Abhay Pasupathy

Coulomb blockade and the Kondo effect in single-atom transistors

Using molecules as electronic components is a powerful new direction in the science and technology of nanometre-scale systems. Experiments to date have examined a multitude of molecules conducting in parallel, or, in some cases, transport through single molecules. The latter includes molecules probed in a two-terminal geometry using mechanically controlled break junctions or scanning probes as well as three-terminal single-molecule transistors made from carbon nanotubes, C60 molecules, and conjugated molecules diluted in a less-conducting molecular layer. The ultimate limit would be a device where electrons hop on to, and off from, a single atom between two contacts. Here we describe transistors incorporating a transition-metal complex designed so that electron transport occurs through well-defined charge states of a single atom. We examine two related molecules containing a Co ion bonded to polypyridyl ligands, attached to insulating tethers of different lengths. Changing the length of the insulating tether alters the coupling of the ion to the electrodes, enabling the fabrication of devices that exhibit either single-electron phenomena, such as Coulomb blockade, or the Kondo effect.

Visualizing Individual Nitrogen Dopants in Monolayer Graphene

Nitrogen atoms that replace carbon atoms in the graphene lattice strongly modify the local electronic structure. In monolayer graphene, substitutional doping during growth can be used to alter its electronic properties. We used scanning tunneling microscopy, Raman spectroscopy, x-ray spectroscopy, and first principles calculations to characterize individual nitrogen dopants in monolayer graphene grown on a copper substrate. Individual nitrogen atoms were incorporated as graphitic dopants, and a fraction of the extra electron on each nitrogen atom was delocalized into the graphene lattice. The electronic structure of nitrogen-doped graphene was strongly modified only within a few lattice spacings of the site of the nitrogen dopant. These findings show that chemical doping is a promising route to achieving high-quality graphene films with a large carrier concentration.

Connecting dopant bond type with electronic structure in n-doped graphene

Robust methods to tune the unique electronic properties of graphene by chemical modification are in great demand due to the potential of the two dimensional material to impact a range of device applications. Here we show that carbon and nitrogen core-level resonant X-ray spectroscopy is a sensitive probe of chemical bonding and electronic structure of chemical dopants introduced in single-sheet graphene films. In conjunction with density functional theory based calculations, we are able to obtain a detailed picture of bond types and electronic structure in graphene doped with nitrogen at the sub-percent level. We show that different N-bond types, including graphitic, pyridinic, and nitrilic, can exist in a single, dilutely N-doped graphene sheet. We show that these various bond types have profoundly different effects on the carrier concentration, indicating that control over the dopant bond type is a crucial requirement in advancing graphene electronics.

Mechanical Control of Spin States in Spin-1 Molecules and the Underscreened Kondo Effect

Spin Control Through Molecular Stretching Molecules with high symmetry, such as metal complexes with several equivalent ligands, can, in principle, have this symmetry broken by stresses that lengthen bonds in one direction. Parks et al. (p. 1370; see the Perspective by Jarillo-Herrero) placed cobalt complexes in a break-junction contact and then applied a mechanical force to slowly open the contact. Low-temperature measurement of differential conductance revealed a splitting of the Kondo peak at zero-applied voltage into two features, which occurred by breaking the degeneracy of S = 1 triplet states. This assignment of the spin state was confirmed by the evolution of splitting with magnetic field and by comparison to theory for a case where the conduction electrons only partially screen the spin states. Controlled stretching of individual transition-metal complexes enables direct manipulation of the molecule’s spin states. The ability to make electrical contact to single molecules creates opportunities to examine fundamental processes governing electron flow on the smallest possible length scales. We report experiments in which we controllably stretched individual cobalt complexes having spin S = 1, while simultaneously measuring current flow through the molecule. The molecule’s spin states and magnetic anisotropy were manipulated in the absence of a magnetic field by modification of the molecular symmetry. This control enabled quantitative studies of the underscreened Kondo effect, in which conduction electrons only partially compensate the molecular spin. Our findings demonstrate a mechanism of spin control in single-molecule devices and establish that they can serve as model systems for making precision tests of correlated-electron theories.

Metal-nanoparticle single-electron transistors fabricated using electromigration

We have fabricated single-electron transistors from individual metal nanoparticles using a geometry that provides improved coupling between the particle and the gate electrode. This is accomplished by incorporating a nanoparticle into a gap created between two electrodes using electromigration, all on top of an oxidized aluminum gate. We achieve sufficient gate coupling to access more than ten charge states of individual gold nanoparticles (5–15 nm in diameter). The devices are sufficiently stable to permit spectroscopic studies of the electron-in-a-box level spectra within the nanoparticle as its charge state is varied.

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.

Large Physisorption Strain in Chemical Vapor Deposition of Graphene on Copper Substrates

Graphene single layers grown by chemical vapor deposition on single crystal Cu substrates are subject to nonuniform physisorption strains that depend on the orientation of the Cu surface. The strains are revealed in Raman spectra and quantitatively interpreted by molecular dynamics (MD) simulations. An average compressive strain on the order of 0.5% is determined in graphene on Cu(111). In graphene on Cu (100), MD simulations interpret the observed highly nonuniform strains.

Visualizing the formation of the Kondo lattice and the hidden order in URu2Si2

Heavy electronic states originating from the f atomic orbitals underlie a rich variety of quantum phases of matter. We use atomic scale imaging and spectroscopy with the scanning tunneling microscope to examine the novel electronic states that emerge from the uranium f states in URu2Si2. We find that, as the temperature is lowered, partial screening of the f electrons’ spins gives rise to a spatially modulated Kondo–Fano resonance that is maximal between the surface U atoms. At T = 17.5 K, URu2Si2 is known to undergo a second-order phase transition from the Kondo lattice state into a phase with a hidden order parameter. From tunneling spectroscopy, we identify a spatially modulated, bias-asymmetric energy gap with a mean-field temperature dependence that develops in the hidden order state. Spectroscopic imaging further reveals a spatial correlation between the hidden order gap and the Kondo resonance, suggesting that the two phenomena involve the same electronic states.

Nature of the quantum metal in a two-dimensional crystalline superconductor

Owing to electron localization, two-dimensional materials are not expected to be metallic at low temperatures, but a field-induced quantum metal phase emerges in NbSe2, whose behaviour is consistent with the Bose-metal model.

Visualization of electron nematicity and unidirectional antiferroic fluctuations at high temperatures in NaFeAs

Superconductivity in iron pnictides seems to be related to the formation of electronic nematic phases that break the rotational symmetry of the crystal lattice. But the nematic phase in NaFeAs is now shown to persist at high temperatures owing to the presence of antiferroic fluctuations.