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.

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.

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.

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.

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.

The role of capillary and surface forces in the crossover behavior of solid nanoparticles at liquid interfaces.

We investigate the interaction between a nanoparticle and an oil-water interface with particular emphasis on the particle crossing through the interface. The formation of a three-phase contact line is investigated in two cases, namely in the presence and in the absence of surface forces. We carefully examine the interplay between capillary and surface forces in such systems. Two instabilities of the interface (snap-in/snap-out) as the particle is moved through the interface are identified and quantitatively described. While the snap-in instability was observed in some AFM studies, the precise interface position and configuration relative to the particle at the instability depends on the nature of the surface forces present in the system. After the snap-in, the particle is adsorbed and must overcome an energy barrier due to the interface deformation in order to cross-over to the other liquid. We make quantitative predictions on the interface configuration at the instabilities and the free energy barrier height. The roles of particle size and different interaction parameters characterizing the system in determining the magnitude of the energy barrier for crossing and in the formation of a three-phase contact line are discussed. Ultimately, this study will enable us to make quantitative predictions on capillary effects in nanoparticle-microemulsions mixtures and other colloidal systems. For particles in the micrometer range and larger the capillary forces dominate over the surface forces and dictate how the snap-in occurs. However, the situation becomes different for particle sizes smaller than about 100 nm. The presence of surface forces modifies the interface configuration and the free energy jump at the snap-in instability.

Self-consistent molecular theory of polymers in melts and solutions.

We propose a self-consistent molecular theory of conformational properties of flexible polymers in melts and solutions. The method employs the polymer reference interaction site model for the intermolecular correlations and the Green function technique for the intramolecular correlations. We demonstrate this method on n-alkane molecules in different environments: water, hexane, and in melt, corresponding to poor, good, and theta condition, respectively. The numerical results of the intramolecular correlation function, the radius of gyration, and the characteristic ratio of a polymer chain are indicative of conformational changes from one environment to another and are in agreement with other findings in the literature. Scaling laws for the chain size with respect to the number of monomers are discussed. We show results for the intra- and intermolecular correlation functions and the medium-induced potential. We also extract the Kuhn length and the characteristic ratio for the infinite chain limit for melts. The latter is compared to the experimental results and computer simulation. The conformational free energy per monomer in different solvents is calculated. Our treatment can be generalized readily to other polymer-solvent systems, for example, those containing branched copolymers and polar solvents.

Controlled coupling and occupation of silicon atomic quantum dots at room temperature.

It is demonstrated that the silicon atom dangling bond (DB) state serves as a quantum dot. Coulomb repulsion causes DBs separated by less, similar2 nm to exhibit reduced localized charge, which enables electron tunnel coupling of DBs. Scanning tunneling microscopy measurements and theoretical modeling reveal that fabrication geometry of multi-DB assemblies determines net occupation and tunnel coupling strength among dots. Electron occupation of DB assemblies can be controlled at room temperature. Electrostatic control over charge distribution within assemblies is demonstrated.

Fundamental mechanism of translocation across liquidlike membranes: toward control over nanoparticle behavior.

We envision and theoretically investigate a novel behavior of a functionalized nanoparticle designed to translocate through a liquidlike membrane. We develop a statistical-mechanical approach to such a system. We predict a new mechanism for the opening of a circular energy-dominated pore on the membrane by a nanoparticle functionalized with a peptide aggregate. Following fluctuations in the position and orientation of the nanoparticle, the peptide aggregate incorporates into the membrane and locally destabilizes it. The nucleation of a pore centered at the peptide aggregate attached to the particle is a precursor to particle translocation. The subsequent opening of the pore is assisted by adhesion of the membrane to the particle. We determine the conditions in which thermal fluctuations in the membrane shape and the pore size can induce translocation of the particle. For different system parameters quantities such as the free energy, entropy, pore size, degree of particle wrapping, and the probability of spontaneous translocation are obtained.

Molecular description of the collapse of hydrophobic polymer chains in water.

We propose a self-consistent molecular theory of conformational properties of flexible polymers in solution. It is applied to the collapse of a hydrophobic polymer chain in water, and can be readily generalized to any polymer-solvent system (e.g., copolymers with high complexity). We stress the potential of this method for a variety of problems, such as protein folding.