G. Dominguez

Gate-tuning of graphene plasmons revealed by infrared nano-imaging

Surface plasmons are collective oscillations of electrons in metals or semiconductors that enable confinement and control of electromagnetic energy at subwavelength scales. Rapid progress in plasmonics has largely relied on advances in device nano-fabrication, whereas less attention has been paid to the tunable properties of plasmonic media. One such medium—graphene—is amenable to convenient tuning of its electronic and optical properties by varying the applied voltage. Here, using infrared nano-imaging, we show that common graphene/SiO2/Si back-gated structures support propagating surface plasmons. The wavelength of graphene plasmons is of the order of 200 nanometres at technologically relevant infrared frequencies, and they can propagate several times this distance. We have succeeded in altering both the amplitude and the wavelength of these plasmons by varying the gate voltage. Using plasmon interferometry, we investigated losses in graphene by exploring real-space profiles of plasmon standing waves formed between the tip of our nano-probe and the edges of the samples. Plasmon dissipation quantified through this analysis is linked to the exotic electrodynamics of graphene. Standard plasmonic figures of merit of our tunable graphene devices surpass those of common metal-based structures.

Tunable Phonon Polaritons in Atomically Thin van der Waals Crystals of Boron Nitride

Nanoimaged Polaritons Engineered heterostructures consisting of thin, weakly bound layers can exhibit many attractive electronic properties. Dai et al. (p. 1125) used infrared nanoimaging on the surface of hexagonal boron nitride crystals to detect phonon polaritons, collective modes that originate in the coupling of photons to optical phonons. The findings reveal the dependence of the polariton wavelength and dispersion on the thickness of the material down to just a few atomic layers. Infrared nanoimaging is used to detect a type of surface collective mode in a representative van der Waals crystal. van der Waals heterostructures assembled from atomically thin crystalline layers of diverse two-dimensional solids are emerging as a new paradigm in the physics of materials. We used infrared nanoimaging to study the properties of surface phonon polaritons in a representative van der Waals crystal, hexagonal boron nitride. We launched, detected, and imaged the polaritonic waves in real space and altered their wavelength by varying the number of crystal layers in our specimens. The measured dispersion of polaritonic waves was shown to be governed by the crystal thickness according to a scaling law that persists down to a few atomic layers. Our results are likely to hold true in other polar van der Waals crystals and may lead to new functionalities.

Infrared Nanoscopy of Dirac Plasmons at the Graphene-SiO₂ Interface

We report on infrared (IR) nanoscopy of 2D plasmon excitations of Dirac fermions in graphene. This is achieved by confining mid-IR radiation at the apex of a nanoscale tip: an approach yielding 2 orders of magnitude increase in the value of in-plane component of incident wavevector q compared to free space propagation. At these high wavevectors, the Dirac plasmon is found to dramatically enhance the near-field interaction with mid-IR surface phonons of SiO(2) substrate. Our data augmented by detailed modeling establish graphene as a new medium supporting plasmonic effects that can be controlled by gate voltage.

Impact Features on Stardust: Implications for Comet 81P/Wild 2 Dust

Particles emanating from comet 81P/Wild 2 collided with the Stardust spacecraft at 6.1 kilometers per second, producing hypervelocity impact features on the collector surfaces that were returned to Earth. The morphologies of these surprisingly diverse features were created by particles varying from dense mineral grains to loosely bound, polymineralic aggregates ranging from tens of nanometers to hundreds of micrometers in size. The cumulative size distribution of Wild 2 dust is shallower than that of comet Halley, yet steeper than that of comet Grigg-Skjellerup.

Characterization of the Single Particle Mixing State of Individual Ship Plume Events Measured at the Port of Los Angeles

Ship emissions contribute significantly to gaseous and particulate pollution worldwide. To better understand the impact of ship emissions on air quality, measurements of the size-resolved chemistry of individual particles in ship emissions were made at the Port of Los Angeles using real-time, single-particle mass spectrometry. Ship plumes were identified through a combination of ship position information and measurements of gases and aerosol particles at a site 500 m from the center of the main shipping channel at the Port of Los Angeles. Single particles containing mixtures of organic carbon, vanadium, and sulfate (OC-V-sulfate) resulted from residual fuel combustion (i.e., bunker fuel), whereas high quantities of fresh soot particles (when OC-V-sulfate particles were not present) represented distinct markers for plumes from distillate fuel combustion (i.e., diesel fuel) from ships as well as trucks in the port area. DC-V-sulfate particles from residual fuel combustion contained significantly higher levels of sulfate and sulfuric acid than plume particles containing no vanadium. These associations may be due to vanadium (or other metals such as iron) in the fuel catalyzing the oxidation of S0(2) to produce sulfate and sulfuric acid on these particles. Enhanced sulfate production on OC-V-sulfate ship emission particles would help explain some of the higher than expected sulfate levels measured in California compared to models based on emissions inventories and typical sulfate production pathways. Understanding the overall impact of ships emissions is critical for controlling regional air quality in the many populated coastal regions of the world.

Ultrafast and Nanoscale Plasmonic Phenomena in Exfoliated Graphene Revealed by Infrared Pump–Probe Nanoscopy

Pump-probe spectroscopy is central for exploring ultrafast dynamics of fundamental excitations, collective modes, and energy transfer processes. Typically carried out using conventional diffraction-limited optics, pump-probe experiments inherently average over local chemical, compositional, and electronic inhomogeneities. Here, we circumvent this deficiency and introduce pump-probe infrared spectroscopy with ∼ 20 nm spatial resolution, far below the diffraction limit, which is accomplished using a scattering scanning near-field optical microscope (s-SNOM). This technique allows us to investigate exfoliated graphene single-layers on SiO2 at technologically significant mid-infrared (MIR) frequencies where the local optical conductivity becomes experimentally accessible through the excitation of surface plasmons via the s-SNOM tip. Optical pumping at near-infrared (NIR) frequencies prompts distinct changes in the plasmonic behavior on 200 fs time scales. The origin of the pump-induced, enhanced plasmonic response is identified as an increase in the effective electron temperature up to several thousand Kelvin, as deduced directly from the Drude weight associated with the plasmonic resonances.

Model for quantitative tip-enhanced spectroscopy and the extraction of nanoscale-resolved optical constants

Near-field infrared spectroscopy by elastic scattering of light from a probe tip resolves optical contrasts in materials at dramatically subwavelength scales across a broad energy range, with the demonstrated capacity for chemical identification at the nanoscale. However, current models of probe-sample near-field interactions still cannot provide a sufficiently quantitatively interpretation of measured near-field contrasts, especially in the case of materials supporting strong surface phonons. We present a model of near-field spectroscopy derived from basic principles and verified by finite-element simulations, demonstrating superb predictive agreement both with tunable quantum cascade laser near-field spectroscopy of SiO2 thin films and with newly presented nanoscale Fourier transform infrared (nanoFTIR) spectroscopy of crystalline SiC. We discuss the role of probe geometry, field retardation, and surface mode dispersion in shaping the measured near-field response. This treatment enables a route to quantitatively determine nanoresolved optical constants, as we demonstrate by inverting newly presented nanoFTIR spectra of an SiO2 thin film into the frequency dependent dielectric function of its mid-infrared optical phonon. Our formalism further enables tip-enhanced spectroscopy as a potent diagnostic tool for quantitative nanoscale spectroscopy.

The physical chemistry of mass-independent isotope effects and their observation in nature.

Historically, the physical chemistry of isotope effects and precise measurements in samples from nature have provided information on processes that could not have been obtained otherwise. With the discovery of a mass-independent isotopic fractionation during the formation of ozone, a new physical chemical basis for isotope effects required development. Combined theoretical and experimental developments have broadened this understanding and extended the range of chemical systems where these unique effects occur. Simultaneously, the application of mass-independent isotopic measurements to an extensive range of both terrestrial and extraterrestrial systems has furthered the understanding of events such as solar system origin and evolution and planetary atmospheric chemistry, present and past.

Near-field spectroscopy of silicon dioxide thin films

We analyze the results of scanning near-field infrared spectroscopy performed on thin films of a-SiO2 on Si substrate. The measured near-field signal exhibits surface-phonon resonances whose strength has a strong thickness dependence in the range from 2 to 300 {nm}. These observations are compared with calculations in which the tip of the near-field infrared spectrometer is modeled either as a point dipole or an elongated spheroid. The latter model accounts for the antenna effect of the tip and gives a better agreement with the experiment. Possible applications of the near-field technique for depth profiling of layered nanostructures are discussed.

Discovery and measurement of an isotopically distinct source of sulfate in Earth's atmosphere

Sulfate (SO4) and its precursors are significant components of the atmosphere, with both natural and anthropogenic sources. Recently, our triple-isotope (16O, 17O, 18O) measurements of atmospheric sulfate have provided specific insights into the oxidation pathways leading to sulfate, with important implications for models of the sulfur cycle and global climate change. Using similar isotopic measurements of aerosol sulfate in a polluted marine boundary layer (MBL) and primary sulfate (p-SO4) sampled directly from a ship stack, we quantify the amount of p-SO4 found in the atmosphere from ships. We find that ships contribute between 10% and 44% of the non-sea-salt sulfate found in fine [diameter (D) < 1.5 μm) particulate matter in coastal Southern California. These fractions are surprising, given that p-SO4 constitutes ≈2–7% of total sulfur emissions from combustion sources [Seinfed JH, Pandis SN (2006) Atmospheric Chemistry and Physics (Wiley–Interscience, New York)]. Our findings also suggest that the interaction of SO2 from ship emissions with coarse hydrated sea salt particles may lead to the rapid removal of SO2 in the MBL. When combined with the longer residence time of p-SO4 emissions in the MBL, these findings suggest that the importance of p-SO4 emissions in marine environments may be underappreciated in global chemical models. Given the expected increase of international shipping in the years to come, these findings have clear implications for public health, air quality, international maritime law, and atmospheric chemistry.