Cameron J. Shearer

Application and Future Challenges of Functional Nanocarbon Hybrids

Hybridizing nanocarbons, such as carbon nanotubes (CNTs) or graphene, with an active material is a powerful strategy towards designing next-generation functional materials for environmental and sustainable energy applications. While research on nanocomposites, created by dispersing the nanocarbon into polymer or ceramic matrices, began almost immediately after the popularization of CNTs and graphene in 1991 and 2004, respectively, nanocarbon hybrids are a relatively recent addition to the family of composite materials. In contrast to nanocomposites, which typically combine the intrinsic properties of both compounds, nanocarbon hybrids additionally provide access to both a large surface area required for gas/liquid-solid interactions and an extended interface, through which charge and energy transfer processes create synergistic effects that result in unique properties and superior performance. This progress report looks at the history of research on nanocarbons (fullerenes, CNTs and graphene) and their composites and hybrids, presents the origin of synergistic effects, reviews the most intriguing results on nanocarbon hybrid performance in heterogeneous catalysis, electrocatalysis, photocatalysis, batteries, supercapacitors, photovoltaics and sensors, and discusses remaining challenges and future research directions.

Dual Silane Surface Functionalization for the Selective Attachment of Human Neuronal Cells to Porous Silicon

Porous silicon (pSi) surfaces were chemically micropatterned through a combination of photolithography and surface silanization reactions. This patterning technique produces discretely defined regions on a pSi surface functionalized with a specific chemical functionality, and the surrounding surface displays a completely different functionality. The generated chemical patterns were characterized by a combination of IR microscopy and the conjugation of two different fluorescent organic dyes. Finally, the chemically patterned pSi surface was used to direct the attachment of neuronal cells to the surface. This patterning strategy will be useful for the development of high-throughput platforms for investigating cell behavior.

Accurate thickness measurement of graphene

Graphene has emerged as a material with a vast variety of applications. The electronic, optical and mechanical properties of graphene are strongly influenced by the number of layers present in a sample. As a result, the dimensional characterization of graphene films is crucial, especially with the continued development of new synthesis methods and applications. A number of techniques exist to determine the thickness of graphene films including optical contrast, Raman scattering and scanning probe microscopy techniques. Atomic force microscopy (AFM), in particular, is used extensively since it provides three-dimensional images that enable the measurement of the lateral dimensions of graphene films as well as the thickness, and by extension the number of layers present. However, in the literature AFM has proven to be inaccurate with a wide range of measured values for single layer graphene thickness reported (between 0.4 and 1.7 nm). This discrepancy has been attributed to tip-surface interactions, image feedback settings and surface chemistry. In this work, we use standard and carbon nanotube modified AFM probes and a relatively new AFM imaging mode known as PeakForce tapping mode to establish a protocol that will allow users to accurately determine the thickness of graphene films. In particular, the error in measuring the first layer is reduced from 0.1-1.3 nm to 0.1-0.3 nm. Furthermore, in the process we establish that the graphene-substrate adsorbate layer and imaging force, in particular the pressure the tip exerts on the surface, are crucial components in the accurate measurement of graphene using AFM. These findings can be applied to other 2D materials.

Interface engineering in nanocarbon–Ta2O5 hybrid photocatalysts

Hybridizing inorganic nanomaterials with carbon nanotubes and graphene constitutes a powerful approach towards creating new functional materials for environmental and sustainable energy applications. Their superior performance originates from synergistic effects based on charge and energy transfer processes at the hybrids interfaces. However, only few studies have been devoted so far towards rationally designing these hybrids. In this work we demonstrate that engineering interfaces as well as the morphology of the functional inorganic compound can maximise the synergistic effects in hybrids, thus further enhancing the hybrids photocatalytic properties. Particularly, we have stimulated the growth of ultra-thin single-crystalline layers of tantalum (V) oxide (Ta2O5) with preferred orientation at substantially reduced crystallisation temperatures, by utilising the graphitic CNT surfaces as seed crystals through heterogeneous nucleation. The resulting hybrids possess outstanding activities for the evolution of hydrogen via sacrificial water splitting that are about 35 times higher than those of comparable materials such as tantalates. The additional improvements in this hybrid are attributed to the single-crystalline nature of the coating, which alleviates transport of electrons to the interface, as well as the formation of a Schottky-type junction between the metallic nanocarbon and the semiconducting metal oxide, which facilitates charge transfer and thus charge separation at the interface.

Solution processed graphene structures for perovskite solar cells

Organometallic trihalide perovskite light absorber based solar cells have drawn increasing attention because of their recent rapid increase in power conversion efficiency (PCE). These photovoltaic cells have relied significantly on transparent conducting oxide (TCO) electrodes which are costly and brittle. Herein, solution processed transparent conductive graphene films (TCGFs) are utilized, for the first time, as an alternative to traditional TCO electrodes at the electron collecting layer in perovskite solar cells (PSCs). By investigating and optimizing the trade-off between transparency and sheet resistance (Rs) of the graphene films, a PCE of 0.62% is achieved. This PCE is further improved to 0.81% by incorporating graphene structures into both compact and mesoporous TiO2 layers of the solar cell. We anticipate that the present study will lead to further work to develop graphene-based transparent conductive electrodes for future solar cell devices.

Micropatterned Arrays of Porous Silicon: Toward Sensory Biointerfaces

We describe the fabrication of arrays of porous silicon spots by means of photolithography where a positive photoresist serves as a mask during the anodization process. In particular, photoluminescent arrays and porous silicon spots suitable for further chemical modification and the attachment of human cells were created. The produced arrays of porous silicon were chemically modified by means of a thermal hydrosilylation reaction that facilitated immobilization of the fluorescent dye lissamine, and alternatively, the cell adhesion peptide arginine-glycine-aspartic acid-serine. The latter modification enabled the selective attachment of human lens epithelial cells on the peptide functionalized regions of the patterns. This type of surface patterning, using etched porous silicon arrays functionalized with biological recognition elements, presents a new format of interfacing porous silicon with mammalian cells. Porous silicon arrays with photoluminescent properties produced by this patterning strategy also have potential applications as platforms for in situ monitoring of cell behavior.

Carbon Nanotubes Anchored to Silicon for Device Fabrication

This report highlights recent progress in the fabrication of vertically aligned carbon nanotubes (VA-CNTs) on silicon-based materials. Research into these nanostructured composite materials is spurred by the importance of silicon as a basis for most current devices and the disruptive properties of CNTs. Various CNT attachments methods of covalent and adsorptive nature are critically compared. Selected examples of device applications where the VA-CNT on silicon assemblies are showing particular promise are discussed. These applications include field emitters, filtration membranes, dry adhesives, sensors and scaffolds for biointerfaces.

Carbon Nanotubes in TiO2 Nanofiber Photoelectrodes for High‐Performance Perovskite Solar Cells

1D semiconducting oxides are unique structures that have been widely used for photovoltaic (PV) devices due to their capability to provide a direct pathway for charge transport. In addition, carbon nanotubes (CNTs) have played multifunctional roles in a range of PV cells because of their fascinating properties. Herein, the influence of CNTs on the PV performance of 1D titanium dioxide nanofiber (TiO2 NF) photoelectrode perovskite solar cells (PSCs) is systematically explored. Among the different types of CNTs, single‐walled CNTs (SWCNTs) incorporated in the TiO2 NF photoelectrode PSCs show a significant enhancement (≈40%) in the power conversion efficiency (PCE) as compared to control cells. SWCNTs incorporated in TiO2 NFs provide a fast electron transfer within the photoelectrode, resulting in an increase in the short‐circuit current (J sc) value. On the basis of our theoretical calculations, the improved open‐circuit voltage (V oc) of the cells can be attributed to a shift in energy level of the photoelectrodes after the introduction of SWCNTs. Furthermore, it is found that the incorporation of SWCNTs into TiO2 NFs reduces the hysteresis effect and improves the stability of the PSC devices. In this study, the best performing PSC device constructed with SWCNT structures achieves a PCE of 14.03%.

A virtual instrument to standardise the calibration of atomic force microscope cantilevers

Atomic force microscope (AFM) users often calibrate the spring constants of cantilevers using functionality built into individual instruments. This calibration is performed without reference to a global standard, hindering the robust comparison of force measurements reported by different laboratories. Here, we describe a virtual instrument (an internet-based initiative) whereby users from all laboratories can instantly and quantitatively compare their calibration measurements to those of others-standardising AFM force measurements-and simultaneously enabling non-invasive calibration of AFM cantilevers of any geometry. This global calibration initiative requires no additional instrumentation or data processing on the part of the user. It utilises a single website where users upload currently available data. A proof-of-principle demonstration of this initiative is presented using measured data from five independent laboratories across three countries, which also allows for an assessment of current calibration.

Heterojunction Solar Cells Based on Silicon and Composite Films of Graphene Oxide and Carbon Nanotubes

Graphene oxide (GO) sheets have been used as the surfactant to disperse single-walled carbon nanotubes (CNT) in water to prepare GO/CNT electrodes that are applied to silicon to form a heterojunction that can be used in solar cells. GO/CNT films with different ratios of the two components and with various thicknesses have been used as semitransparent electrodes, and the influence of both factors on the performance of the solar cell has been studied. The degradation rate of the GO/CNT-silicon devices under ambient conditions has also been explored. The influence of the film thickness on the device performance is related to the interplay of two competing factors, namely, sheet resistance and transmittance. CNTs help to improve the conductivity of the GO/CNT film, and GO is able to protect the silicon from oxidation in the atmosphere.