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Register a new userCatalytic sub-surface etching of nanoscale channels in graphite
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Catalytic hydrogenation of graphite has recently attracted renewed attention, as a route for nano-patterning of graphene and to produce graphene nano-ribbons. These reports show that metallic nanoparticles etch surface layers of graphite, or graphene anisotropically along the crystallographic zigzag <11-20> or armchair <1010> directions. On graphene the etching direction can be influenced by external magnetic fields or the substrate. Here we report the sub-surface etching of highly oriented pyrolytic graphite (HOPG) by Ni nanoparticles, to form a network of tunnels, as seen by SEM and STM. In this new nanoporous form of graphite, the top layers bend inward on top of the tunnels, while their local density of states remains fundamentally unchanged. Engineered nanoporous tunnel networks in graphite allow further chemical modification and may find applications in storage or sensing.
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We investigate the etching of a pure hydrogen plasma on graphite samples and graphene flakes on SiO$_2$ and hexagonal Boron-Nitride (hBN) substrates. The pressure and distance dependence of the graphite exposure experiments reveals the existence of two distinct plasma regimes: the direct and the remote plasma regime. Graphite surfaces exposed directly to the hydrogen plasma exhibit numerous etch pits of various size and depth, indicating continuous defect creation throughout the etching process. In contrast, anisotropic etching forming regular and symmetric hexagons starting only from preexisting defects and edges is seen in the remote plasma regime, where the sample is located downstream, outside of the glowing plasma. This regime is possible in a narrow window of parameters where essentially all ions have already recombined, yet a flux of H-radicals performing anisotropic etching is still present. At the required process pressures, the radicals can recombine only on surfaces, not in the gas itself. Thus, the tube material needs to exhibit a sufficiently low H radical recombination coefficient, such a found for quartz or pyrex. In the remote regime, we investigate the etching of single layer and bilayer graphene on SiO$_2$ and hBN substrates. We find isotropic etching for single layer graphene on SiO$_2$, whereas we observe highly anisotropic etching for graphene on a hBN substrate. For bilayer graphene, anisotropic etching is observed on both substrates. Finally, we demonstrate the use of artificial defects to create well defined graphene nanostructures with clean crystallographic edges.
We investigate by low-temperature transport experiments the sub-threshold behavior of triple-gate silicon field-effect transistors. These three-dimensional nano-scale devices consist of a lithographically defined silicon nanowire surrounded by a gate with an active region as small as a few tens of nanometers, down to 50x60x35 nm^3. Conductance versus gate voltage show Coulomb-blockade oscillations with a large charging energy due to the formation of a small potential well below the gate. According to dependencies on device geometry and thermionic current analysis, we conclude that sub-threshold channels, a few nanometers wide, appear at the nanowire edges, hence providing an experimental evidence for the corner-effect.
We describe a method for fabrication of uniform aluminum nanowires with diameters below 15 nm. Electron beam lithography is used to define narrow wires, which are then etched using a sodium bicarbonate solution, while their resistance is simultaneously measured in-situ. The etching process can be stopped when the desired resistance is reached, and can be restarted at a later time. The resulting nanowires show a superconducting transition as a function of temperature and magnetic field that is consistent with their diameter. The width of the transition is similar to that of the lithographically defined wires, indicating that the etching process is uniform and that the wires are undamaged. This technique allows for precise control over the normal state resistance and can be used to create a variety of aluminum nanodevices.
We studied, by scanning tunneling microscopy, the morphology of nanopits of monolayer depth created at graphite surfaces by hydrogen plasma etching under various conditions such as H$_2$ pressure, temperature, etching time, and RF power of the plasma generation. In addition to the known pressure-induced transition of the nanopit morphology, we found a sharp temperature-induced transition from many small rather round nanopits of ~150 nm size to few large hexagonal ones of 300-600 nm within a narrow temperature range. The remote and direct plasma modes switching mechanism, which was proposed to explain the pressure-induced transition, is not directly applicable to this newly found transition. Scanning tunneling spectroscopy (STS) measurements of edges of the hexagonal nanopits fabricated at graphite surfaces by this method show clear signatures of the peculiar electronic state localized at the zigzag edge (edge state), i.e., a prominent peak near the Fermi energy accompanied by suppressions on either side in the local density of states. These observations indicate that the hexagonal nanopits consist of a high density of zigzag edges. The STS data also revealed a domain structure of the edge state in which the electronic state varies over a length scale of ~3 nm along the edge. The present study will pave the way for microscopic understanding of the anisotropic etching mechanism and of spin polarization in zigzag nanoribbons which are promising key elements for future graphene nanoelectronics.
Of the two stable forms of graphite, hexagonal (HG) and rhombohedral (RG), the former is more common and has been studied extensively. RG is less stable, which so far precluded its detailed investigation, despite many theoretical predictions about the abundance of exotic interaction-induced physics. Advances in van der Waals heterostructure technology have now allowed us to make high-quality RG films up to 50 graphene layers thick and study their transport properties. We find that the bulk electronic states in such RG are gapped and, at low temperatures, electron transport is dominated by surface states. Because of topological protection, the surface states are robust and of high quality, allowing the observation of the quantum Hall effect, where RG exhibits phase transitions between gapless semimetallic phase and gapped quantum spin Hall phase with giant Berry curvature. An energy gap can also be opened in the surface states by breaking their inversion symmetry via applying a perpendicular electric field. Moreover, in RG films thinner than 4 nm, a gap is present even without an external electric field. This spontaneous gap opening shows pronounced hysteresis and other signatures characteristic of electronic phase separation, which we attribute to emergence of strongly-correlated electronic surface states.
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