Lijie Zhang

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.

Scanning tunneling spectroscopy study of the Dirac spectrum of germanene.

The temperature dependence of the density of states of germanene, synthesized on Ge/Pt crystals, has been investigated with scanning tunneling spectroscopy. After correction for thermal broadening, a virtually perfect V-shaped density of states, which is a hallmark of a two-dimensional Dirac system, has been found. In an attempt to directly measure the energy dispersion relation via quasiparticle interference we have recorded spatial maps of the differential conductivity near the edges and defects of germanene. Unfortunately, we did not find any sign of Friedel oscillations. The absence of these Friedel oscillations hints to the occurrence of Klein tunneling.

Spatially resolved electronic structure of twisted graphene

We have used scanning tunneling microscopy and spectroscopy to resolve the spatial variation of the density of states of twisted graphene layers on top of a highly oriented pyrolytic graphite substrate. Owing to the twist a moire pattern develops with a periodicity that is substantially larger than the periodicity of a single layer graphene. The twisted graphene layer has electronic properties that are distinctly different from that of a single layer graphene due to the nonzero interlayer coupling. For small twist angles (∼1-3.5) the integrated differential conductivity spectrum exhibits two well-defined Van Hove singularities. Spatial maps of the differential conductivity that are recorded at energies near the Fermi level exhibit a honeycomb structure that is comprised of two inequivalent hexagonal sublattices. For energies |E-EF|>0.3eV the hexagonal structure in the differential conductivity maps vanishes. We have performed tight-binding calculations of the twisted graphene system using the propagation method, in which a third graphene layer is added to mimic the substrate. This third layer lowers the symmetry and explains the development of the two hexagonal sublattices in the moire pattern. Our experimental results are in excellent agreement with the tight-binding calculations.

Nanoscale Investigation of Defects and Oxidation of HfSe2

HfSe2 is a very good candidate for a transition metal dichalcogenide-based field-effect transistor owing to its moderate band gap of about 1 eV and its high-κ dielectric native oxide. Unfortunately, the experimentally determined charge carrier mobility is about 3 orders of magnitude lower than the theoretically predicted value. This strong deviation calls for a detailed investigation of the physical and electronic properties of HfSe2. Here, we have studied the structure, density, and density of states of several types of defects that are abundant on the HfSe2 surface using scanning tunneling microscopy and spectroscopy. Compared to MoS2 and WSe2, HfSe2 exhibits similar type of defects, albeit with a substantially higher density of 9 × 1011 cm–2. The most abundant defect is a subsurface defect, which shows up as a dim feature in scanning tunneling microscopy images. These dim dark defects have a substantially larger band gap (1.25 eV) than the pristine surface (1 eV), suggesting a substitution of the Hf atom by another atom. The high density of defects on the HfSe2 surface leads to very low Schottky barrier heights. Conductive atomic force microscopy measurements reveal a very small dependence of the Schottky barrier height on the work function of the metals, suggesting a strong Fermi-level pinning. We attribute the observed Fermi-level pinning (pinning factor ∼0.1) to surface distortions and Se/Hf defects. In addition, we have also studied the HfSe2 surface after the exposure to air by scanning tunneling microscopy and conductive atomic force microscopy. Partly oxidized layers with band gaps of 2 eV and Schottky barrier heights of ∼0.6 eV were readily found on the surface. Our experiments reveal that HfSe2 is very air-sensitive, implying that capping or encapsulating of HfSe2, in order to protect it against oxidation, is a necessity for technological applications.