Low-temperature plasma-enhanced atomic layer deposition of 2-D MoS2: large area, thickness control and tuneable morphology.

Low-temperature controllable synthesis of monolayer-to-multilayer thick MoS2 with tuneable morphology is demonstrated by using plasma enhanced atomic layer deposition (PEALD). The characteristic self-limiting ALD growth with a growth-per-cycle of 0.1 nm per cycle and digital thickness control down to a monolayer are observed with excellent wafer scale uniformity. The as-deposited films are found to be polycrystalline in nature showing the signature Raman and photoluminescence signals for the mono-to-few layered regime. Furthermore, a transformation in film morphology from in-plane to out-of-plane orientation of the 2-dimensional layers as a function of growth temperature is observed. An extensive study based on high-resolution transmission electron microscopy is presented to unravel the nucleation mechanism of MoS2 on SiO2/Si substrates at 450 °C. In addition, a model elucidating the film morphology transformation (at 450 °C) is hypothesized. Finally, the out-of-plane oriented films are demonstrated to outperform the in-plane oriented films in the hydrogen evolution reaction for water splitting applications.

Graphene nanoribbon blends with P3HT for organic electronics.

In organic field-effect transistors (OFETs) the electrical characteristics of polymeric semiconducting materials suffer from the presence of structural/morphological defects and grain boundaries as well as amorphous domains within the film, hindering an efficient transport of charges. To improve the percolation of charges we blend a regioregular poly(3-hexylthiophene) (P3HT) with newly designed N = 18 armchair graphene nanoribbons (GNRs). The latter, prepared by a bottom-up solution synthesis, are expected to form solid aggregates which cannot be easily interfaced with metallic electrodes, limiting charge injection at metal-semiconductor interfaces, and are characterized by a finite size, thus by grain boundaries, which negatively affect the charge transport within the film. Both P3HT and GNRs are soluble/dispersible in organic solvents, enabling the use of a single step co-deposition process. The resulting OFETs show a three-fold increase in the charge carrier mobilities in blend films, when compared to pure P3HT devices. This behavior can be ascribed to GNRs, and aggregates thereof, facilitating the transport of the charges within the conduction channel by connecting the domains of the semiconductor film. The electronic characteristics of the devices such as the Ion/Ioff ratio are not affected by the addition of GNRs at different loads. Studies of the electrical characteristics under illumination for potential use of our blend films as organic phototransistors (OPTs) reveal a tunable photoresponse. Therefore, our strategy offers a new method towards the enhancement of the performance of OFETs, and holds potential for technological applications in (opto)electronics.

Controlling subnanometer gaps in plasmonic dimers using graphene.

Graphene is used as the thinnest possible spacer between gold nanoparticles and a gold substrate. This creates a robust, repeatable, and stable subnanometer gap for massive plasmonic field enhancements. White light spectroscopy of single 80 nm gold nanoparticles reveals plasmonic coupling between the particle and its image within the gold substrate. While for a single graphene layer, spectral doublets from coupled dimer modes are observed shifted into the near-infrared, these disappear for increasing numbers of layers. These doublets arise from charger-transfer-sensitive gap plasmons, allowing optical measurement to access out-of-plane conductivity in such layered systems. Gating the graphene can thus directly produce plasmon tuning.

Spatially resolved electrostatic potential and photocurrent generation in carbon nanotube array devices.

We have used laser-excited photocurrent microscopy to map the internal electrostatic potential profile of semiconducting single-walled carbon nanotube (S-SWCNT) array devices with a spatial resolution of 250 nm. The measurements of S-SWCNTs on optically transparent samples provide new insights into the physical principles of device operation and reveal performance-limiting local heterogeneities in the electrostatic potential profile not observable with other imaging techniques. The experiments deliver photocurrent images from the underside of the S-SWCNT-metal contacts and thus enable the direct measurement of the charge carrier transfer lengths at the palladium-S-SWCNT and aluminum-S-SWCNT interfaces. We use the experimental results to formulate design rules for optimized layouts of S-SWCNT-based photovoltaic devices. Furthermore, we demonstrate the external control of the electrostatic potential profile in S-SWCNT array devices equipped with local metal gates.

The graphene-gold interface and its implications for nanoelectronics.

We combine optical microspectroscopy and electronic measurements to study how gold deposition affects the physical properties of graphene. We find that the electronic structure, the electron-phonon coupling, and the doping level in gold-plated graphene are largely preserved. The transfer lengths for electrons and holes at the graphene-gold contact have values as high as 1.6 µm. However, the interfacial coupling of graphene and gold causes local temperature drops of up to 500 K in operating electronic devices.

Raman and photocurrent imaging of electrical stress-induced p-n junctions in graphene.

Electrostatically doped graphene p-n junctions can be formed by applying large source-drain and source-gate biases to a graphene field-effect transistor, which results in trapped charges in part of the channel gate oxide. We measure the temperature distribution in situ during the electrical stress and characterize the resulting p-n junctions by Raman spectroscopy and photocurrent microscopy. Doping levels, the size of the doped graphene segments, and the abruptness of the p-n junctions are all extracted. Additional voltage probes can limit the length of the doped segments by acting as heat sinks. The spatial location of the identified potential steps coincides with the position where a photocurrent is generated, confirming the creation of p-n junctions.

Atomic structure of reduced graphene oxide.

Using high resolution transmission electron microscopy, we identify the specific atomic scale features in chemically derived graphene monolayers that originate from the oxidation-reduction treatment of graphene. The layers are found to comprise defect-free graphene areas with sizes of a few nanometers interspersed with defect areas dominated by clustered pentagons and heptagons. Interestingly, all carbon atoms in these defective areas are bonded to three neighbors maintaining a planar sp(2)-configuration, which makes them undetectable by spectroscopic techniques. Furthermore, we observe that they introduce significant in-plane distortions and strain in the surrounding lattice.

Electrical conduction mechanism in chemically derived graphene monolayers.

We have performed a detailed study of the intrinsic electrical conduction process in individual monolayers of chemically reduced graphene oxide down to a temperature of 2 K. The observed conductance can be consistently interpreted in the framework of two-dimensional variable-range hopping in parallel with electric-field-driven tunneling. The latter mechanism is found to dominate the electrical transport at very low temperatures and high electric fields. Our results are consistent with a model of highly conducting graphene regions interspersed with disordered regions, across which charge carrier hopping and tunneling are promoted by strong local electric fields.