In this work we present a simple pathway to obtain large single-crystal graphene on copper (Cu) foils with high growth rates using a commercially available cold-wall chemical vapour deposition (CVD) reactor. We show that graphene nucleation density is drastically reduced and crystal growth is accelerated when: i) using ex-situ oxidised foils; ii) performing annealing in an inert atmosphere prior to growth; iii) enclosing the foils to lower the precursor impingement flux during growth. Growth rates as high as 14.7 and 17.5 µm per minute are obtained on flat and folded foils, respectively. Thus, single-crystal grains with lateral size of about one millimetre can be obtained in just one hour. The samples are characterised by optical microscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy as well as selected area electron diffraction (SAED) and low-energy electron diffraction (LEED), which confirm the high quality and homogeneity of the films. The development of a process for the quick production of large grain graphene in a commonly used commercial CVD reactor is a significant step towards an increased accessibility to millimetre-sized graphene crystals.

The surface structure of Few-Layer Graphene (FLG) epitaxially grown on the C-face of SiC has been investigated by TM-AFM in ambient air and upon interaction with dilute aqueous solutions of bio-organic molecules (l-methionine and dimethyl sulfoxide, DMSO). Before interaction with molecular solutions, we observe nicely ordered, three-fold oriented rippled domains, with a 4.7 ± 0.2 nm periodicity (small periodicity, SP) and a peak-to-valley distance in the range 0.1-0.2 nm. Upon mild interaction with the molecular solution, the ripple periodicity "relaxes" to 6.2 ± 0.2 nm (large periodicity, LP), while the peak-to-valley height increases to 0.2-0.3 nm. When additional energy is transferred to the system through sonication in solution, graphene planes are peeled off, as shown by quantitative analysis of Raman spectroscopy and X-ray photoelectron spectroscopy which indicate a neat reduction of thickness. Upon exfoliation rippled domains are no longer observed. In comparative experiments on cleaved HOPG, we could not observe ripples on pristine samples in ambient air, while LP ripples develop upon interaction with the molecular solutions. Recent literature on similar systems is not univocal regarding the interpretation of rippling. The ensemble of our comparative observations on FLG and HOPG can be hardly rationalized solely on the basis of the surface assembly of molecules, either organic molecules coming from the solution or adventitious species. We propose to consider rippling as the manifestation of the free-energy minimization of quasi-2D layers, eventually affected by factors such as interplanar stacking, and interactions with molecules and/or with the AFM tip.

We report an investigation of the graphene/substrate interface morphology in large-area polycrystalline graphene grown by chemical-vapour deposition and wet-transferred onto Si wafers. We combined spectroscopic ellipsometry, X-ray photoelectron spectroscopy and atomic-force microscopy in order to yield morphological and chemical information about the system. The data showed that wet-transferred samples may randomly exhibit nanosized relief patterns indicative of small water nanopockets trapped between graphene and the underlying substrate. These pockets affect the adhesion of graphene to the substrate, but can be efficiently removed upon a mild annealing in high vacuum. We show that ellipsometry is capable of successfully and reliably detecting, via multilayer dielectric modelling, both the presence of such a spurious intercalation layer and its removal. The fast, broadly applicable and non-invasive character of this technique can therefore promote its application for quickly and reliably assessing the degree of adhesion of graphene transferred onto target substrates, either for ex-post evaluation or in-line process monitoring

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