coexisting metallic and insulating domains intercepted and altered by ferroelastic domains, unlike previous reports on high-aspect-ratio VO2 crystals where the coexisting metal/insulator domains appear as alternating stripe phases perpendicular to the growth axis. The metallic domains nucleate below the crystal surface and grow towards the surface with increasing temperature as suggested by the near-field plasmonic response of the gold nanorod antennas.