Pantelis Bampoulis

Germanene: the germanium analogue of graphene

Recently, several research groups have reported the growth of germanene, a new member of the graphene family. Germanene is in many aspects very similar to graphene, but in contrast to the planar graphene lattice, the germanene honeycomb lattice is buckled and composed of two vertically displaced sub-lattices. Density functional theory calculations have revealed that free-standing germanene is a 2D Dirac fermion system, i.e. the electrons behave as massless relativistic particles that are described by the Dirac equation, which is the relativistic variant of the Schrödinger equation. Germanene is a very appealing 2D material. The spin-orbit gap in germanene (~24 meV) is much larger than in graphene (<0.05 meV), which makes germanene the ideal candidate to exhibit the quantum spin Hall effect at experimentally accessible temperatures. Additionally, the germanene lattice offers the possibility to open a band gap via for instance an externally applied electrical field, adsorption of foreign atoms or coupling with a substrate. This opening of the band gap paves the way to the realization of germanene based field-effect devices. In this topical review we will (1) address the various methods to synthesize germanene (2) provide a brief overview of the key results that have been obtained by density functional theory calculations and (3) discuss the potential of germanene for future applications as well for fundamentally oriented studies.

Germanene termination of Ge2Pt crystals on Ge(110)

We have investigated the growth of Pt on Ge(1 1 0) using scanning tunneling microscopy and spectroscopy. The deposition of several monolayers of Pt on Ge(1 1 0) followed by annealing at 1100 K results in the formation of 3D metallic Pt-Ge nanocrystals. The outermost layer of these crystals exhibits a honeycomb structure. The honeycomb structure is composed of two hexagonal sub-lattices that are displaced vertically by 0.2 Å with respect to each other. The nearest-neighbor distance of the atoms in the honeycomb lattice is 2.5  ±  0.1 Å, i.e. very close to the predicted nearest-neighbor distance in germanene (2.4 Å). Scanning tunneling spectroscopy reveals that the atomic layer underneath the honeycomb layer is more metallic than the honeycomb layer itself. These observations are in line with a model recently proposed for metal di-(silicides/)germanides: a hexagonal crystal with metal layers separated by semiconductor layers with a honeycomb lattice. Based on our observations we propose that the outermost layer of the Ge(2)Pt nanocrystal is a germanene layer.

Two-dimensional Dirac signature of germanene

The structural and electronic properties of germanene coated Ge 2Pt clusters have been determined by scanning tunneling microscopy and spectroscopy at room temperature. The interior of the germanene sheet exhibits a buckled honeycomb structure with a lattice constant of 4.3 A and a buckling of 0.2 A. The zigzag edges of germanene are reconstructed and display a 4× periodicity. The differential conductivity of the interior of the germanene sheet has a V-shape, which is reminiscent of the density of states of a two-dimensional Dirac system. The minimum of the differential conductivity is located close to the Fermi level and has a non-zero value, which we ascribe to the metallic character of the underlying Ge 2Pt substrate. Near the reconstructed germanene zigzag edges the shape of the differential conductivity changes from a V-shape to a more parabolic-like shape, revealing that the reconstructed germanene zigzag edges do not exhibit a pronounced metallic edge state.

Defect Dominated Charge Transport and Fermi Level Pinning in MoS2/Metal Contacts

Understanding the electronic contact between molybdenum disulfide (MoS2) and metal electrodes is vital for the realization of future MoS2-based electronic devices. Natural MoS2 has the drawback of a high density of both metal and sulfur defects and impurities. We present evidence that subsurface metal-like defects with a density of ∼1011 cm–2 induce negative ionization of the outermost S atom complex. We investigate with high-spatial-resolution surface characterization techniques the effect of these defects on the local conductance of MoS2. Using metal nanocontacts (contact area < 6 nm2), we find that subsurface metal-like defects (and not S-vacancies) drastically decrease the metal/MoS2 Schottky barrier height as compared to that in the pristine regions. The magnitude of this decrease depends on the contact metal. The decrease of the Schottky barrier height is attributed to strong Fermi level pinning at the defects. Indeed, this is demonstrated in the measured pinning factor, which is equal to ∼0.1 at defect locations and ∼0.3 at pristine regions. Our findings are in good agreement with the theoretically predicted values. These defects provide low-resistance conduction paths in MoS2-based nanodevices and will play a prominent role as the device junction contact area decreases in size.

Structure and dynamics of confined alcohol-water mixtures

The effect of confinement between mica and graphene on the structure and dynamics of alcohol-water mixtures has been studied in situ and in real time at the molecular level by atomic force microscopy (AFM) at room temperature. AFM images reveal that the adsorbed molecules are segregated into faceted alcohol-rich islands on top of an ice layer on mica, surrounded by a pre-existing multilayer water-rich film. These faceted islands are in direct contact with the graphene surface, revealing a preferred adsorption site. Moreover, alcohol adsorption at low relative humidity (RH) reveals a strong preference of the alcohol molecules for the ordered ice interface. The growth dynamics of the alcohol islands is governed by supersaturation, temperature, the free energy of attachment of molecules to the island edge and two-dimensional (2D) diffusion. The measured diffusion coefficients display a size dependence on the molecular size of the alcohols, and are about 6 orders of magnitude smaller than the bulk diffusion coefficients, demonstrating the effect of confinement on the behavior of the alcohols. These experimental results provide new insights into the behavior of multicomponent fluids in confined geometries, which is of paramount importance in nanofluidics and biology.

Electronically stabilized nanowire growth

Metallic nanowires show unique physical properties owing to their one-dimensional nature. Many of these unique properties are intimately related to electron-electron interactions, which have a much more prominent role in one dimension than in two or three dimensions. Here we report the direct visualization of quantum size effects responsible for preferred lengths of self-assembled metallic iridium nanowires grown on a germanium (001) surface. The nanowire length distribution shows a strong preference for nanowire lengths that are an integer multiple of 4.8 nm. Spatially resolved scanning tunneling spectroscopic measurements reveal the presence of electron standing waves patterns in the nanowires. These standing waves are caused by conduction electrons, that is the electrons near the Fermi level, which are scattered at the ends of the nanowire.

Graphene Visualizes the Ion Distribution on Air-Cleaved Mica

The distribution of potassium (K+) ions on air-cleaved mica is important in many interfacial phenomena such as crystal growth, self-assembly and charge transfer on mica. However, due to experimental limitations to nondestructively probe single ions and ionic domains, their exact lateral organization is yet unknown. We show, by the use of graphene as an ultra-thin protective coating and scanning probe microscopies, that single potassium ions form ordered structures that are covered by an ice layer. The K+ ions prefer to minimize the number of nearest neighbour K+ ions by forming row-like structures as well as small domains. This trend is a result of repulsive ionic forces between adjacent ions, weakened due to screening by the surrounding water molecules. Using high resolution conductive atomic force microscopy maps, the local conductance of the graphene is measured, revealing a direct correlation between the K+ distribution and the structure of the ice layer. Our results shed light on the local distribution of ions on the air-cleaved mica, solving a long-standing enigma. They also provide a detailed understanding of charge transfer from the ionic domains towards graphene.

Hydrophobic Ice Confined between Graphene and MoS2

The structure and nature of water confined between hydrophobic molybdenum disulfide (MoS2) and graphene (Gr) are investigated at room temperature by means of atomic force microscopy. We find the formation of two-dimensional (2D) crystalline ice layers. In contrast to the hexagonal ice “bilayers” of bulk ice, these 2D crystalline ice phases consist of two planar hexagonal layers. Additional water condensation leads to either lateral expansion of the ice layers or to the formation of three-dimensional water droplets on top or at the edges of the two-layer ice, indicating that water does not wet these planar ice films. The results presented here are in line with a recent theory suggesting that water confined between hydrophobic walls forms 2D crystalline two-layer ice with a nontetrahedral geometry and intrahydrogen bonding. The lack of dangling bonds on either surface of the ice film gives rise to a hydrophobic character. The unusual geometry of these ice films is of great potential importance in biological...

Electrochemically Induced Nanobubbles between Graphene and Mica

We present a new method to create dynamic nanobubbles. The nanobubbles are created between graphene and mica by reducing intercalated water to hydrogen. The nanobubbles have a typical radius of several hundred nanometers, a height of a few tens of nanometers and an internal pressure in the range of 0.5-8 MPa. Our approach paves the way to the realization of nanobubbles of which both size and internal pressure are tunable.

Water-Induced Blister Formation in a Thin Film Polymer

A failure mechanism of thin film polymers immersed in water is presented: the formation of blisters. The growth of blisters is counterintuitive as the substrates were noncorroding and the polymer does not swell in water. We identify osmosis as the driving force behind the blister formation. The dynamics of the blister formation is studied experimentally as well as theoretically, and a quantitative model describing the blister growth is developed, which accurately describes the temporal evolution of the blisters.