Dopant segregation in polycrystalline monolayer graphene.

Heterogeneity in dopant concentration has long been important to the electronic properties in chemically doped materials. In this work, we experimentally demonstrate that during the chemical vapor deposition process, in contrast to three-dimensional polycrystals, the substitutional nitrogen atoms avoid crystal grain boundaries and edges over micron length scales while distributing uniformly in the interior of each grain. This phenomenon is universally observed independent of the details of the growth procedure such as temperature, pressure, substrate, and growth precursor.

Segregation of sublattice domains in nitrogen-doped graphene.

Atomic-level details of dopant distributions can significantly influence the material properties. Using scanning tunneling microscopy, we investigate the distribution of substitutional dopants in nitrogen-doped graphene with regard to sublattice occupancy within the honeycomb structure. Samples prepared by chemical vapor deposition (CVD) using pyridine on copper exhibit well-segregated domains of nitrogen dopants in the same sublattice, extending beyond 100 nm. On the other hand, samples prepared by postsynthesis doping of pristine graphene exhibit a random distribution between sublattices. On the basis of theoretical calculations, we attribute the formation of sublattice domains to the preferential attachment of nitrogen to the edge sites of graphene during the CVD growth process. The breaking of sublattice symmetry in doped graphene can have important implications in its electronic applications, such as the opening of a tunable band gap in the material.

Local atomic and electronic structure of boron chemical doping in monolayer graphene.

We use scanning tunneling microscopy and X-ray spectroscopy to characterize the atomic and electronic structure of boron-doped and nitrogen-doped graphene created by chemical vapor deposition on copper substrates. Microscopic measurements show that boron, like nitrogen, incorporates into the carbon lattice primarily in the graphitic form and contributes ~0.5 carriers into the graphene sheet per dopant. Density functional theory calculations indicate that boron dopants interact strongly with the underlying copper substrate while nitrogen dopants do not. The local bonding differences between graphitic boron and nitrogen dopants lead to large scale differences in dopant distribution. The distribution of dopants is observed to be completely random in the case of boron, while nitrogen displays strong sublattice clustering. Structurally, nitrogen-doped graphene is relatively defect-free while boron-doped graphene films show a large number of Stone-Wales defects. These defects create local electronic resonances and cause electronic scattering, but do not electronically dope the graphene film.

Stereo-isomerism controls surface reactivity: 1-chloropentane-pairs on Si(100)-2×1.

Chloropentane forms asymmetric ('A') and symmetric ('S') pairs on Si(100)-2×1, differing in the direction of curvature of one pentane tail. Surprisingly this renders the rate of thermal reaction of 'A' fifteen times greater than 'S' in chlorinating room-temperature silicon. Correspondingly, for electron-induced reaction the energy threshold for A is 1 eV less than for S.

Directed long-range molecular migration energized by surface reaction.

The recoil of adsorbates away (desorption) and towards (reaction) surfaces is well known. Here, we describe the long-range recoil of adsorbates in the plane of a surface, and accordingly the novel phenomenon of reactions occurring at a substantial distance from the originating event. Three thermal and three electron-induced surface reactions are shown by scanning tunnelling microscopy to propel their physisorbed ethylenic products across the rough surface of Si(100) over a distance of up to 200 Å before an attachment reaction. The recoil energy in the ethylenic products comes from thermal exoergicity or from electronic excitation of chemisorbed alkenes. We propose that the mechanism of migration is a rolling motion, because the recoiling molecule overcomes raised surface obstacles. Electronic excitation of propene causes directional recoil and often end-to-end inversion, suggesting cartwheeling. Ab initio calculations of the halogenation and electron-induced reactions support a model in which asymmetric forces between the molecule and the surface induce rotation and therefore migration.

Imprinting self-assembled patterns of lines at a semiconductor surface, using heat, light, or electrons.

The fabrication of nano devices at surfaces makes conflicting demands of mobility for self-assembly (SA) and immobility for permanence. The solution proposed in earlier work from this laboratory involved pattern formation in physisorbed molecules by SA, followed by localized reaction to chemically imprint the pattern substantially unchanged, a procedure we termed molecular-scale imprinting (MSI). Here, as proof of generality we extended this procedure, previously applied to imprinting circles on Si(111)-7 × 7, to SA lines of 1-chloropentane (CP) on Si(100)-2 × 1. The physisorbed lines consisted of pairs of CP that grew perpendicular to the Si dimer rows, as shown by scanning tunneling microscopy and ab initio theory. Chemical reaction of these lines with the surface was triggered in separate experiments by three different modes of energization: heat, electrons, or light. In all cases the CP molecules underwent MSI with a Si atom beneath so that the physisorbed lines of CP pairs were imprinted as chemisorbed lines of Cl pairs.

Metal to insulator transition in films of molecularly linked gold nanoparticles.

We report a metal to insulator transition (MIT) in disordered films of molecularly linked gold nanoparticles (NPs). As the number of carbons (n) of alkanedithiol linker molecules (C(n)S2) is varied, resistance (R) at low temperature (T = 2 K) and at 200 K, as well as trends in R vs T data at intermediate temperatures, all point to an MIT occurring at n = 5. We describe these results in a context of a Mott-Hubbard MIT. We find that all insulating samples (n > or = 5) exhibit a universal scaling behavior R approximately exp[(T0/T)nu] with nu = 0.65, and all metallic samples (n < or = 5) exhibit weaker R-T dependencies than bulk gold. We discuss these observations in terms of competitive thermally activated processes and strong, T-independent elastic scattering, respectively.

Influence of linker molecules on charge transport through self-assembled single-nanoparticle devices.

We investigate electrical characteristics of single-electron electrode/nanoisland/electrode devices formed by alkanedithiol assisted self-assembly. Contrary to predictions of the orthodox model for double tunnel junction devices, we find a significant ( approximately fivefold) discrepancy in single-electron charging energies determined by Coulomb blockade (CB) voltage thresholds in current-voltage measurements versus those determined by an Arrhenius analysis of conductance in the CB region. The energies do, however, scale with particle sizes, consistent with single-electron charging phenomena. We propose that the discrepancy is caused by a multibarrier junction potential that leads to a voltage divider effect. Temperature and voltage dependent conductance measurements performed outside the blockade region are consistent with this picture. We simulated our data using a suitably modified orthodox model.