Slaven Garaj

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.

Molecule-hugging graphene nanopores

It has recently been recognized that solid-state nanopores in single-atomic-layer graphene membranes can be used to electronically detect and characterize single long charged polymer molecules. We have now fabricated nanopores in single-layer graphene that are closely matched to the diameter of a double-stranded DNA molecule. Ionic current signals during electrophoretically driven translocation of DNA through these nanopores were experimentally explored and theoretically modeled. Our experiments show that these nanopores have unusually high sensitivity (0.65 nA/Å) to extremely small changes in the translocating molecule’s outer diameter. Such atomically short graphene nanopores can also resolve nanoscale-spaced molecular structures along the length of a polymer, but do so with greatest sensitivity only when the pore and molecule diameters are closely matched. Modeling confirms that our most closely matched pores have an inherent resolution of ≤0.6 nm along the length of the molecule.

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.

Molecular transport through capillaries made with atomic-scale precision

Nanometre-scale pores and capillaries have long been studied because of their importance in many natural phenomena and their use in numerous applications. A more recent development is the ability to fabricate artificial capillaries with nanometre dimensions, which has enabled new research on molecular transport and led to the emergence of nanofluidics. But surface roughness in particular makes it challenging to produce capillaries with precisely controlled dimensions at this spatial scale. Here we report the fabrication of narrow and smooth capillaries through van der Waals assembly, with atomically flat sheets at the top and bottom separated by spacers made of two-dimensional crystals with a precisely controlled number of layers. We use graphene and its multilayers as archetypal two-dimensional materials to demonstrate this technology, which produces structures that can be viewed as if individual atomic planes had been removed from a bulk crystal to leave behind flat voids of a height chosen with atomic-scale precision. Water transport through the channels, ranging in height from one to several dozen atomic planes, is characterized by unexpectedly fast flow (up to 1 metre per second) that we attribute to high capillary pressures (about 1,000 bar) and large slip lengths. For channels that accommodate only a few layers of water, the flow exhibits a marked enhancement that we associate with an increased structural order in nanoconfined water. Our work opens up an avenue to making capillaries and cavities with sizes tunable to ångström precision, and with permeation properties further controlled through a wide choice of atomically flat materials available for channel walls.

Field emission properties of carbon nanohorn films

Self-supporting carbon films were prepared from a carbonaceous material, nanohorns. Nanohorns are spherical particles built of sharp cones of a single graphene sheet. The films show good field emission characteristics due to the sharp horn-like structures, in particular a low turn-on field and good long-term stability.

Diffusion-Mediated Synthesis of MoS2/WS2 Lateral Heterostructures

Controlled growth of two-dimensional transition metal dichalcogenide (TMD) lateral heterostructures would enable on-demand tuning of electronic and optoelectronic properties in this new class of materials. Prior to this work, compositional modulations in lateral TMD heterostructures have been considered to depend solely on the growth chronology. We show that in-plane diffusion can play a significant role in the chemical vapor deposition of MoS2/WS2 lateral heterostructures leading to a variety of nontrivial structures whose composition does not necessarily follow the growth order. Optical, structural, and compositional studies of TMD crystals captured at different growth temperatures and in different diffusion stages suggest that compositional mixing versus segregation are favored at high and low growth temperatures, respectively. The observed diffusion mechanism will expand the realm of possible lateral heterostructures, particularly ones that cannot be synthesized using traditional methods.

Gate-Defined Quantum Dots on Carbon Nanotubes

We report the realization of nanotube-based multiple quantum dots that are fully defined and controlled with electrostatic gates. Metallic top-gates are used to produce localized depletion regions in the underlying tubes; a pair of such depletion regions in a nanotube with ohmic contact electrodes defines the quantum dot. Top-gate voltages tune the transparencies of tunnel barriers as well as the electrostatic energies within single and multiple dots. This approach allows precise control over multiple devices on a single tube, and serves as a design paradigm for nanotube-based electronics and quantum systems.

Role of dynamic Jahn-Teller distortions in Na2C60 and Na2CsC60 studied by NMR.

Through 13C NMR spin lattice relaxation ( T1) measurements in cubic Na2C60, we detect a gap in its electronic excitations, similar to that observed in tetragonal A4C60. This establishes that Jahn-Teller distortions (JTD) and strong electronic correlations must be considered to understand the behavior of even electron systems, regardless of the structure. Furthermore, in metallic Na2CsC60, a similar contribution to T1 is also detected for 13C and 133Cs NMR, implying the occurrence of excitations typical of JT distorted C( 2-)60 (or equivalently C( 4-)60). This supports the idea that dynamic JTD can induce attractive electronic interactions in odd electron systems.

Electronic and Mechanical Properties of Carbon Nanotubes

Interest in carbon nanotubes has grown at a very rapid rate because of their many exceptional properties, which span the spectrum from mechanical and chemical robustness to novel electronic transport properties. Their physics, chemistry and perspectives for applications are very challenging. Below we highlight the main results of the Lausanne group and their collaborators on transport, electron spin resonance, elastic and field emission properties of single wall (SWNT) and multi-wall (MWNT) carbon nanotubes.

Gaps and excitations in fullerides with partially filled bands: NMR study of Na 2 C 60 and K 4 C 60

We present a nuclear magnetic resonance (NMR) study of