ALD-grown two-dimensional TiSx metal contacts for MoS2 field-effect transistors.

Metal contacts to MoS2 field-effect transistors (FETs) play a determinant role in the device electrical characteristics and need to be chosen carefully. Because of the Schottky barrier (SB) and the Fermi level pinning (FLP) effects that occur at the contact/MoS2 interface, MoS2 FETs often suffer from high contact resistance (Rc). One way to overcome this issue is to replace the conventional 3D bulk metal contacts with 2D counterparts. Herein, we investigate 2D metallic TiSx (x ∼ 1.8) as top contacts for MoS2 FETs. We employ atomic layer deposition (ALD) for the synthesis of both the MoS2 channels as well as the TiSx contacts and assess the electrical performance of the fabricated devices. Various thicknesses of TiSx are grown on MoS2, and the resultant devices are electrically compared to the ones with the conventional Ti metal contacts. Our findings show that the replacement of 5 nm Ti bulk contacts with only ∼1.2 nm of 2D TiSx is beneficial in improving the overall device metrics. With such ultrathin TiSx contacts, the ON-state current (ION) triples and increases to ∼35 µA µm-1. Rc also reduces by a factor of four and reaches ∼5 MΩ µm. Such performance enhancements were observed despite the SB formed at the TiSx/MoS2 interface is believed to be higher than the SB formed at the Ti/MoS2 interface. These device metric improvements could therefore be mainly associated with an increased level of electrostatic doping in MoS2, as a result of using 2D TiSx for contacting the 2D MoS2. Our findings are also well supported by TCAD device simulations.

On the Contact Optimization of ALD-Based MoS2 FETs: Correlation of Processing Conditions and Interface Chemistry with Device Electrical Performance.

Despite the extensive ongoing research on MoS2 field effect transistors (FETs), the key role of device processing conditions in the chemistry involved at the metal-to-MoS2 interface and their influence on the electrical performance are often overlooked. In addition, the majority of reports on MoS2 contacts are based on exfoliated MoS2, whereas synthetic films are even more susceptible to the changes made in device processing conditions. In this paper, working FETs with atomic layer deposition (ALD)-based MoS2 films and Ti/Au contacts are demonstrated, using current-voltage (I-V) characterization. In pursuit of optimizing the contacts, high-vacuum thermal annealing as well as O2/Ar plasma cleaning treatments are introduced, and their influence on the electrical performance is studied. The electrical findings are linked to the interface chemistry through X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM) analyses. XPS evaluation reveals that the concentration of organic residues on the MoS2 surface, as a result of resist usage during the device processing, is significant. Removal of these contaminations with O2/Ar plasma changes the MoS2 chemical state and enhances the MoS2 electrical properties. Based on the STEM analysis, the observed progress in the device electrical characteristics could also be associated with the formation of a continuous TiS x layer at the Ti-to-MoS2 interface. Scaling down the Ti interlayer thickness and replacing it with Cr is found to be beneficial as well, leading to further device performance advancements. Our findings are of value for attaining optimal contacts to synthetic MoS2 films.

Templating effect of single-layer graphene supported by an insulating substrate on the molecular orientation of lead phthalocyanine.

The influence of single-layer graphene on top of a SiO2/Si surface on the orientation of nonplanar lead phthalocyanine (PbPc) molecules is studied using two-dimensional grazing incidence X-ray diffraction. The studies indicate the formation of a mixture of polymorphs, i.e., monoclinic and triclinic forms of PbPc with face-on (lying down) and edge-on (standing up) PbPc orientations, respectively. The formation of monoclinic fractions is attributed to the presence of the graphene layer directing the π interactions between the highly delocalized macrocycles. The competing interfacial van der Waals forces and molecule-molecule interactions lead to the formation of a small fraction of triclinic moieties. The nanoscale electrical characterization of the thin PbPc layer on graphene by means of conducting atomic force microscopy shows enhanced vertical conductance with interconnected conducting domains consisting of ordered monoclinic crystallites through which the charge transfer occurs via tunneling. These results show the importance of a templating layer to induce the formation of a required phase of PbPc suitable for specific device applications.

A carbon nanotube-graphene nanoribbon seamless junction transistor.

The nature and type of intramolecular junctions are very important for nanoelectronics. Here, a new way of fabricating seamless junctions between carbon nanotubes and graphene nanoribbons (GNRs) is demonstrated. Dielectrophoretically aligned multi-walled carbon nanotubes (CNTs) across metal electrodes are etched with an Ar ion beam at low pressure. We show that grounding of metal electrodes plays an important role in the etching of CNTs in contact with the metal electrodes. If electrodes are grounded, that portion of the CNT doesn't get etched due to the discharge of ions through the ground, and CNT to GNR conversion occurs in the gap region between the metal electrodes. Thus produced GNRs have a large aspect ratio of ∼90, and Raman spectroscopy analysis shows that the distance between the defects is ∼65 nm. The CNT-GNR-CNT seamless junctions are ohmic in nature and the transistor shows a current on/off ratio of 27 with a hole mobility of 350 cm2 V-1 s-1.

Dirac-Point Shift by Carrier Injection Barrier in Graphene Field-Effect Transistor Operation at Room Temperature.

A positive shift in the Dirac point in graphene field-effect transistors was observed with Hall-effect measurements coupled with Kelvin-probe measurements at room temperature. This shift can be explained by the asymmetrical behavior of the contact resistance by virtue of the electron injection barrier at the source contact. As an outcome, an intrinsic resistance is given to allow a retrieval of an intrinsic carrier mobility found to be decreased with increasing gate bias, suggesting the dominance of short-range scattering in a single-layer graphene field-effect transistor. These results analytically correlate the field-effect parameters with intrinsic graphene properties.

Engineering the Photoresponse of InAs Nanowires.

We report on individual-InAs nanowire optoelectronic devices which can be tailored to exhibit either negative or positive photoconductivity (NPC or PPC). The NPC photoresponse time and magnitude is found to be highly tunable by varying the nanowire diameter under controlled growth conditions. Using hysteresis characterization, we decouple the observed photoexcitation-induced hot electron trapping from conventional electric field-induced trapping to gain a fundamental insight into the interface trap states responsible for NPC. Furthermore, we demonstrate surface passivation without chemical etching which both enhances the field-effect mobility of the nanowires by approximately an order of magnitude and effectively eliminates the hot carrier trapping found to be responsible for NPC, thus restoring an "intrinsic" positive photoresponse. This opens pathways toward engineering semiconductor nanowires for novel optical-memory and photodetector applications.

Parameter Space of Atomic Layer Deposition of Ultrathin Oxides on Graphene.

Atomic layer deposition (ALD) of ultrathin aluminum oxide (AlOx) films was systematically studied on supported chemical vapor deposition (CVD) graphene. We show that by extending the precursor residence time, using either a multiple-pulse sequence or a soaking period, ultrathin continuous AlOx films can be achieved directly on graphene using standard H2O and trimethylaluminum (TMA) precursors even at a high deposition temperature of 200 °C, without the use of surfactants or other additional graphene surface modifications. To obtain conformal nucleation, a precursor residence time of >2s is needed, which is not prohibitively long but sufficient to account for the slow adsorption kinetics of the graphene surface. In contrast, a shorter residence time results in heterogeneous nucleation that is preferential to defect/selective sites on the graphene. These findings demonstrate that careful control of the ALD parameter space is imperative in governing the nucleation behavior of AlOx on CVD graphene. We consider our results to have model system character for rational two-dimensional (2D)/non-2D material process integration, relevant also to the interfacing and device integration of the many other emerging 2D materials.

Towards a Graphene-Based Low Intensity Photon Counting Photodetector.

Graphene is a highly promising material in the development of new photodetector technologies, in particular due its tunable optoelectronic properties, high mobilities and fast relaxation times coupled to its atomic thinness and other unique electrical, thermal and mechanical properties. Optoelectronic applications and graphene-based photodetector technology are still in their infancy, but with a range of device integration and manufacturing approaches emerging this field is progressing quickly. In this review we explore the potential of graphene in the context of existing single photon counting technologies by comparing their performance to simulations of graphene-based single photon counting and low photon intensity photodetection technologies operating in the visible, terahertz and X-ray energy regimes. We highlight the theoretical predictions and current graphene manufacturing processes for these detectors. We show initial experimental implementations and discuss the key challenges and next steps in the development of these technologies.

Infrared transparent graphene heater for silicon photonic integrated circuits.

Thermo-optical tuning of the refractive index is one of the pivotal operations performed in integrated silicon photonic circuits for thermal stabilization, compensation of fabrication tolerances, and implementation of photonic operations. Currently, heaters based on metal wires provide the temperature control in the silicon waveguide. The strong interaction of metal and light, however, necessitates a certain gap between the heater and the photonic structure to avoid significant transmission loss. Here we present a graphene heater that overcomes this constraint and enables an energy efficient tuning of the refractive index. We achieve a tuning power as low as 22 mW per free spectral range and fast response time of 3 µs, outperforming metal based waveguide heaters. Simulations support the experimental results and suggest that for graphene heaters the spacing to the silicon can be further reduced yielding the best possible energy efficiency and operation speed.

Experimental verification of electro-refractive phase modulation in graphene.

Graphene has been considered as a promising material for opto-electronic devices, because of its tunable and wideband optical properties. In this work, we demonstrate electro-refractive phase modulation in graphene at wavelengths from 1530 to 1570 nm. By integrating a gated graphene layer in a silicon-waveguide based Mach-Zehnder interferometer, the key parameters of a phase modulator like change in effective refractive index, insertion loss and absorption change are extracted. These experimentally obtained values are well reproduced by simulations and design guidelines are provided to make graphene devices competitive to contemporary silicon based phase modulators for on-chip applications.

Highly air stable passivation of graphene based field effect devices.

The sensitivity of graphene based devices to surface adsorbates and charge traps at the graphene/dielectric interface requires proper device passivation in order to operate them reproducibly under ambient conditions. Here we report on the use of atomic layer deposited aluminum oxide as passivation layer on graphene field effect devices (GFETs). We show that successful passivation produce hysteresis free DC characteristics, low doping level GFETs stable over weeks though operated and stored in ambient atmosphere. This is achieved by selecting proper seed layer prior to deposition of encapsulation layer. The passivated devices are also demonstrated to be robust towards the exposure to chemicals and heat treatments, typically used during device fabrication. Additionally, the passivation of high stability and reproducible characteristics is also shown for functional devices like integrated graphene based inverters.

Ultrafast response humidity sensor using supramolecular nanofibre and its application in monitoring breath humidity and flow.

Measuring humidity in dynamic situations calls for highly sensitive fast response sensors. Here we report, a humidity sensor fabricated using solution processed supramolecular nanofibres as active resistive sensing material. The nanofibres are built via self- assembly of donor and acceptor molecules (coronene tetracarboxylate and dodecyl methyl viologen respectively) involved in charge transfer interactions. The conductivity of the nanofibre varied sensitively over a wide range of relative humidity (RH) with unprecedented fast response and recovery times. Based on UV-vis, XRD and AFM measurements, it is found that the stacking distance in the nanofibre decreases slightly while the charge transfer band intensity increases, all observations implying enhanced charge transfer interaction and hence the conductivity. It is demonstrated to be as a novel breath sensor which can monitor the respiration rate. Using two humidity sensors, a breath flow sensor was made which could simultaneously measure RH and flow rate of exhaled nasal breath. The integrated device was used for monitoring RH in the exhaled breath from volunteers undergoing exercise and alcohol induced dehydration.

A charge transfer single crystal field effect transistor operating at low voltages.

An organic FET employing a single crystal of a donor-acceptor system based on coronene tetracarboxylate and a methyl viologen derivative exhibited an impressive mobility of 0.53 cm(2) V(-1) s(-1), operating under 2 V in the ambient atmosphere. Quantum mechanical calculations have provided an insight into the hole-dominant transport in the crystal.

High-mobility field effect transistors based on supramolecular charge transfer nanofibres.

Self-assembled charge transfer supramolecular nanofibres of coronene tetracarboxylate (CS) and dodecyl substituted unsymmetric viologen derivative (DMV) behave as active channel in field effect transistors exhibiting high mobility. These devices work in ambient conditions and can regenerate in the presence of a single drop of water.

Dynamic self-assembly of charge-transfer nanofibers of tetrathiafulvalene derivatives with F4TCNQ.

One-dimensional charge-transfer nanostructures were constructed by the supramolecular coassembly of amphiphilic (Amph-TTF) and hydrophobic (TDD-TTF) tetrathiafulvalene (TTF) donor derivatives with the acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)TCNQ), in appropriate solvent composition mixtures. Microscopic analyses show that TDD-TTF retains its self-assembled fibrillar morphology even in the charge-transfer state, whereas Amph-TTF undergoes a spherical to nanorod transition upon coassembly. Time-dependent optical spectroscopy studies have shown a spontaneous change in molecular organization in TDD-TTF-based donor-acceptor costacks, which suggests a dynamic behavior, in contrast to the kinetically stable amphiphilic TTF assemblies. We have also tried to get an insight into the observed time-dependent change in molecular packing of these nanostructures through spectroscopic analyses by commenting on whether the TTF-TCNQ pair is cofacially arranged or present in the classical herringbone (orthogonal) fashion. Furthermore, our two-probe electrical measurements showed that these charge-transfer fibers are conducting. A supramolecular approach that yields 1D charge-transfer nanostructures of donor and acceptor molecules will be an alternative to existing crystalline substances with high conductivity and hence can be a viable tool for nanoelectronics.

Flexible and semitransparent strain sensors based on micromolded Pd nanoparticle-carbon µ-stripes.

Flexible resistive strain sensors have been fabricated by micromolding Pd alkanethiolate on polyimide substrates and subjecting to thermolysis in air. Thus produced stripes were ∼1 µm wide with spacing of ∼0.5 µm and contained Pd nanoparticles in carbon matrix. The nanoparticle size and the nature of carbon are much dependent on the thermolysis temperature as is also the resistance of the microstripes. Generally, lower thermolysis temperatures (<230 °C) produced stripes containing small Pd nanoparticles with significant fraction of carbon from the precursor decomposition. The stripes were poorly conducting yet interestingly, exhibited change of resistance under tensile and compressive strain. Particularly noteworthy are the stripes produced from 195 °C thermolysis, which showed a high gauge factor of ∼390 with strain sensitivity, 0.09%. With molding at 230 °C, the stripes obtained were highly conducting, and amazingly did not change the resistance with strain even after several bending cycles. The latter are ideal as flexible conduits and interconnects. Thus, the article reports a method of producing flexible sensitive strain sensors on one hand and on the other, flexible conduits with unchanging resistance, merely by fine-tuning the precursor decomposition under the molding conditions.

Direct micromolding of Pd micro-stripes for electronic applications.

A simple, one-step direct micromolding process has been realised to produce highly conducting Pd micro-stripes over large areas on various substrates including flexible polyimide. Under a PDMS micromold, Pd octanethiolate served as a precursor at 250 degrees C, a temperature at which the precursor gets neatly metallised. Thus produced micro-stripes are robust under bending and can be utilised for flexible electronics. Hydrogen sensing by Pd micro-stripes is demonstrated. By electrolessly depositing Cu on the stripes, they can be made to peel off to form free standing Cu-Pd micro-ribbons.