Benjamin Robinson

Optical investigation of the natural electron doping in thin MoS2 films deposited on dielectric substrates

Two-dimensional (2D) compounds provide unique building blocks for novel layered devices and hybrid photonic structures. However, large surface-to-volume ratio in thin films enhances the significance of surface interactions and charging effects requiring new understanding. Here we use micro-photoluminescence (PL) and ultrasonic force microscopy to explore the influence of the dielectric environment on optical properties of a few monolayer MoS2 films. PL spectra for MoS2 films deposited on SiO2 substrates are found to vary widely. This film-to-film variation is suppressed by additional capping of MoS2 with SiO2 and SixNy, improving mechanical coupling of MoS2 with surrounding dielectrics. We show that the observed PL non-uniformities are related to strong variation in the local electron charging of MoS2 films. In completely encapsulated films, negative charging is enhanced leading to uniform optical properties. Observed great sensitivity of optical characteristics of 2D films to surface interactions has important implications for optoelectronics applications of layered materials.

Dipole reversal in Langmuir–Blodgett films of an optically nonlinear dye and its effect on the polarity for molecular rectification

Langmuir–Blodgett (LB) films of isomeric donor–(π-bridge)–acceptor molecules with either a hydrophobically substituted acceptor [D–π–A–C16H33 (1)] or donor [A–π–D–C16H33 (2)] exhibit second-harmonic generation and asymmetric current–voltage characteristics: a reversed polarity for rectification arises from an inversion of the dipole orientations in the two types of monolayer.

Structural, optical and electrostatic properties of single and few-layers MoS2: effect of substrate

We have decoupled the intrinsic electrostatic effects arising in monolayer and few-layer MoS2 from those influenced by the flake-substrate interaction. Using ultrasonic force microscopy nanomechanical mapping, we identify the change from supported to suspended flake regions on a trenched substrate. These regions are correlated with the surface potential as measured by scanning Kelvin probe microscopy. Relative to the supported region, we observe an increase in surface potential contrast due to suppressed charge transfer for the suspended monolayer. Using Raman spectroscopy we observe a red shift of the E12g mode for monolayer MoS2 deposited on Si, consistent with a more strained MoS2 on the Si substrate compared to the Au substrate.

Molecular Bridging of Silicon Nanogaps

The highly doped electrodes of a vertical silicon nanogap device have been bridged by a 5.85 nm long molecular wire, which was synthesized in situ by grafting 4-ethynylbenzaldehyde via C-Si links to the top and bottom electrodes and thereafter by coupling an amino-terminated fluorene unit to the aldehyde groups of the activated electrode surfaces. The number of bridging molecules is constrained by relying on surface roughness to match the 5.85 nm length with an electrode gap that is nominally 1 nm wider and may be controlled by varying the reaction time: the device current increases from ≤1 pA at 1 V following the initial grafting step to 10-100 nA at 1 V when reacted for 5-15 min with the amino-terminated linker and 10 μA when reacted for 16-53 h. It is the first time that both ends of a molecular wire have been directly grafted to silicon electrodes, and these molecule-induced changes are reversible. The bridges detach when the device is rinsed with dilute acid solution, which breaks the imine links of the in situ formed wire and causes the current to revert to the subpicoampere leakage value of the 4-ethynylbenzaldehyde-grafted nanogap structure.

Photoluminescence of two-dimensional GaTe and GaSe films

Gallium chalcogenides are promising building blocks for novel van der Waals heterostructures. We report on the low-temperature micro-photoluminescence (PL) of GaTe and GaSe films with thicknesses ranging from 200 nm to a single unit cell. In both materials, PL shows a dramatic decrease by 10^4–10^5 when film thickness is reduced from 200 to 10 nm. Based on evidence from continuous-wave (cw) and time-resolved PL, we propose a model explaining the PL decrease as a result of non-radiative carrier escape via surface states. Our results emphasize the need for special passivation of two-dimensional films for optoelectronic applications.

Functional molecular wires

The properties of self-assembled molecules may be tuned by sequentially coupling components on a gold surface, the molecular electronics toolbox of chemically reactive building blocks yielding molecular wires with diode-like current-voltage (I-V) characteristics. The bias for rectification in each case is dependent upon the sequence of electron-donating and electron-accepting moieties and similar behaviour has been achieved for four different contacting techniques.

Realization of Vertically Aligned, Ultrahigh Aspect Ratio InAsSb Nanowires on Graphite

The monolithic integration of InAs(1-x)Sb(x) semiconductor nanowires on graphitic substrates holds enormous promise for cost-effective, high-performance, and flexible devices in optoelectronics and high-speed electronics. However, the growth of InAs(1-x)Sb(x) nanowires with high aspect ratio essential for device applications is extremely challenging due to Sb-induced suppression of axial growth and enhancement in radial growth. We report the realization of high quality, vertically aligned, nontapered and ultrahigh aspect ratio InAs(1-x)Sb(x) nanowires with Sb composition (xSb(%)) up to ∼12% grown by indium-droplet assisted molecular beam epitaxy on graphite substrate. Low temperature photoluminescence measurements show that the InAs(1-x)Sb(x) nanowires exhibit bright band-to-band related emission with a distinct redshift as a function of Sb composition providing further confirmation of successful Sb incorporation in as-grown nanowires. This study reveals that the graphite substrate is a more favorable platform for InAs(1-x)Sb(x) nanowires that could lead to hybrid heterostructures possessing potential device applications in optoelectronics.

Adhesive ligand tether length affects the size and length of focal adhesions and influences cell spreading and attachment

Cells are known to respond to physical cues from their microenvironment such as matrix rigidity. Discrete adhesive ligands within flexible strands of fibronectin connect cell surface integrins to the broader extracellular matrix and are thought to mediate mechanosensing through the cytoskeleton-integrin-ECM linkage. We set out to determine if adhesive ligand tether length is another physical cue that cells can sense. Substrates were covalently modified with adhesive arginylglycylaspartic acid (RGD) ligands coupled with short (9.5 nm), medium (38.2 nm) and long (318 nm) length inert polyethylene glycol tethers. The size and length of focal adhesions of human foreskin fibroblasts gradually decreased from short to long tethers. Furthermore, we found cell adhesion varies in a linker length dependent manner with a remarkable 75% reduction in the density of cells on the surface and a 50% reduction in cell area between the shortest and longest linkers. We also report the interplay between RGD ligand concentration and tether length in determining cellular spread area. Our findings show that without varying substrate rigidity or ligand density, tether length alone can modulate cellular behaviour.

Synthesis of Covalently Linked Molecular Bridges between Silicon Electrodes in CMOS-Based Arrays of Vertical Si/SiO2/Si Nanogaps

Silicon nanogaps were bridged in situ by grafting 4-ethynylbenzaldehyde to activate the electrodes and coupling 2,6-diaminoanthra-9,10-quinone to link the coatings. The bridged structures exhibit currents of 11-14 nA at 1 V. The process is reversed by soaking in acidified solution, which causes the current to diminish. Copyright

Electromechanical sensing of substrate charge hidden under atomic 2D crystals

The functionality of graphene and other two-dimensional materials in electronic devices is highly influenced by the film-substrate charge transfer affecting local carrier density. We demonstrate that charges buried under the few layer graphene on/in the insulating substrate can be detected using electromechanical actuation of the conductive atomically thin layers, allowing measurements of areal density of film-substrate transferred charges under few layer graphene and MoS2 suspended films.