From electroburning to sublimation: substrate and environmental effects in the electrical breakdown process of monolayer graphene

We report on the characterization of the electrical breakdown (EB) process for the formation of tunneling nanogaps in single-layer graphene. In particular, we investigated the role of oxygen in the breakdown process by varying the environmental conditions (vacuum and ambient conditions). We show that the density of oxygen molecules in the chamber is a crucial parameter that defines the physical breakdown process: at low density, the graphene lattice is sublimating, whereas at high density, the process involved is oxidation, independent of the substrate material. To estimate the activation energies of the two processes, we use a scheme which consists of applying voltage pulses across the junction during the breakdown. By systematically varying the voltage pulse length, and estimating the junction temperature from a 1D thermal model, we extract activation energies which are consistent with the sublimation of graphene under high vacuum and the electroburning process under air. Our study demonstrates that, in our system, a better control of the gap formation is achieved in the sublimation regime

Charge transport in a single molecule transistor probed by scanning tunneling microscopy

We report on the scanning tunneling microscopy/spectroscopy (STM/STS) study of cobalt phthalocyanine (CoPc) molecules deposited onto a back-gated graphene device. We observe a clear gate voltage ( V g ) dependence of the energy position of the features originating from the molecular states. Based on the analysis of the energy shifts of the molecular features upon tuning  V g , we are able to determine the nature of the electronic states that lead to a gapped differential conductance. Our measurements show that capacitive couplings of comparable strengths exist between the CoPc molecule and the STM tip as well as between CoPc and graphene, thus facilitating electronic transport involving only unoccupied molecular states for both tunneling bias polarities. These findings provide novel information on the interaction between graphene and organic molecules and are of importance for further studies, which envisage the realization of single molecule transistors with non-metallic electrodes

Graphene transistors are insensitive to pH changes in solution

We observe very small gate-voltage shifts in the transfer characteristic of as-prepared graphene field-effect transistors (GFETs) when the pH of the buffer is changed. This observation is in strong contrast to Si-based ion-sensitive FETs. The low gate-shift of a GFET can be further reduced if the graphene surface is covered with a hydrophobic fluorobenzene layer. If a thin Al-oxide layer is applied instead, the opposite happens. This suggests that clean graphene does not sense the chemical potential of protons. A GFET can therefore be used as a reference electrode in an aqueous electrolyte. Our finding sheds light on the large variety of pH-induced gate shifts that have been published for GFETs in the recent literature

Contacting strategies for molecular electronics

In the last twenty years, new sophisticated tools to contact single molecules were developed. However, a molecular junction (MJ) constituted by two atomic contacts and bridged by a single or a few molecules does not form a rigid system, in particular at room temperature. A major challenge consists therefore in understanding and optimizing the arrangement of stable and reproducible contacts. To get more insight into contact formation and rupture, new tools are needed. Conducting atomic force microscopy is an attractive approach enabling the correlation of mechanical and electrical properties in individual MJs. In the first part of this thesis we report on measurements of gold-gold and gold-octanedithiol-gold junctions. We introduce two-dimensional histograms in the form of scatter plots to better analyze the correlation between force and conductance. In this representation, the junction-forming octanedithiol compounds lead to a very clear step in the force-conductance data, which is not observed for control monothiol compounds. The conductance found for octanedithiols is in agreement with the idea that junction conductance is dominated by a single molecule. Until now, gold is the preferred electrode material within the field, as it allows a covalent or coordinative binding of the molecules for several binding groups and is easy to handle. Gold however also presents major disadvantages: the relative thick metal electrodes lead to a large screening of a backgate potential; and the mobility of surface atoms at room temperature strongly limits the junctions mechanical stability. A particularly promising approach to overcome these issues is based on using graphene as electrode material. In the second part of this thesis we demonstrate the controlled and reproducible fabrication of sub-5 nm wide gaps in single-layer graphene electrodes. The process is implemented for graphene grown via chemical vapor deposition (CVD) using an electroburning process at room temperature and in vacuum. A yield of over 95% for the gap formation is obtained. This approach allows producing single-layer graphene electrodes for molecular electronics at a large scale. Additionally, from Raman spectroscopy and electroburning carried out simultaneously, we can follow the heating process and infer the temperature at which the gap formation happens. Furthermore we briefly discuss the properties of graphene field effect transistors (FETs) and the first results of using our graphene electrodes to contact molecules

High mobility graphene ion-sensitive field-effect transistors by noncovalent functionalization

Noncovalent functionalization is a well-known nondestructive process for property engineering of carbon nanostructures, including carbon nanotubes and graphene. However, it is not clear to what extend the extraordinary electrical properties of these carbon materials can be preserved during the process. Here, we demonstrated that noncovalent functionalization can indeed delivery graphene field-effect transistors (FET) with fully preserved mobility. In addition, these high-mobility graphene transistors can serve as a promising platform for biochemical sensing applications

Multiple Physical Time Scales and Dead Time Rule in Few-Nanometers Sized Graphene–SiOx-Graphene Memristors

The resistive switching behavior in SiOx-based phase change memory devices confined by few nanometer wide graphene nanogaps is investigated. Our experiments and analysis reveal that the switching dynamics is not only determined by the commonly observed bias voltage dependent set and reset times. We demonstrate that an internal time scale, the dead time, plays a fundamental role in the system’s response to various driving signals. We associate the switching behavior with the formation of microscopically distinct SiOx amorphous and crystalline phases between the graphene electrodes. The reset transition is attributed to an amorphization process due to a voltage driven self-heating; it can be triggered at any time by appropriate voltage levels. In contrast, the formation of the crystalline ON state is conditional and only occurs after the completion of a thermally assisted structural rearrangement of the as-quenched OFF state which takes place within the dead time after a reset operation. Our results demonstrate the technological relevance of the dead time rule which enables a zero bias access of both the low and high resistance states of a phase change memory device by unipolar voltage pulses

Enhanced Drug Delivery for Cardiac Microvascular Obstruction with an Occlusion-Infusion-Catheter.

Microvascular Obstruction (MVO) is a common consequence of acute myocardial infarction. MVO is underdiagnosed and treatment is often nonspecific and ineffective. A multi-scale in-vitro benchtop model was established to investigate drug perfusion in MVO affected microcirculation. The central element of the benchtop model was a fluidic microchip containing channels with diameters between [Formula: see text] and 50 μm representing [Formula: see text] of the microvascular tree fed by the left anterior descending artery (LAD). The outlets of the chip could be closed to mimic MVO. Two methods for intracoronary infusion of pharmacologic agents (simulated by dye) to regions with MVO were investigated using an occlusion-infusion catheter. The first case was a simple, bolus-like infusion into the LAD, whereas the second case consisted of infusion with concomitant proximal occlusion of the LAD phantom with a balloon. Results show that local dye concentration maxima in the chip with MVO were 2.2-3.2 times higher for the case with proximal balloon occlusion than for the conventional infusion method. The cumulated dose could be raised by a factor 4.6-5.2. These results suggest that drug infusion by catheter is more effective if the blood supply to the treated vascular bed is temporarily blocked by a balloon catheter

Sensing with liquid-gated graphene field-effect transistors

Liquid-gated graphene field-effect transistors (GFETs) with reliable performance are developed. It is revealed that ideal defect-free graphene should be inert to electrolyte composition changes in solution, whereas a defective one responses to electrolyte composition. This finding sheds light on the large variety of pH or ion-induced gate shifts that have been published for GFETs in the recent literature. As a next step to target graphene-based (bio-) chemical sensing platform, non-covalent functionalization of graphene has to be introduced