Near-Monochromatic Tuneable Cryogenic Niobium Electron Field Emitter.

Creating, manipulating, and detecting coherent electrons is at the heart of future quantum microscopy and spectroscopy technologies. Leveraging and specifically altering the quantum features of an electron beam source at low temperatures can enhance its emission properties. Here, we describe electron field emission from a monocrystalline, superconducting niobium nanotip at a temperature of 5.9 K. The emitted electron energy spectrum reveals an ultranarrow distribution down to 16 meV due to tunable resonant tunneling field emission via localized band states at a nanoprotrusion's apex and a cutoff at the sharp low-temperature Fermi edge. This is an order of magnitude lower than for conventional field emission electron sources. The self-focusing geometry of the tip leads to emission in an angle of 3.7°, a reduced brightness of 3.8×10^{8} A/(m^{2} sr V), and a stability of hours at 4.1 nA beam current and 69 meV energy width. This source will decrease the impact of lens aberration and enable new modes in low-energy electron microscopy, electron energy loss spectroscopy, and high-resolution vibrational spectroscopy.

Reaching the theoretical resonance quality factor limit in coaxial plasmonic nanoresonators fabricated by helium ion lithography.

Optical antenna structures have revolutionized the field of nano-optics by confining light to deep subwavelength dimensions for spectroscopy and sensing. In this work, we fabricated coaxial optical antennae with sub-10-nanometer critical dimensions using helium ion lithography (HIL). Wavelength dependent transmission measurements were used to determine the wavelength-dependent optical response. The quality factor of 11 achieved with our HIL fabricated structures matched the theoretically predicted quality factor for the idealized flawless gold resonators calculated by finite-difference time-domain (FDTD). For comparison, coaxial antennae with 30 nm critical dimensions were fabricated using both HIL and the more common Ga focus ion beam lithography (Ga-FIB). The quality factor of the Ga-FIB resonators was 60% of the ideal HIL results for the same design geometry due to limitations in the Ga-FIB fabrication process.

Extended mapping and exploration of the vanadium dioxide stress-temperature phase diagram.

Single-crystal micro- and nanomaterials often exhibit higher yield strength than their bulk counterparts. This enhancement is widely recognized in structural materials but is rarely exploited to probe fundamental physics of electronic materials. Vanadium dioxide exhibits coupled electronic and structural phase transitions that involve different structures existing at different strain states. Full understanding of the driving mechanism of these coupled transitions necessitates concurrent structural and electrical measurements over a wide phase space. Taking advantages of the superior mechanical property of micro/nanocrystals of VO(2), we map and explore its stress-temperature phase diagram over a phase space that is more than an order of magnitude broader than previously attained. New structural and electronic aspects were observed crossing phase boundaries at high-strain states. Our work shows that the actively tuning strain in micro/nanoscale electronic materials provides an effective route to investigate their fundamental properties beyond what can be accessed in their bulk counterpart.

Functional plasmonic antenna scanning probes fabricated by induced-deposition mask lithography.

We have fabricated plasmonic bowtie antennae on the apex of silicon atomic-force microscope cantilever tips that enhance the local silicon Raman scattering intensity by approximately 4 x 10(4) when excited near the antenna resonance. The antennae were fabricated using a novel method, induced-deposition mask lithography (IDML), capable of creating high-purity metallic nanostructures on non-planar, non-conducting substrates with high repeatability. IDML involves electron-beam-induced deposition of a W or SiO(x) hard mask on the material to be pattered, here a 20 nm Au film, followed by Ar ion etching to remove the mask and the unmasked gold, leaving a chemically pure Au bowtie antenna. Antenna function and reproducibility was confirmed by comparing Raman spectra for excitation polarized parallel and perpendicular to the antenna axis, as well as by dark-field spectroscopic characterization of resonant modes. The field enhancement of these plasmonic AFM antennae tips was comparable with antennae produced by electron-beam lithography on flat substrates.

Imaging the condensation and evaporation of molecularly thin films of water with nanometer resolution.

The polarization force between an electrically charged atomic force microscope tip and a substrate has been used to follow the processes of condensation and evaporation of a monolayer of water on mica at room temperature. Condensation proceeds in two distinct structural phases. Up to about 25 percent humidity, the water film grows by forming two-dimensional clusters of less than a few 1000 angstroms in diameter. Above about 25 percent humidity, a second phase grows, forming large two-dimensional islands with geometrical shapes in epitaxial relation with the underlaying mica lattice. The growth of this second water phase is completed when the humidity reaches about 45 percent. The reverse process of evaporation has also been imaged.

Direct observation of native DNA structures with the scanning tunneling microscope.

Uncoated double-stranded DNA dissolved in a salt solution was deposited on graphite and imaged in air with the scanning tunneling microscope (STM). The resolution was such that the major and minor grooves could be distinguished. The pitch of the helix varied between 27 and 63 angstroms in the images obtained. Thus the STM can be useful for structural studies of a variety of uncoated and isolated biomolecules.

Atomic force microscopy imaging of T4 bacteriophages on silicon substrates.

A new atomic force microscope incorporating microfabricated cantilevers and employing laser beam deflection for force detection has been constructed and is being applied to studies of biological material. In this study, T4 bacteriophage virus particles were deposited from solution onto electronic-grade flat silicon wafers and imaged in air with the microscope. Microliter droplets of the solution were deposited and either allowed to dry or removed with blotting paper. The images show both isolated viruses and aggregates of various sizes. The external structure as well as strands believed to be DNA streaming out of the virus could be observed. The construction of the microscope and its performance are also described.

Mapping local charge recombination heterogeneity by multidimensional nanospectroscopic imaging.

As materials functionality becomes more dependent on local physical and electronic properties, the importance of optically probing matter with true nanoscale spatial resolution has increased. In this work, we mapped the influence of local trap states within individual nanowires on carrier recombination with deeply subwavelength resolution. This is achieved using multidimensional nanospectroscopic imaging based on a nano-optical device. Placed at the end of a scan probe, the device delivers optimal near-field properties, including highly efficient far-field to near-field coupling, ultralarge field enhancement, nearly background-free imaging, independence from sample requirements, and broadband operation. We performed ~40-nanometer-resolution hyperspectral imaging of indium phosphide nanowires via excitation and collection through the probes, revealing optoelectronic structure along individual nanowires that is not accessible with other methods.

Strain engineering and one-dimensional organization of metal-insulator domains in single-crystal vanadium dioxide beams.

Correlated electron materials can undergo a variety of phase transitions, including superconductivity, the metal-insulator transition and colossal magnetoresistance. Moreover, multiple physical phases or domains with dimensions of nanometres to micrometres can coexist in these materials at temperatures where a pure phase is expected. Making use of the properties of correlated electron materials in device applications will require the ability to control domain structures and phase transitions in these materials. Lattice strain has been shown to cause the coexistence of metallic and insulating phases in the Mott insulator VO(2). Here, we show that we can nucleate and manipulate ordered arrays of metallic and insulating domains along single-crystal beams of VO(2) by continuously tuning the strain over a wide range of values. The Mott transition between a low-temperature insulating phase and a high-temperature metallic phase usually occurs at 341 K in VO(2), but the active control of strain allows us to reduce this transition temperature to room temperature. In addition to device applications, the ability to control the phase structure of VO(2) with strain could lead to a deeper understanding of the correlated electron materials in general.

A study of the topographic and electrical properties of self-assembled islands of alkylsilanes on mica using a combination of non-contact force microscopy techniques.

We use a combination of non-contact scanning force microscope operation modes to study the changes in topographic and electrostatic properties of self-assembled monolayer islands of alkylsilanes on mica. The combined technique uses simultaneous electrical and mechanical modulation and feedback modes to produce four images that reveal the topography, phase, surface potential and dielectric constant. The results show significant advantages with this combined method. As an example we show that the interaction of water with self-assembled monolayer islands of alkylsilanes produces changes in the surface potential of the system but not in the topography.

Electronic control of friction in silicon pn junctions.

A remarkable dependence of the friction force on carrier concentration was found on doped silicon substrates. The sample was a nearly intrinsic n-type Si(100) wafer patterned with 2-micrometer-wide stripes of highly B-doped p-type material. The counter surface was the tip of an atomic force microscope coated with conductive titanium nitride. The local carrier concentration was controlled through application of forward or reverse bias voltages between the tip and the sample in the p and the n regions. Charge depletion or accumulation resulted in substantial differences in friction force. The results demonstrate the capability to electronically control friction in semiconductor devices, with potential applications in nanoscale machines containing moving parts.

Diffusion and pair interactions of CO molecules on Pd(111).

The diffusion and interactions of CO molecules on Pd(111) were studied by scanning tunneling microscopy. By following the random walk motion of individual molecules as a function of temperature, an activation energy barrier for diffusion of 118 +/- 5 meV was determined. The interaction between CO molecules was found to be repulsive for pairs separated by one or two Pd(111) lattice distances, and weakly attractive at a separation of sqrt[3].

Atomic force microscopy study of beta-substituted-T7 oligothiophene films on mica: mechanical properties and humidity-dependent phases.

The structural and mechanical properties of Langmuir-Blodgett monolayer and multilayer films of 3",4""-didecyl-5,2'; 5',2"; 5",2'''; 5''',2""; 5"",2'''''; 5''''',2"""-heptathiophene-4'''-acetic acid on mica have been studied by atomic force microscopy (AFM) as a function of humidity, temperature, and applied force. The molecules orient with the carboxylic acid group pointing toward the mica surface and expose the alkyl side chains to the air interface. As the load applied by the AFM tip increases, the film is compressed easily from an initial height of 2 to 1.2 nm. After compression the films can support much higher loads without loss of height. The state of aggregation of the molecules was found to be sensitive to the environmental humidity, which induced reversible changes. Annealing the samples with monolayer or multilayer films resulted in irreversible changes when the temperature exceeded approximately 100 degrees C.

High frictional anisotropy of periodic and aperiodic directions on a quasicrystal surface.

Strong friction anisotropy is found when the twofold surface of an atomically clean aluminum-nickel-cobalt quasicrystal slides against a thiol-passivated titanium-nitride tip. Friction along the aperiodic direction is one-eighth as much as that along the periodic direction. This anisotropy, which is about three times as large as the highest value observed in anisotropic crystalline surfaces, disappears after the surface is oxidized in air. These results reveal a strong connection between interface atomic structure and the mechanisms by which energy is dissipated, which likely include electronic or phononic contributions, or both.

Sensing dipole fields at atomic steps with combined scanning tunneling and force microscopy.

The electric field of dipoles localized at the atomic steps of metal surfaces due to the Smoluchowski effect were measured from the electrostatic force exerted on the biased tip of a scanning tunneling microscope. By varying the tip-sample bias the contribution of the step dipole was separated from changes in the force due to van der Waals and polarization forces. Combined with electrostatic calculations, the method was used to determine the local dipole moment in steps of different heights on Au(111) and on the twofold surface of an Al-Ni-Co decagonal quasicrystal.

Dissociative hydrogen adsorption on palladium requires aggregates of three or more vacancies.

During reaction, a catalyst surface usually interacts with a constantly fluctuating mix of reactants, products, 'spectators' that do not participate in the reaction, and species that either promote or inhibit the activity of the catalyst. How molecules adsorb and dissociate under such dynamic conditions is often poorly understood. For example, the dissociative adsorption of the diatomic molecule H2--a central step in many industrially important catalytic processes--is generally assumed to require at least two adjacent and empty atomic adsorption sites (or vacancies). The creation of active sites for H2 dissociation will thus involve the formation of individual vacancies and their subsequent diffusion and aggregation, with the coupling between these events determining the activity of the catalyst surface. But even though active sites are the central component of most reaction models, the processes controlling their formation, and hence the activity of a catalyst surface, have never been captured experimentally. Here we report scanning tunnelling microscopy observations of the transient formation of active sites for the dissociative adsorption of H2 molecules on a palladium (111) surface. We find, contrary to conventional thinking, that two-vacancy sites seem inactive, and that aggregates of three or more hydrogen vacancies are required for efficient H2 dissociation.

Membrane specific mapping and colocalization of malarial and host skeletal proteins in the Plasmodium falciparum infected erythrocyte by dual-color near-field scanning optical microscopy.

Accurate localization of proteins within the substructure of cells and cellular organelles enables better understanding of structure-function relationships, including elucidation of protein-protein interactions. We describe the use of a near-field scanning optical microscope (NSOM) to simultaneously map and detect colocalized proteins within a cell, with superresolution. The system we elected to study was that of human red blood cells invaded by the human malaria parasite Plasmodium falciparum. During intraerythrocytic growth, the parasite expresses proteins that are transported to the erythrocyte cell membrane. Association of parasite proteins with host skeletal proteins leads to modification of the erythrocyte membrane. We report on colocalization studies of parasite proteins with an erythrocyte skeletal protein. Host and parasite proteins were selectively labeled in indirect immunofluorescence antibody assays. Simultaneous dual-color excitation and detection with NSOM provided fluorescence maps together with topography of the cell membrane with subwavelength (100 nm) resolution. Colocalization studies with laser scanning confocal microscopy provided lower resolution (310 nm) fluorescence maps of cross sections through the cell. Because the two excitation colors shared the exact same near-field aperture, the two fluorescence images were acquired in perfect, pixel-by-pixel registry, free from chromatic aberrations, which contaminate laser scanning confocal microscopy measurements. Colocalization studies of the protein pairs of mature parasite-infected erythrocyte surface antigen (MESA) (parasite)/protein4.1(host) and P. falciparum histidine rich protein (PfHRP1) (parasite)/protein4.1(host) showed good real-space correlation for the MESA/protein4.1 pair, but relatively poor correlation for the PfHRP1/protein4.1 pair. These data imply that NSOM provides high resolution information on in situ interactions between proteins in biological membranes. This method of detecting colocalization of proteins in cellular structures may have general applicability in many areas of current biological research.

Water diffusion and clustering on Pd(111).

The adsorption, diffusion, and clustering of water molecules on a Pd(111) surface were studied by scanning tunneling microscopy. At 40 kelvin, low-coverage water adsorbs in the form of isolated molecules, which diffuse by hopping to nearest neighbor sites. Upon collision, they form first dimers, then trimers, tetramers, and so on. The mobility of these species increased by several orders of magnitude when dimers, trimers, and tetramers formed, and decreased again when the cluster contained five or more molecules. Cyclic hexamers were found to be particularly stable. They grow with further exposure to form a commensurate hexagonal honeycomb structure relative to the Pd(111) substrate. These observations illustrate the change in relative strength between intermolecular hydrogen bonds and molecule-substrate bonds as a function of water cluster size, the key property that determines the wetting properties of materials.

Preparation and nanoscale mechanical properties of self-assembled carboxylic acid functionalized pentathiophene on mica.

The oligothiophene derivative 4-(5' " '-decyl-[2,2';5',2' ';5' ',2' ";5' ",2' " '] pentathiophen-5-yl)-butyric acid (D5TBA) was synthesized by Stille cross-coupling methods using functionalized thiophene monomers. The structural and mechanical properties of D5TBA self-assembled monolayers on mica have been studied by atomic force microscopy (AFM). The self-assembled films were prepared by immersing the mica in dilute chloroform or tetrahydrofuran (THF) solutions. The films were predominantly of monolayer thickness with molecules packed in nearly upright orientations. In regions covered with multilayers, the molecules in each monolayer were oriented opposite to those in the neighboring ones, that is, with COOH-COOH and CH3-CH3 contact. The nature of the end group in contact with the substrate depended on the solvent used and the degree of hydration of the substrate, with hydrophobic chloroform solvent favoring the methyl end down and hydrophilic THF favoring the acid group end down. The orientation could also be controlled by dipping using the Langmuir-Blodgett technique.

Probing the interaction between two single molecules: fluorescence resonance energy transfer between a single donor and a single acceptor.

We extend the sensitivity of fluorescence resonance energy transfer (FRET) to the single molecule level by measuring energy transfer between a single donor fluorophore and a single acceptor fluorophore. Near-field scanning optical microscopy (NSOM) is used to obtain simultaneous dual color images and emission spectra from donor and acceptor fluorophores linked by a short DNA molecule. Photodestruction dynamics of the donor or acceptor are used to determine the presence and efficiency of energy transfer. The classical equations used to measure energy transfer on ensembles of fluorophores are modified for single-molecule measurements. In contrast to ensemble measurements, dynamic events on a molecular scale are observable in single pair FRET measurements because they are not canceled out by random averaging. Monitoring conformational changes, such as rotations and distance changes on a nanometer scale, within single biological macromolecules, may be possible with single pair FRET.