Initiating and Monitoring the Evolution of Single Electrons Within Atom-Defined Structures.

Using a noncontact atomic force microscope, we track and manipulate the position of single electrons confined to atomic structures engineered from silicon dangling bonds on the hydrogen terminated silicon surface. An attractive tip surface interaction mechanically manipulates the equilibrium position of a surface silicon atom, causing rehybridization that stabilizes a negative charge at the dangling bond. This is applied to controllably switch the charge state of individual dangling bonds. Because this mechanism is based on short range interactions and can be performed without applied bias voltage, we maintain both site-specific selectivity and single-electron control. We extract the short range forces involved with this mechanism by subtracting the long range forces acquired on a dimer vacancy site. As a result of relaxation of the silicon lattice to accommodate negatively charged dangling bonds, we observe charge configurations of dangling bond structures that remain stable for many seconds at 4.5 K. Subsequently, we use charge manipulation to directly prepare the ground state and metastable charge configurations of dangling bond structures composed of up to six atoms.

Quantum Transport in Gated Dangling-Bond Atomic Wires.

A single line of dangling bonds (DBs) on Si(100)-2 × 1:H surface forms a perfect metallic atomic-wire. In this work, we investigate quantum transport properties of such dangling bond wires (DBWs) by a state-of-the-art first-principles technique. It is found that the conductance of the DBW can be gated by electrostatic potential and orbital overlap due to only a single DB center (DBC) within a distance of ∼16 Å from the DBW. The gating effect is more pronounced for two DBCs and especially, when these two DB "gates" are within ∼3.9 Å from each other. These effective length scales are in excellent agreement with those measured in scanning tunnelling microscope experiments. By analyzing transmission spectrum and density of states of DBC-DBW systems, with or without subsurface doping, for different length of the DBW, distance between DBCs and the DBW, and distance between DB gates, we conclude that charge transport in a DBW can be regulated to have both an on-state and an off-state using only one or two DBs.

Time-Resolved Imaging of Negative Differential Resistance on the Atomic Scale.

Negative differential resistance remains an attractive but elusive functionality, so far only finding niche applications. Atom scale entities have shown promising properties, but the viability of device fabrication requires a fuller understanding of electron dynamics than has been possible to date. Using an all-electronic time-resolved scanning tunneling microscopy technique and a Green's function transport model, we study an isolated dangling bond on a hydrogen terminated silicon surface. A robust negative differential resistance feature is identified as a many body phenomenon related to occupation dependent electron capture by a single atomic level. We measure all the time constants involved in this process and present atomically resolved, nanosecond time scale images to simultaneously capture the spatial and temporal variation of the observed feature.

Conductivity of Si(111)-(7×7): the role of a single atomic step.

While it is known that the Si-(7×7) is a conducting surface, measured conductivity values differ by 7 orders of magnitude. Here we report a combined STM and transport method capable of surface conductivity measurement of step-free or single-step containing surface regions and having minimal interaction with the sample, and by which we quantitatively determine the intrinsic conductivity of the Si-(7×7) surface. We found that a single step has a conductivity per unit length about 50 times smaller than the flat surface. Our first principles quantum transport calculations confirm and lend insight into the experimental observation.

Single-electron dynamics of an atomic silicon quantum dot on the H-Si(100)-(2×1) surface.

Here we report the direct observation of single electron charging of a single atomic dangling bond (DB) on the H-Si(100)-2×1 surface. The tip of a scanning tunneling microscope is placed adjacent to the DB to serve as a single-electron sensitive charge detector. Three distinct charge states of the dangling bond--positive, neutral, and negative--are discerned. Charge state probabilities are extracted from the data, and analysis of current traces reveals the characteristic single-electron charging dynamics. Filling rates are found to decay exponentially with increasing tip-DB separation, but are not a function of sample bias, while emptying rates show a very weak dependence on tip position, but a strong dependence on sample bias, consistent with the notion of an atomic quantum dot tunnel coupled to the tip on one side and the bulk silicon on the other.

Evaluating angular ion current density for atomically defined nanotips.

In this paper we investigate methods to characterize angular current density from atomically defined gas field ion sources. We show that the ion beam emitted from a single apex atom is described by a two-dimensional Gaussian profile. Owing to the Gaussian shape of the beam and the requirement to collect the majority of the ion current, fixed apertures have inhomogeneous illumination. Therefore, angular current density measurements through a fixed aperture record averaged angular current density. This makes comparison of data difficult as averaged angular current density depends on aperture size. For the same reasons, voltage normalization cannot be performed for fixed aperture measurements except for aperture sizes that are infinitely small. Consistent determination of angular current density and voltage normalization, however, can be achieved if the beam diameter as well as total ion current are known. In cases where beam profile cannot be directly imaged with a field ion microscope, the beam profile could be extracted from measurements taken at multiple acceleration voltages and/or with multiple aperture sizes.

Atomically Precise Manufacturing of Silicon Electronics.

Atomically precise manufacturing (APM) is a key technique that involves the direct control of atoms in order to manufacture products or components of products. It has been developed most successfully using scanning probe methods and has received particular attention for developing atom scale electronics with a focus on silicon-based systems. This review captures the development of silicon atom-based electronics and is divided into several sections that will cover characterization and atom manipulation of silicon surfaces with scanning tunneling microscopy and atomic force microscopy, development of silicon dangling bonds as atomic quantum dots, creation of atom scale devices, and the wiring and packaging of those circuits. The review will also cover the advance of silicon dangling bond logic design and the progress of silicon quantum atomic designer (SiQAD) simulators. Finally, an outlook of APM and silicon atom electronics will be provided.

Organic nanostructures on hydrogen-terminated silicon report on electric field modulation of dangling bond charge state.

We pursue dynamic charge and occupancy modulation of silicon dangling bond sites on H-Si(100)-2 × 1 with a biased scanning tunneling microscope tip and demonstrate that the reactivity and mechanism of product formation of cyclobutylmethylketone (CBMK) on the surface at the active sites may be thus spatially regulated. Reactivity is observed to be dependent on the polarity between tip and surface while the area over which reactivity modulation is established scales according to the dopant concentration in the sample. We account for these observations with examination of the competition kinetics applicable to the CBMK/H-Si reaction and determine how said kinetics are affected by the charge state of DB sites associated with reaction initiation and propagation. Our experiments demonstrate a new paradigm in lithographic control of a self-assembly process on H-Si and reveal a variant to the well-known radical mediated chain reaction chemistry applicable to the H-Si surface where self-assembly is initiated with dative bond formation between the molecule and a DB site.

Creation and recovery of a W(111) single atom gas field ion source.

Tungsten single atom tips have been prepared from a single crystal W(111) oriented wire using the chemical assisted field evaporation and etching method. Etching to a single atom tip occurs through a symmetric structure and leads to a predictable last atom unlike etching with polycrystalline tips. The single atom tip formation procedure is shown in an atom by atom removal process. Rebuilds of single atom tips occur on the same crystalline axis as the original tip such that ion emission emanates along a fixed direction for all tip rebuilds. This preparation method could be utilized and developed to prepare single atom tips for ion source development.

Field regulation of single-molecule conductivity by a charged surface atom.

Electrical transport through molecules has been much studied since it was proposed that individual molecules might behave like basic electronic devices, and intriguing single-molecule electronic effects have been demonstrated. But because transport properties are sensitive to structural variations on the atomic scale, further progress calls for detailed knowledge of how the functional properties of molecules depend on structural features. The characterization of two-terminal structures has become increasingly robust and reproducible, and for some systems detailed structural characterization of molecules on electrodes or insulators is available. Here we present scanning tunnelling microscopy observations and classical electrostatic and quantum mechanical modelling results that show that the electrostatic field emanating from a fixed point charge regulates the conductivity of nearby substrate-bound molecules. We find that the onset of molecular conduction is shifted by changing the charge state of a silicon surface atom, or by varying the spatial relationship between the molecule and that charged centre. Because the shifting results in conductivity changes of substantial magnitude, these effects are easily observed at room temperature.

Tunnel coupled dangling bond structures on hydrogen terminated silicon surfaces.

We study both experimentally and theoretically the electronic behavior of dangling bonds (DBs) at a hydrogen terminated Si(100)-2×1 surface. Dangling bonds behave as quantum dots and, depending on their separation, can be tunnel coupled with each other or completely isolated. On n-type highly doped silicon, the latter have a net charge of -1e, while coupled DBs exhibit altered but predictable filling behavior derived from an interplay between interdot tunneling and Coulomb repulsion. We found good correlation between many scanning tunneling micrographs of dangling bond structures and our theoretical results of a corresponding extended Hubbard model. We also demonstrated chemical methods to prevent tunnel coupling and isolate charge on a single dangling bond.

Indications of field-directing and self-templating effects on the formation of organic lines on silicon.

It has previously been shown that multimolecular organic nanostructures form on H-Si(100)-2×1 via a radical mediated growth process. In this mechanism, growth begins through the addition of a molecule to a silicon surface dangling bond, followed by the abstraction of a neighboring H atom and generation of a new dangling bond on the neighboring site. Nanostructures formed by this mechanism grow along one edge of a dimer row. Here, we explored the possibility of using lithographically prepared, biased metal contacts on the silicon surface to generate an electric field that orients molecules during the growth process to achieve growth in the perpendicular-to-row direction. The formation of some nanostructures in a direction that was nearly perpendicular to the dimer rows was achieved, whereas such features were not formed in the absence of the field. Analysis of the scanning tunneling microscopy images suggests that the formation of these nanostructures may involve self-templating effects in addition to dangling bond diffusion rather than a straightforward addition∕abstraction mechanism. These initial results offer some indication that a molecular pattern writer can be achieved.

Ohmic Contact to Two-Dimensional Nanofabricated Silicon Structures with a Two-Probe Scanning Tunneling Microscope.

We used multiprobe scanning tunneling microscope (STM) to fabricate and electrically characterize nanostructures on Si surfaces. We overcame resistive contacts by using field evaporation to clean tip apexes in order to create Ohmic contact with the Si surface states on a Si substrate. A two-probe (2P-) STM with Ohmic contact allowed for measurement at very low bias, limiting conduction through space-charge layer and bulk states. The Ohmic 2P-STM measurement clarified the surface conductivity of the Si(111)-(7 × 7) surface. We also confirmed that Ohmic 2P-STM can be replaced with more convenient Ohmic one-probe STM for the conductance measurements on the Si surface. We prepared nanostructures using STM lithography to define electronically isolated two-dimensional (2D) regions with various aspect ratios. Their surface conduction properties are described well by the conventional sheet model, proving the diffusive 2D conduction on the Si surface. Constrictions and breaks in 2D structures were also evaluated. Ohmic 2P-STM will be helpful for the investigation of exploratory atomic-scale circuitry or cutting-edge materials sciences.

Ionic charge distributions in silicon atomic surface wires.

Using a non-contact atomic force microscope (nc-AFM), we examine continuous dangling bond (DB) wire structures patterned on the hydrogen terminated silicon (100)-2 × 1 surface. By probing the DB structures at varying energies, we identify the formation of previously unobserved ionic charge distributions which are correlated to the net charge of DB wires and their predicted degrees of freedom in lattice distortions. Performing spectroscopic analysis, we identify higher energy configurations corresponding to alternative lattice distortions as well as tip-induced charging effects. By varying the length and orientation of these DB structures, we further highlight key features in the formation of these ionic surface phases.

Detecting and Directing Single Molecule Binding Events on H-Si(100) with Application to Ultradense Data Storage.

Many diverse material systems are being explored to enable smaller, more capable and energy efficient devices. These bottom up approaches for atomic and molecular electronics, quantum computation, and data storage all rely on a well-developed understanding of materials at the atomic scale. Here, we report a versatile scanning tunneling microscope (STM) charge characterization technique, which reduces the influence of the typically perturbative STM tip field, to develop this understanding even further. Using this technique, we can now observe single molecule binding events to atomically defined reactive sites (fabricated on a hydrogen-terminated silicon surface) through electronic detection. We then developed a simplified error correction tool for automated hydrogen lithography, quickly directing molecular hydrogen binding events using these sites to precisely repassivate surface dangling bonds (without the use of a scanned probe). We additionally incorporated this molecular repassivation technique as the primary rewriting mechanism in ultradense atomic data storage designs (0.88 petabits per in2).

Conduction pathway of pi-stacked ethylbenzene molecular wires on Si(100).

One of the most important challenges of molecular electronics is to enable systematic fabrication of molecular functional components on well-characterized solid-state substrates in a controlled manner. Recently, experimental techniques were developed to achieve such fabrication where lines of pi-stacked ethylbenzene molecules are induced to self-assemble on an H-terminated Si(100) surface at precise locations and along precise directions. In this work, we theoretically analyze charge transport properties of these ethylbenzene wires using a state-of-the-art first-principles technique where density functional theory (DFT) is used within the nonequilibrium Green's function formalism (NEGF). Our device model consists of ethylbenzene stacks bonded to an H-terminated Si(100) surface and bridging two metal leads. The electron transmission spectrum and its associated scattering states as well as the resistance of the molecular wire are determined by the self-consistent NEGF-DFT formalism. The transmission spectrum has a resonance nature for energies around the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the ethylbenzene wires. However, near the Fermi level of the device, which sits inside the HOMO-LUMO gap, the Si substrate is found to play an important role in providing additional pathways for conduction. It has emerged that, within our model system, the transmission peak nearest to the Fermi level corresponds to transport through the Si substrate and not the pi-stacked molecular line. The low-bias resistance R is found to increase exponentially with the length of the molecular line n, as R approximately e(betan), indicating a tunneling behavior in conduction. We further found that the exponential scaling has two regimes characterized by two different scaling parameters beta: a high value for conduction through the molecular stack in short lines and a lower value for conduction through the substrate in longer lines. Our results suggest that when the conduction of molecular wires bonded to semiconductor substrates is theoretically analyzed, conduction pathways through the substrate need to be taken into account.

Electrostatic Landscape of a Hydrogen-Terminated Silicon Surface Probed by a Moveable Quantum Dot.

With nanoelectronics reaching the limit of atom-sized devices, it has become critical to examine how irregularities in the local environment can affect device functionality. Here, we characterize the influence of charged atomic species on the electrostatic potential of a semiconductor surface at the subnanometer scale. Using noncontact atomic force microscopy, two-dimensional maps of the contact potential difference are used to show the spatially varying electrostatic potential on the (100) surface of hydrogen-terminated highly doped silicon. Three types of charged species, one on the surface and two within the bulk, are examined. An electric field sensitive spectroscopic signature of a single probe atom reports on nearby charged species. The identity of one of the near-surface species has been uncertain in the literature, and we suggest that its character is more consistent with either a negatively charged interstitial hydrogen or a hydrogen vacancy complex.

In-line holographic electron microscopy in the presence of external magnetic fields.

It is now a well-known fact that the phase of electron waves is altered by external magnetic fields via the Aharonov-Bohm effect. This implies that any electron interference effects will be to some degree affected by the presence of such fields. In this study we examine the distortion effects of external (constant and variable) magnetic fields on electron interference and holography. For digital holography, the reconstruction of the object is done via numerical calculations and this leaves the door open for correcting phase distortions in the hologram reconstruction. We design and quantitatively assess such correction schemes, which decidedly depend on our knowledge of the magnetic field values in the holographic recording process. For constant fields of known value we are able to correct for magnetic distortions to a great extent. We find that variable fields are more destructive to the holographic process than constant fields. We define two criteria, related respectively to global and local contrast of the hologram to establish the maximum allowed external field which does not significantly hinder the accuracy of in-line holographic microscopy with electrons.

Theoretical investigation of electron transport modulation through benzenedithiol by substituent groups.

Density functional theory combined with nonequilibrium Green's function techniques was used to model the conduction through disubstituted benzenedithiol molecules bonded to leads composed of 3x3, 5x5 gold and 3x3 aluminum. For the disubstituted 3x3 Au-benzenedithiol-Au systems, the small lead cross section results in a region of nearly zero transmission from -0.4 to -0.2 eV, relative to E(F), due to the absence of lead states. This feature results in negative differential resistance in the current-voltage curves and also causes the main peaks in the transmission spectra, which are dominated by the highest occupied molecular orbitals, to be centered near E(F). The zero-bias transmissions for the disubstituted benzenedithiol, as well as currents at applied biases, correlate very well with the Hammett parameter sigma(p), a quantity that relates the electron donating or withdrawing strength of a substituent. Calculations on disubstituted benzenedithiol connected to 5x5 Au leads produced transmission spectra that showed no gaps over the energy range considered and no negative differential resistance. The transmission in these cases also predominately involves the highest occupied molecular orbitals, and electron donating and withdrawing groups are able to increase and decrease current, respectively. However, there is no strong correlation between current and sigma(p) for this system. This suggests that the correlation observed in the 3x3 Au systems arises from the abrupt cutoff of the main transmission peaks near E(F). The disubstituted 3x3 Al-benzenedithiol-Al systems displayed markedly different behavior from the Au analogs. Electron donating groups and H benzenedithiol-substituted systems display almost no transmission over the energy range considered. However, electron withdrawing group disubstituted benzenedithiol systems had significant peaks in the transmission spectra near E(F), which are associated with the lowest-energy, unoccupied pi-type molecular orbitals. Higher currents are calculated for cases where the substituents have pi-type orbitals that are conjugated with the ring moiety of benzenedithiol. In all cases, the current through the 3x3 Al-benzenedithiol-Al systems is about a factor of 2 less than that through the analogous Au systems. These simulations reveal that the electrical conductance behavior through nanosystems of the type investigated in this work depends on the nature of the molecule as well as the size and composition of the leads to which it is connected. The results suggest that rational design of nanoelectronic systems might be possible under certain conditions but that structure-function relationships cannot be transferred from one system to another.

Prediction of the resonant frequency of piezoelectric tube scanners through three-dimensional finite element modeling of a tube assembly.

In this paper, we study the resonant behavior of a piezoelectric tube scanner used in scanning probe microscopes. In particular, we use a finite element model to allow the inclusion of boundary effects, i.e., nonrigid bonding layers and elastic tip holder, on the dynamic response of the scanner. We show that although existing analytical models provide a good estimation of the axial resonant frequency, their predictions of the first bending resonance may have up to a 100% error. In addition, a simple procedure is proposed that combines some precalculated factors to predict the lowest resonant frequency for a wide range of typical scanner dimensions. An experiment is carried out to illustrate the procedure and validate the prediction.