Axel Eckmann

Strong Light-Matter Interactions in Heterostructures of Atomically Thin Films

Atomic Layer Heterostructures—More Is More The isolation of stable layers of various materials, only an atom or several atoms thick, has provided the opportunity to fabricate devices with novel functionality and to probe fundamental physics. Britnell et al. (p. 1311, published online 2 May; see the Perspective by Hamm and Hess) sandwiched a single layer of the transition metal dichalcogenide WS2 between two sheets of graphene. The photocurrent response of the heterostructure device was enhanced, compared to that of the bare layer of WS2. The prospect of combining single or several-atom-thick layers into heterostructures should help to develop materials with a wide range of properties. Transition metal dichalcogenides sandwiched between two layers of graphene produce an enhanced photoresponse. [Also see Perspective by Hamm and Hess] The isolation of various two-dimensional (2D) materials, and the possibility to combine them in vertical stacks, has created a new paradigm in materials science: heterostructures based on 2D crystals. Such a concept has already proven fruitful for a number of electronic applications in the area of ultrathin and flexible devices. Here, we expand the range of such structures to photoactive ones by using semiconducting transition metal dichalcogenides (TMDCs)/graphene stacks. Van Hove singularities in the electronic density of states of TMDC guarantees enhanced light-matter interactions, leading to enhanced photon absorption and electron-hole creation (which are collected in transparent graphene electrodes). This allows development of extremely efficient flexible photovoltaic devices with photoresponsivity above 0.1 ampere per watt (corresponding to an external quantum efficiency of above 30%).

Commensurate-incommensurate transition in graphene on hexagonal boron nitride

When a crystal is subjected to a periodic potential, under certain circumstances it can adjust itself to follow the periodicity of the potential, resulting in a commensurate state. Of particular interest are topological defects between the two commensurate phases, such as solitons and domain walls. Here we report a commensurate-incommensurate transition for graphene on top of hexagonal boron nitride (hBN). Depending on the rotation angle between the lattices of the two crystals, graphene can either stretch to adapt to a slightly different hBN periodicity (for small angles, resulting in a commensurate state) or exhibit little adjustment (the incommensurate state). In the commensurate state, areas with matching lattice constants are separated by domain walls that accumulate the generated strain. Such soliton-like objects are not only of significant fundamental interest, but their presence could also explain recent experiments where electronic and optical properties of graphene-hBN heterostructures were observed to be considerably altered.

Raman spectroscopy of boron-doped single-layer graphene

The introduction of foreign atoms, such as nitrogen, into the hexagonal network of an sp(2)-hybridized carbon atom monolayer has been demonstrated and constitutes an effective tool for tailoring the intrinsic properties of graphene. Here, we report that boron atoms can be efficiently substituted for carbon in graphene. Single-layer graphene substitutionally doped with boron was prepared by the mechanical exfoliation of boron-doped graphite. X-ray photoelectron spectroscopy demonstrated that the amount of substitutional boron in graphite was ~0.22 atom %. Raman spectroscopy demonstrated that the boron atoms were spaced 4.76 nm apart in single-layer graphene. The 7-fold higher intensity of the D-band when compared to the G-band was explained by the elastically scattered photoexcited electrons by boron atoms before emitting a phonon. The frequency of the G-band in single-layer substitutionally boron-doped graphene was unchanged, which could be explained by the p-type boron doping (stiffening) counteracting the tensile strain effect of the larger carbon-boron bond length (softening). Boron-doped graphene appears to be a useful tool for engineering the physical and chemical properties of graphene.

Electrochemical Behavior of Monolayer and Bilayer Graphene

Results of a study on the electrochemical properties of exfoliated single and multilayer graphene flakes are presented. Graphene flakes were deposited on silicon/silicon oxide wafers to enable fast and accurate characterization by optical microscopy and Raman spectroscopy. Conductive silver paint and silver wires were used to fabricate contacts; epoxy resin was employed as a masking coating in order to expose a stable, well-defined area of graphene. Both multilayer and monolayer graphene microelectrodes showed quasi-reversible behavior during voltammetric measurements in potassium ferricyanide. However, the standard heterogeneous charge transfer rate constant, k°, was estimated to be higher for monolayer graphene flakes.

Heterostructures Produced from Nanosheet-Based Inks

The new paradigm of heterostructures based on two-dimensional (2D) atomic crystals has already led to the observation of exciting physical phenomena and creation of novel devices. The possibility of combining layers of different 2D materials in one stack allows unprecedented control over the electronic and optical properties of the resulting material. Still, the current method of mechanical transfer of individual 2D crystals, though allowing exceptional control over the quality of such structures and interfaces, is not scalable. Here we show that such heterostructures can be assembled from chemically exfoliated 2D crystals, allowing for low-cost and scalable methods to be used in device fabrication.

Doping mechanisms in graphene-MoS2 hybrids

We present a joint theoretical and experimental investigation of charge doping and electronic potential landscapes in hybrid structures composed of graphene and semiconducting single layer molybdenum disulfide (MoS2). From first-principles simulations, we find electron doping of graphene due to the presence of rhenium impurities in MoS2. Furthermore, we show that MoS2 edges give rise to charge reordering and a potential shift in graphene, which can be controlled through external gate voltages. The interplay of edge and impurity effects allows the use of the graphene-MoS2 hybrid as a photodetector. Spatially resolved photocurrent signals can be used to resolve potential gradients and local doping levels in the sample.

Raman Fingerprint of Aligned Graphene/h-BN Superlattices

Graphene placed on hexagonal-boron nitride (h-BN) experiences a superlattice (Moiré) potential, which leads to a strong reconstruction of graphenes electronic spectrum with new Dirac points emerging at sub-eV energies. Here we study the effect of such superlattices on graphenes Raman spectrum. In particular, the 2D Raman peak is found to be exquisitely sensitive to the misalignment between graphene and h-BN lattices, probably due to the presence of a strain distribution with the same periodicity of the Moiré potential. This feature can be used to identify graphene superlattices with a misalignment angle smaller than 2°.

Controlled modification of mono- and bilayer graphene in O, H and CF plasmas

In this work, covalent modification of mono- and bilayer graphene is achieved using tetrafluoromethane (CF₄), oxygen and hydrogen RF plasma. Controlled modification of graphene is usually difficult to achieve, in particular with oxygen plasma, which is rather aggressive and usually leads to etching of graphene. Here we use x-ray photoelectron spectroscopy and Raman spectroscopy to show that mild plasma conditions and fine tuning of the number of functional groups can be obtained in all plasmas by varying parameters such as exposure time and sample position inside the chamber. We found that even for the usual harsh oxygen treatment the defect density could be lowered, down to one defect for 3.5 × 10⁴ carbon atoms. Furthermore, we show that CF₄ plasma leads to functionalization without etching and that graphene becomes an insulator at saturation coverage. In addition, the reactivity of mono- and bilayer graphene was studied revealing faster modification of monolayer in oxygen and CF₄ plasma, in agreement with previous works. In contrast, similar modification rates were observed for both mono- and bilayer during hydrogenation. We attribute this discrepancy to the presence of more energetic species in the hydrogen plasma such as positive ions that could play a role in the functionalization process.

Single- and double- sided chemical functionalization of bilayer graphene

An experimental study on the interaction between the top and bottom layer of a chemically functionalized graphene bilayer by mild oxygen plasma is reported. Structural, chemical, and electrical properties are monitored using Raman spectroscopy, transport measurements, conductive atomic force microscopy and X-ray photoelectron spectroscopy. Single- and double-sided chemical functionalization are found to give very different results: single-sided modified bilayers show relatively high mobility (200-600 cm(2) V(-1) s(-1) at room temperature) and a stable structure with a limited amount of defects, even after long plasma treatment (>60 s). This is attributed to preferential modification and limited coverage of the top layer during plasma exposure, while the bottom layer remains almost unperturbed. This could eventually lead to decoupling between top and bottom layers. Double-sided chemical functionalization leads to a structure containing a high concentration of defects, very similar to graphene oxide. This opens the possibility to use plasma treatment not only for etching and patterning of graphene, but also to make heterostructures (through single-sided modification of bilayers) for sensors and transistors and new graphene-derivatives materials (through double-sided modification).

High-Yield Production and Transfer of Graphene Flakes Obtained by Anodic Bonding

We report large-yield production of graphene flakes on glass by anodic bonding. Under optimum conditions, we counted several tens of flakes with lateral size around 20-30 μm and a few tens of flakes with larger size. About 60-70% of the flakes have a negligible D peak. We show that it is possible to easily transfer the flakes by the wedging technique. The transfer on silicon does not damage graphene and lowers the doping. The charge mobility of the transferred flakes on silicon is on the order of 6000 cm(2)/V s (at a carrier concentration of 10(12) cm(-2)), which is typical for devices prepared on this substrate with exfoliated graphene.