Luca Camilli

Light harvesting with multiwall carbon nanotube/silicon heterojunctions

We report on a significant photocurrent generation from a planar device obtained by coating a bare n doped silicon substrate with a random network of multiwall carbon nanotubes (MWCNTs). This MWCNT/n-Si hybrid device exhibits an incident photon to current efficiency reaching up to 34% at 670 nm. We also show that MWCNTs covering a quartz substrate still exhibit photocurrent, though well below than that of the MWCNTs coating the silicon substrate. These results suggest that MWCNTs are able to generate photocurrent and that the silicon substrate plays a fundamental role in our planar device. The former effect is particularly interesting because MWCNTs are generally known to mimic the electronic properties of graphite, which does not present any photocurrent generation. On the basis of theoretical calculations revealing a weak metallic character for MWCNTs, we suggest that both metallic and semiconducting nanotubes are able to generate e-h pairs upon illumination. This can be ascribed to the presence of van Hove singularities in the density of states of each single wall carbon nanotube constituting the MWCNT and to the low density of electrons at the Fermi level. Finally, we suggest that though both MWCNTs and Si substrate are involved in the photocurrent generation process, MWCNT film mainly acts as a semitransparent electrode in our silicon-based device.

Pressure-dependent electrical conductivity of freestanding three-dimensional carbon nanotube network”

The dependence of electrical conductivity on compression of a freestanding three-dimensional carbon nanotube (CNT) network is investigated. This macrostructure is made of mm-long and entangled CNTs, forming a random skeleton with open pores. The conductivity linearly increases with the applied compression. This behaviour is due to increase of percolating pathways—contacts among neighbouring CNTs—under loads that is highlighted by in situ scanning electron microscopy analysis. The network sustains compressions up to 75% and elastically recovers its morphology and conductivity during the release period. The repeatability coupled with the high mechanical properties makes the CNT network interesting for pressure-sensing applications.

Self-assembly of ordered graphene nanodot arrays

The ability to fabricate nanoscale domains of uniform size in two-dimensional materials could potentially enable new applications in nanoelectronics and the development of innovative metamaterials. However, achieving even minimal control over the growth of two-dimensional lateral heterostructures at such extreme dimensions has proven exceptionally challenging. Here we show the spontaneous formation of ordered arrays of graphene nano-domains (dots), epitaxially embedded in a two-dimensional boron–carbon–nitrogen alloy. These dots exhibit a strikingly uniform size of 1.6 ± 0.2 nm and strong ordering, and the array periodicity can be tuned by adjusting the growth conditions. We explain this behaviour with a model incorporating dot-boundary energy, a moiré-modulated substrate interaction and a long-range repulsion between dots. This new two-dimensional material, which theory predicts to be an ordered composite of uniform-size semiconducting graphene quantum dots laterally integrated within a larger-bandgap matrix, holds promise for novel electronic and optoelectronic properties, with a variety of potential device applications.The nanoscale patterning of two-dimensional materials offers the possibility of novel optoelectronic properties; however, it remains challenging. Here, Camilli et al. show the self-assembly of large arrays of highly-uniform graphene dots imbedded in a BCN matrix, enabling novel devices.

Real-time oxide evolution of copper protected by graphene and boron nitride barriers

Applying protective or barrier layers to isolate a target item from the environment is a common approach to prevent or delay its degradation. The impermeability of two-dimensional materials such as graphene and hexagonal boron nitride (hBN) has generated a great deal of interest in corrosion and material science. Owing to their different electronic properties (graphene is a semimetal, whereas hBN is a wide-bandgap insulator), their protection behaviour is distinctly different. Here we investigate the performance of graphene and hBN as barrier coatings applied on copper substrates through a real-time study in two different oxidative conditions. Our findings show that the evolution of the copper oxidation is remarkably different for the two coating materials.

Failure of multi-layer graphene coatings in acidic media

Being impermeable to all gases, graphene has been proposed as an effective ultrathin barrier film and protective coating. However, here it is shown how the gastight property of graphene-based coatings may indirectly lead to their catastrophic failure under certain conditions. When nickel coated with thick, high-quality chemical vapor deposited multilayered graphene is exposed to acidic solutions, a dramatic evolution of gas is observed at the coating–substrate interface. The gas bubbles grow and merge, eventually rupturing and delaminating the coating. This behavior, attributed to cathodic hydrogen evolution, can also occur spontaneously on a range of other technologically important metals and alloys based on iron, zinc, aluminum and manganese; this makes these findings relevant for practical applications of graphene-based coatings.

Raman spectral indicators of catalyst decoupling for transfer of CVD grown 2D materials

Through a combination of monitoring the Raman spectral characteristics of 2D materials grown on copper catalyst layers, and wafer scale automated detection of the fraction of transferred material, we reproducibly achieve transfers with over 97.5% monolayer hexagonal boron nitride and 99.7% monolayer graphene coverage, for up to 300 mm diameter wafers. We find a strong correlation between the transfer coverage obtained for graphene and the emergence of a lower wavenumber 2D− peak component, with the concurrent disappearance of the higher wavenumber 2D+ peak component during oxidation of the catalyst surface. The 2D peak characteristics can therefore act as an unambiguous predictor of the success of the transfer. The combined monitoring and transfer process presented here is highly scalable and amenable for roll-to-roll processing.

Complete long-term corrosion protection with chemical vapor deposited graphene

Abstract Despite numerous reports regarding the potential of graphene for corrosion protection, examples of chemical vapor deposited (CVD) graphene-based anticorrosive coatings able to provide long-term protection (i.e. several months) of metals have so far been absent. Here, we present a polymer-graphene hybrid coating, comprising two single layers of CVD graphene sandwiched by three layers of polyvinyl butyral, which provides complete corrosion protection of commercial aluminum alloys even after 120 days of exposure to simulated seawater. The essential role played by graphene in the hybrid coating is evident when we compare the results from a polymer-only coating of the same thickness, which fails in protecting the metal after less than 30 days. With the emergence of commercially available large-area CVD graphene, our work demonstrates a straightforward approach towards high-performance anticorrosive coatings, which can be extended to other two-dimensional materials and polymers, for long-term protection of various relevant metals and alloys.

CVD Graphene/Ni Interface Evolution in Sulfuric Electrolyte

Systems comprising single and multilayer graphene deposited on metals and immersed in acid environments have been investigated, with the aim of elucidating the mechanisms involved, for instance, in hydrogen production or metal protection from corrosion. In this work, a relevant system, namely chemical vapor deposited (CVD) multilayer graphene/Ni (MLGr/Ni), is studied when immersed in a diluted sulfuric electrolyte. The MLGr/Ni electrochemical and morphological properties are studied in situ and interpreted in light of the highly oriented pyrolytic graphite (HOPG) electrode behavior, when immersed in the same electrolyte. Following this interpretative framework, the dominant role of the Ni substrate in hydrogen production is clarified.

Nondestructive Thickness Mapping of Wafer-Scale Hexagonal Boron Nitride Down to a Monolayer

The availability of an accurate, nondestructive method for measuring thickness and continuity of two-dimensional (2D) materials with monolayer sensitivity over large areas is of pivotal importance for the development of new applications based on these materials. While simple optical contrast methods and electrical measurements are sufficient for the case of metallic and semiconducting 2D materials, the low optical contrast and high electrical resistivity of wide band gap dielectric 2D materials such as hexagonal boron nitride (hBN) hamper their characterization. In this work, we demonstrate a nondestructive method to quantitatively map the thickness and continuity of hBN monolayers and bilayers over large areas. The proposed method is based on acquisition and subsequent fitting of ellipsometry spectra of hBN on Si/SiO2 substrates. Once a proper optical model is developed, it becomes possible to identify and map the commonly observed polymer residuals from the transfer process and obtain submonolayer thickness sensitivity for the hBN film. With some assumptions on the optical functions of hBN, the thickness of an as-transferred hBN monolayer on SiO2 is measured as 4.1 Å ± 0.1 Å, whereas the thickness of an air-annealed hBN monolayer on SiO2 is measured as 2.5 Å ± 0.1 Å. We argue that the difference in the two measured values is due to the presence of a water layer trapped between the SiO2 surface and the hBN layer in the latter case. The procedure can be fully automated to wafer scale and extended to other 2D materials transferred onto any polished substrate, as long as their optical functions are approximately known.

Erratum: Self-assembly of ordered graphene nanodot arrays

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