Graphene as a subnanometre trans-electrode membrane.

Isolated, atomically thin conducting membranes of graphite, called graphene, have recently been the subject of intense research with the hope that practical applications in fields ranging from electronics to energy science will emerge. The atomic thinness, stability and electrical sensitivity of graphene motivated us to investigate the potential use of graphene membranes and graphene nanopores to characterize single molecules of DNA in ionic solution. Here we show that when immersed in an ionic solution, a layer of graphene becomes a new electrochemical structure that we call a trans-electrode. The trans-electrode's unique properties are the consequence of the atomic-scale proximity of its two opposing liquid-solid interfaces together with graphene's well known in-plane conductivity. We show that several trans-electrode properties are revealed by ionic conductance measurements on a graphene membrane that separates two aqueous ionic solutions. Although our membranes are only one to two atomic layers thick, we find they are remarkable ionic insulators with a very small stable conductance that depends on the ion species in solution. Electrical measurements on graphene membranes in which a single nanopore has been drilled show that the membrane's effective insulating thickness is less than one nanometre. This small effective thickness makes graphene an ideal substrate for very high resolution, high throughput nanopore-based single-molecule detectors. The sensitivity of graphene's in-plane electronic conductivity to its immediate surface environment and trans-membrane solution potentials will offer new insights into atomic surface processes and sensor development opportunities.

Atom-by-atom nucleation and growth of graphene nanopores.

Graphene is an ideal thin membrane substrate for creating molecule-scale devices. Here we demonstrate a scalable method for creating extremely small structures in graphene with atomic precision. It consists of inducing defect nucleation centers with energetic ions, followed by edge-selective electron recoil sputtering. As a first application, we create graphene nanopores with radii as small as 3 Å, which corresponds to 10 atoms removed. We observe carbon atom removal from the nanopore edge in situ using an aberration-corrected electron microscope, measure the cross-section for the process, and obtain a mean edge atom displacement energy of 14.1 ± 0.1 eV. This approach does not require focused beams and allows scalable production of single nanopores and arrays of monodisperse nanopores for atomic-scale selectively permeable membranes.

Ice-assisted electron beam lithography of graphene.

We demonstrate that a low energy focused electron beam can locally pattern graphene coated with a thin ice layer. The irradiated ice plays a crucial role in the process by providing activated species that locally remove graphene from a silicon dioxide substrate. After patterning the graphene, the ice resist is easily removed by sublimation to leave behind a clean surface with no further processing. More generally, our findings demonstrate that ice-assisted e-beam lithography can be used to pattern very thin materials deposited on substrate surfaces. The procedure is performed in situ in a modified scanning electron microscope. Desirable structures such as nanoribbons are created using the method. Defects in graphene from electrons backscattered from the bulk substrate are identified. They extend several microns from the e-beam writing location. We demonstrate that these defects can be greatly reduced and localized by using thinner substrates and/or gentle thermal annealing.

Field ionization of cold atoms near the wall of a single carbon nanotube.

We observe the capture and field ionization of individual atoms near the side wall of a single suspended nanotube. Extremely large cross sections for ionization from an atomic beam are observed at modest voltages due to the nanotube's small radius and extended length. The effects of the field strength on both the atomic capture and the ionization process are clearly distinguished in the data, as are prompt and delayed ionizations related to the locations at which they occur. Efficient and sensitive neutral atom detectors can be based on the nanotube capture and wall ionization processes.

The tunneling microscope: a new look at the atomic world.

A new instrument called the tunneling microscope has recently been developed that is capable of generating real-space images of surfaces showing atomic structure. These images offer a new view of matter on an atomic scale. The current capabilities and limitations and the physics involved in the technique are discussed along with specific results from a study of silicon crystal surfaces.

Mobile point defects and atomic basis for structural transformations of a crystal surface.

Structural transformations on elemental semiconductor surfaces typically occur above several hundred degrees Celsius, and the atomic motions involved are extremely rapid and difficult to observe. However, on the (111) surface of germanium, a few lead atoms catalyze atomic motions so that they can be observed with a tunneling microscope at temperatures below 80 degrees C. Mass transport and structural changes are caused by the creation and propagation of both vacancy-like and interstitial-like point defects within the crystal surface. The availability of dangling bonds on the surface is critical. A detailed atomic model for the observed motions has been developed and is used to explain the structural phase transition Ge(111)-c(2x8) <--> 1x1, which occurs near 300 degrees C.

Optical matter: crystallization and binding in intense optical fields.

Properly fashioned electromagnetic fields coupled to microscopic dielectric objects can be used to create arrays of extended crystalline and noncrystalline structures. Organization can be achieved in two ways: In the first, dielectric matter is transported in direct response to the externally applied standing wave optical fields. In the second, the external optical fields induce interactions between dielectric objects that can also result in the creation of complex structures. In either case, these new ordered structures, whose existence depends on the presence of both light and polarizable matter, are referred to as optical matter.

A capacitance-based micropositioning system for x-ray rocking curve measurements.

Certain types of x-ray experiments require very precise angular positioning of crystals in the vicinity of the Bragg reflection condition. A system applicable to some measurement of this type is described which achieves a long-term angular stability of approximately 10(-7) radians, coupled with a linear angular readout. This is achieved through a novel capacitance sensing system which provides angle measurement, together with the use of an auxilliary servo loop based on the Bragg condition to ensure long-term overall angular stability.

Tunable nanometer electrode gaps by MeV ion irradiation.

We report the use of MeV ion-irradiation-induced plastic deformation of amorphous materials to fabricate electrodes with nanometer-sized gaps. Plastic deformation of the amorphous metal Pd(80)Si(20) is induced by 4.64 MeV O(2+) ion irradiation, allowing the complete closing of a sub-micrometer gap. We measure the evolving gap size in situ by monitoring the field emission current-voltage (I-V) characteristics between electrodes. The I-V behavior is consistent with Fowler-Nordheim tunneling. We show that using feedback control on this signal permits gap size fabrication with atomic-scale precision. We expect this approach to nanogap fabrication will enable the practical realization of single molecule controlled devices and sensors.

An ice lithography instrument.

We describe the design of an instrument that can fully implement a new nanopatterning method called ice lithography, where ice is used as the resist. Water vapor is introduced into a scanning electron microscope (SEM) vacuum chamber above a sample cooled down to 110 K. The vapor condenses, covering the sample with an amorphous layer of ice. To form a lift-off mask, ice is removed by the SEM electron beam (e-beam) guided by an e-beam lithography system. Without breaking vacuum, the sample with the ice mask is then transferred into a metal deposition chamber where metals are deposited by sputtering. The cold sample is then unloaded from the vacuum system and immersed in isopropanol at room temperature. As the ice melts, metal deposited on the ice disperses while the metals deposited on the sample where the ice had been removed by the e-beam remains. The instrument combines a high beam-current thermal field emission SEM fitted with an e-beam lithography system, cryogenic systems, and a high vacuum metal deposition system in a design that optimizes ice lithography for high throughput nanodevice fabrication. The nanoscale capability of the instrument is demonstrated with the fabrication of nanoscale metal lines.

Graphene synthesis by ion implantation.

We demonstrate an ion implantation method for large-scale synthesis of high quality graphene films with controllable thickness. Thermally annealing polycrystalline nickel substrates that have been ion implanted with carbon atoms results in the surface growth of graphene films whose average thickness is controlled by implantation dose. The graphene film quality, as probed with Raman and electrical measurements, is comparable to previously reported synthesis methods. The implantation synthesis method can be generalized to a variety of metallic substrates and growth temperatures, since it does not require a decomposition of chemical precursors or a solvation of carbon into the substrate.

Recapturing and trapping single molecules with a solid-state nanopore.

The development of solid-state nanopores, inspired by their biological counterparts, shows great potential for the study of single macromolecules. Applications such as DNA sequencing and the exploration of protein folding require control of the dynamics of the molecule's interaction with the pore, but DNA capture by a solid-state nanopore is not well understood. By recapturing individual molecules soon after they pass through a nanopore, we reveal the mechanism by which double-stranded DNA enters the pore. The observed recapture rates and times agree with solutions of a drift-diffusion model. Electric forces draw DNA to the pore over micrometer-scale distances, and upon arrival at the pore, molecules begin translocation almost immediately. Repeated translocation of the same molecule improves measurement accuracy, offers a way to probe the chemical transformations and internal dynamics of macromolecules on sub-millisecond time and sub-micrometre length scales, and demonstrates the ability to trap, study and manipulate individual macromolecules in solution.

Nanoscale volcanoes: accretion of matter at ion-sculpted nanopores.

We demonstrate the formation of nanoscale volcano-like structures induced by ion-beam irradiation of nanoscale pores in freestanding silicon nitride membranes. Accreted matter is delivered to the volcanoes from micrometer distances along the surface. Volcano formation accompanies nanopore shrinking and depends on geometrical factors and the presence of a conducting layer on the membrane's back surface. We argue that surface electric fields play an important role in accounting for the experimental observations.

Probing nanotube-nanopore interactions.

We demonstrate a new nanoscale system consisting of a nanotube threaded through a nanopore in aqueous solution. Its electrical and mechanical properties are sensitive to experimentally controllable conformational changes on sub-Angstrom length scales. Ionic current transport through a nanopore is significantly suppressed by the threading nanotube and the mechanical interactions between the nanotube and pore are accounted for by a folding geometry. The experiments provide first measurements of the longitudinal resolution and metrology of a solid-state nanopore "microscope." This new nanostructure provides a means to study molecule-nanotube interactions in conducting ionic solutions as well as geometrical and surface properties of nanopores and nanotubes.

Detection and quantized conductance of neutral atoms near a charged carbon nanotube.

We describe a novel single atom detector that uses the high electric field surrounding a charged single-walled carbon nanotube to attract and subsequently field-ionize neutral atoms. A theoretical study of the field-ionization tunneling rates for atomic trajectories in the attractive potential near a nanowire shows that a broadly applicable, high spatial resolution, low-power, neutral-atom detector with nearly 100% efficiency is realizable with present-day technology. Calculations also show that the system can provide the first opportunity to study quantized conductance phenomena when detecting cold neutral atoms with mean velocities less than 15 m/s.

Deflection and diffraction of x rays bound to curved surfaces.

We present two new x-ray optical effects observed on a whispering-gallery waveguide. The first is a gradual in-surface deflection of guided waves caused by the non-Euclidean intrinsic curvature of the waveguide surface. The second is the excitation of in-surface dynamical diffraction modes that reflects the strong influence of the surface photonic band structure of a crystalline waveguide. Both phenomena portend a rich array of basic and applied x-ray optical potentialities.

Confinement-enhanced electron transport across a metal-semiconductor interface.

We present a combined scanning tunneling microscopy and ballistic electron emission microscopy study of electron transport across an epitaxial Pb/Si(111) interface. Experiments with a self-assembled Pb nanoscale wedge reveal the phenomenon of confinement-enhanced interfacial transport: a proportional increase of the electron injection rate into the semiconductor with the frequency of electron oscillations in the Pb quantum well.

DNA molecules and configurations in a solid-state nanopore microscope.

A nanometre-scale pore in a solid-state membrane provides a new way of electronically probing the structure of single linear polymers, including those of biological interest in their native environments. Previous work with biological protein pores wide enough to let through and sense single-stranded DNA molecules demonstrates the power of using nanopores, but many future tasks and applications call for a robust solid-state pore whose nanometre-scale dimensions and properties may be selected, as one selects the lenses of a microscope. Here we demonstrate a solid-state nanopore microscope capable of observing individual molecules of double-stranded DNA and their folding behaviour. We discuss extensions of the nanopore microscope concept to alternative probing mechanisms and applications, including the study of molecular structure and sequencing.

Ion-beam sculpting at nanometre length scales.

Manipulating matter at the nanometre scale is important for many electronic, chemical and biological advances, but present solid-state fabrication methods do not reproducibly achieve dimensional control at the nanometre scale. Here we report a means of fashioning matter at these dimensions that uses low-energy ion beams and reveals surprising atomic transport phenomena that occur in a variety of materials and geometries. The method is implemented in a feedback-controlled sputtering system that provides fine control over ion beam exposure and sample temperature. We call the method "ion-beam sculpting", and apply it to the problem of fabricating a molecular-scale hole, or nanopore, in a thin insulating solid-state membrane. Such pores can serve to localize molecular-scale electrical junctions and switches and function as masks to create other small-scale structures. Nanopores also function as membrane channels in all living systems, where they serve as extremely sensitive electro-mechanical devices that regulate electric potential, ionic flow, and molecular transport across cellular membranes. We show that ion-beam sculpting can be used to fashion an analogous solid-state device: a robust electronic detector consisting of a single nanopore in a Si3N4 membrane, capable of registering single DNA molecules in aqueous solution.