Electrical coupling between cells and graphene transistors.

In this work, both experimental data and a model are presented on the coupling between living cells and graphene solution-gated field-effect transistors. Modified HEK 293 cells are successfully cultured on graphene transistor arrays and electrically accessed by the patch clamp method. Transistor recordings are presented, showing the opening and closing of voltage-gated potassium ion channels in the cell membrane. The experimental data is compared with the broadly used standard point-contact model. The ion dynamics in the cell-transistor cleft are analyzed to account for the differences between the model and the experimental data revealing a significant increase in the total ionic strength in the cleft. In order to describe the influence of the ion concentration resulting from the cell activity, the ion-sensitivity of graphene solution-gated field-effect transistors is investigated experimentally and modelled by considering the screening effect of the ions on the surface potential at the graphene/electrolyte interface. Finally, the model of the cell-transistor coupling is extended to include the effect of ion accumulation and ion sensitivity. The experimental data shows a very good agreement with this extended model, emphasizing the importance of considering the ion concentration in the cleft to properly understand the cell-transistor coupling.

Emergence of photoswitchable states in a graphene-azobenzene-Au platform.

The perfect transmission of charge carriers through potential barriers in graphene (Klein tunneling) is a direct consequence of the Dirac equation that governs the low-energy carrier dynamics. As a result, localized states do not exist in unpatterned graphene, but quasibound states can occur for potentials with closed integrable dynamics. Here, we report the observation of resonance states in photoswitchable self-assembled molecular(SAM)-graphene hybrid. Conductive AFM measurements performed at room temperature reveal strong current resonances, the strength of which can be reversibly gated on- and off- by optically switching the molecular conformation of the mSAM. Comparisons of the voltage separation between current resonances (∼ 70-120 mV) with solutions of the Dirac equation indicate that the radius of the gating potential is ∼ 7 ± 2 nm with a strength ≥ 0.5 eV. Our results and methods might provide a route toward optically programmable carrier dynamics and transport in graphene nanomaterials.

Polymer brushes on graphene.

A critical bottleneck for the widespread use of single layer graphene is the absence of a facile method of chemical modification which does not diminish the outstanding properties of the two-dimensional sp(2) network. Here, we report on the direct chemical modification of graphene by photopolymerization with styrene. We demonstrate that photopolymerization occurs at existing defect sites and that there is no detectable disruption of the basal plane conjugation of graphene. This method thus offers a route to define graphene functionality without degrading its electronic properties. Furthermore, we show that photopolymerization with styrene results in self-organized intercalative growth and delamination of few layer graphene. Under these reaction conditions, we find that a range of other vinyl monomers exhibits no reactivity with graphene. However, we demonstrate an alternative route by which the surface reactivity can be precisely tuned, and these monomers can be locally grafted via electron-beam-induced carbon deposition on the graphene surface.

Ultrafast electronic readout of diamond nitrogen-vacancy centres coupled to graphene.

Non-radiative transfer processes are often regarded as loss channels for an optical emitter because they are inherently difficult to access experimentally. Recently, it has been shown that emitters, such as fluorophores and nitrogen-vacancy centres in diamond, can exhibit a strong non-radiative energy transfer to graphene. So far, the energy of the transferred electronic excitations has been considered to be lost within the electron bath of the graphene. Here we demonstrate that the transferred excitations can be read out by detecting corresponding currents with a picosecond time resolution. We detect electronically the spin of nitrogen-vacancy centres in diamond and control the non-radiative transfer to graphene by electron spin resonance. Our results open the avenue for incorporating nitrogen-vacancy centres into ultrafast electronic circuits and for harvesting non-radiative transfer processes electronically.

A 2D semiconductor-self-assembled monolayer photoswitchable diode.

A switchable diode in a 2D semiconductor-molecular junction heterostructure is reported. MoS2 is exfoliated on top of a monolayer of azobenzene-substituted thiols on gold. Photoisomerization of the azobenzenes results in switching between a rectifier with rectifying ratios of 10(4) and a conductive state, as revealed by conducting atomic force microscopy.

Graphene transistors with multifunctional polymer brushes for biosensing applications.

Exhibiting a combination of exceptional structural and electronic properties, graphene has a great potential for the development of highly sensitive sensors. To date, many challenging chemical, biochemical, and biologic sensing tasks have been realized based on graphene. However, many of these sensors are rather unspecific. To overcome this problem, for instance, the sensor surface can be modified with analyte-specific transducers such as enzymes. One problem associated with the covalent attachment of such biomolecular systems is the introduction of crystal defects that have a deleterious impact on the electronic properties of the sensor. In this work, we present a versatile platform for biosensing applications based on polymer-modified CVD-grown graphene transistors. The functionalization method of graphene presented here allows one to integrate several functional groups within surface-bound polymer brushes without the introduction of additional defects. To demonstrate the potential of this polymer brush functionalization scaffold, we modified solution-gated graphene field-effect transistors with the enzyme acetylcholinesterase and a transducing group, allowing the detection of the neurotransmitter acetylcholine. Taking advantage of the transducing capability of graphene transistors and the versatility of polymer chemistry and enzyme biochemistry, this study presents a novel route for the fabrication of highly sensitive, multipurpose transistor sensors that can find application for a multitude of biologically relevant analytes.

Role of intertube interactions in double- and triple-walled carbon nanotubes.

Resonant Raman spectroscopy studies are performed to access information about the intertube interactions and wall-to-wall distances in double- and triple-walled carbon nanotubes. Here, we explain how the surroundings of the nanotubes in a multiwalled system influence their radial breathing modes. Of particular interest, the innermost tubes in double- and triple-walled carbon nanotube systems are shown to be significantly shielded from environmental interactions, except for those coming from the intertube interaction with their own respective host tubes. From a comparison of the Raman results for bundled as well as individual fullerene-peapod-derived double- and triple-walled carbon nanotubes, we observe that metallic innermost tubes, when compared to their semiconducting counterparts, clearly show weaker intertube interactions. Additionally, we discuss a correlation between the wall-to-wall distances and the frequency upshifts of the radial breathing modes observed for the innermost tubes in individual double- and triple-walled carbon nanotubes. All results allow us to contemplate fundamental properties related to DWNTs and TWNTs, as for example diameter- and chirality-dependent intertube interactions. We also discuss differences in fullerene-peapod-derived and chemical vapor deposition grown double- and triple-walled systems with the focus on mechanical coupling and interference effects.