Raman Fingerprints of Graphene Produced by Anodic Electrochemical Exfoliation.

Electrochemical exfoliation is one of the most promising methods for scalable production of graphene. However, limited understanding of its Raman spectrum as well as lack of measurement standards for graphene strongly limit its industrial applications. In this work, we show a systematic study of the Raman spectrum of electrochemically exfoliated graphene, produced using different electrolytes and types of solvents in varying amounts. We demonstrate that no information on the thickness can be extracted from the shape of the 2D peak as this type of graphene is defective. Furthermore, the number of defects and the uniformity of the samples strongly depend on the experimental conditions, including postprocessing. Under specific conditions, the formation of short conductive trans-polyacetylene chains has been observed. Our Raman analysis provides guidance for the community on how to get information on defects coming from electrolyte, temperature, and other experimental conditions, by making Raman spectroscopy a powerful metrology tool.

Intercalation, decomposition, entrapment - a new route to graphene nanobubbles.

Graphene nanobubbles (GNBs) have become the subject of recent research due to their novel physical properties. However, present methods to create them involve either extreme conditions or complex sample fabrication. We present a novel approach which relies on the intercalation of small molecules (NH3), their surface-mediated decomposition and the formation of larger molecules (N2) which are then entrapped beneath the graphene in bubbles. Our hypothesised reaction mechanism requires the copper substrate, on which our graphene is grown via chemical vapour deposition (CVD), to be oxidised before the reaction can occur. This was confirmed through X-ray photoelectron spectroscopy (XPS) data of both oxidised and reduced Cu substrate samples. The GNBs have been analysed through atomic force microscopy (AFM, after NH3 treatment) and XPS, which reveals the formation of five distinct N 1s peaks, attributed to N2 entrapment, N doping species and atomic nitrogen bonded with the Cu within the substrate. This method is simple, occurs at low temperatures (520 K) and integrates very easily with conventional CVD graphene growth, so presents an opportunity to open up this field of research further.

Crystallization of molecular layers produced under confinement onto a surface.

It is well known that molecules confined very close to a surface arrange into molecular layers. Because solid-liquid interfaces are ubiquitous in the chemical, biological and physical sciences, it is crucial to develop methods to easily access molecular layers and exploit their distinct properties by producing molecular layered crystals. Here we report a method based on crystallization in ultra-thin puddles enabled by gas blowing, which allows to produce molecular layered crystals with thickness down to the monolayer onto a surface, making them directly accessible for characterization and further processing. By selecting four molecules with different types of polymorphs, we observed exclusive crystallization of polymorphs with Van der Waals interlayer interactions, which have not been observed with traditional confinement methods. In conclusion, the gas blowing approach unveils the opportunity to perform materials chemistry under confinement onto a surface, enabling the formation of distinct crystals with selected polymorphism.

Anisotropic Thermal Conductivity of Inkjet-Printed 2D Crystal Films: Role of the Microstructure and Interfaces.

Two-dimensional (2D) materials are uniquely suited for highly anisotropic thermal transport, which is important in thermoelectrics, thermal barrier coatings, and heat spreaders. Solution-processed 2D materials are attractive for simple, low-cost, and large-scale fabrication of devices on, virtually, any substrate. However, to date, there are only few reports with contrasting results on the thermal conductivity of graphene films, while thermal transport has been hardly measured for other types of solution-processed 2D material films. In this work, inkjet-printed graphene, h-BN and MoS2 films are demonstrated with thermal conductivities of ∼10 Wm-1K-1 and ∼0.3 Wm-1K-1 along and across the basal plane, respectively, giving rise to an anisotropy of ∼30, hardly dependent on the material type and annealing treatment. First-principles calculations indicate that portion of the phonon spectrum is cut-off by the quality of the thermal contact for transport along the plane, yet the ultra-low conductivity across the plane is associated with high-transmissivity interfaces. These findings can drive the design of highly anisotropic 2D material films for heat management applications.

Hybrid MoS2/PEDOT:PSS transporting layers for interface engineering of nanoplatelet-based light-emitting diodes.

Colloidal semiconductor nanoplatelets (NPLs) are a subgroup of quantum confined materials that have recently emerged as promising active materials for solution processed light-emitting diodes (LEDs) thanks to their peculiar structural and electronic properties as well as their reduced dimensionality. Nowadays, the conventional structure for NPL-based LEDs makes use of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as a hole transporting layer (HTL). This is a well-known conjugated conductive polymer because it leads to high LED efficiency, though it has limited stability in air due to its intrinsic acidity and hygroscopicity. Here, we develop a nanocomposite aqueous ink, obtained by blending commercial PEDOT:PSS with water-based, stable and highly concentrated molybdenum disulfide (MoS2) nanosheets, obtained via liquid phase exfoliation (LPE), which is suitable as a HTL for solution processed NPL-based LEDs. We demonstrate that the MoS2 additive effectively works as a performance booster in unpackaged devices, thereby prolonging the lifetime up to 1000 hours under ambient conditions. Moreover, the addition of MoS2 induces a modification of the anode interface properties, including a change in the work function and a significant enhancement of the permittivity of the HTL.

Exploiting the Surface Properties of Graphene for Polymorph Selectivity.

Producing crystals of the desired form (polymorph) is currently a challenge as nucleation is yet to be fully understood. Templated crystallization is an efficient approach to achieve polymorph selectivity; however, it is still unclear how to design the template to achieve selective crystallization of specific polymorphs. More insights into the nanoscale interactions happening during nucleation are needed. In this work, we investigate crystallization of glycine using graphene, with different surface chemistry, as a template. We show that graphene induces the preferential crystallization of the metastable α-polymorph compared to the unstable ß-form at the contact region of an evaporating droplet. Computer modeling indicates the presence of a small amount of oxidized moieties on graphene to be responsible for the increased stabilization of the α-form. In conclusion, our work shows that graphene could become an attractive material for polymorph selectivity and screening by exploiting its tunable surface chemistry.

Gas Blow Coating: A Deposition Technique To Control the Crystal Morphology in Thin Films of Organic Semiconductors.

Rapid, large-scale, and low-cost coating methods that enable precise control of the crystal growth of organic semiconductors are essential to deliver high-performance devices that are robust and reproducible. In this work, a novel method is presented based on a gas blow coating technique, enabling the deposition of thin films of organic semiconductors, whose morphology can be optimized by adjusting the deposition parameters. We demonstrate the deposition of aligned single crystals of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) by gas blow coating and their use as active layers in organic field-effect transistor (OFET) devices. The OFETs of TIPS-pentacene and C8-BTBT have charge mobilities of 0.15 and 1.4 cm2 V-1 s-1, respectively, with low threshold voltages and on/off ratios exceeding 105. This coating method can also be extended to polymeric semiconductors: films based on poly(3-hexylthiophene) and poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)] are realized, establishing gas blow coating as a novel and efficient technique for the deposition of thin films of organic semiconductors.

All-2D Material Inkjet-Printed Capacitors: Toward Fully Printed Integrated Circuits.

A well-defined insulating layer is of primary importance in the fabrication of passive ( e.g., capacitors) and active ( e.g., transistors) components in integrated circuits. One of the most widely known two-dimensional (2D) dielectric materials is hexagonal boron nitride (hBN). Solution-based techniques are cost-effective and allow simple methods to be used for device fabrication. In particular, inkjet printing is a low-cost, noncontact approach, which also allows for device design flexibility, produces no material wastage, and offers compatibility with almost any surface of interest, including flexible substrates. In this work, we use water-based and biocompatible graphene and hBN inks to fabricate all-2D material and inkjet-printed capacitors. We demonstrate an areal capacitance of 2.0 ± 0.3 nF cm-2 for a dielectric thickness of ∼3 µm and negligible leakage currents, averaged across more than 100 devices. This gives rise to a derived dielectric constant of 6.1 ± 1.7. The inkjet printed hBN dielectric has a breakdown field of 1.9 ± 0.3 MV cm-1. Fully printed capacitors with sub-micrometer hBN layer thicknesses have also been demonstrated. The capacitors are then exploited in two fully printed demonstrators: a resistor-capacitor (RC) low-pass filter and a graphene-based field effect transistor.