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Various properties of water are affected by confinement as the space-filling of the water molecules is very different from bulk water. In our study, we challenged the creation of a stable system in which water molecules are permanently locked in nanodimensional graphene traps. For that purpose, we developed a technique, nitrocellulose-assisted transfer of graphene grown by chemical vapor deposition, which enables capturing of the water molecules below an atomically thin graphene membrane structured into a net of regular wrinkles with a lateral dimension of about 4 nm. After successfully confining water molecules below a graphene monolayer, we employed cryogenic Raman spectroscopy to monitor the phase changes of the confined water as a function of the temperature. In our experiment system, the graphene monolayer structured into a net of fine wrinkles plays a dual role: (i) it enables water confinement and (ii) serves as an extremely sensitive probe for phase transitions involving water via graphene-based spectroscopic monitoring of the underlying water structure. Experimental findings were supported with classical and path integral molecular dynamics simulations carried out on our experimental system., Comment: 27 pages, 3 Figures + 1 Cover Image

The stacking and bending of graphene are trivial but extremely powerful agents of control over graphene's manifold physics. By changing the twist angle, one can drive the system over a plethora of exotic states via strong electron correlation, thanks to the moir\'e superlattice potentials, while the periodic or triaxial strains induce discretization of the band structure into Landau levels without the need for an external magnetic field. We fabricated a hybrid system comprising both the stacking and bending tuning knobs. We have grown the graphene monolayers by chemical vapor deposition, using $^{12}$C and $^{13}$C precursors, which enabled us to individually address the layers through Raman spectroscopy mapping. We achieved the long-range spatial modulation by sculpturing the top layer ($^{13}$C) over uniform magnetic nanoparticles (NPs) deposited on the bottom layer ($^{12}$C). An atomic force microscopy study revealed that the top layer tends to relax into pyramidal corrugations with C$_3$ axial symmetry at the position of the NPs, which have been widely reported as a source of large pseudomagnetic fields (PMFs) in graphene monolayers. The modulated graphene bilayer (MGBL) also contains a few micrometer large domains, with the twist angle ~ 10$^{\circ}$, which were identified via extreme enhancement of the Raman intensity of the G-mode due to formation of Van Hove singularities (VHSs). We thereby conclude that the twist induced VHSs coexist with the PMFs generated in the strained pyramidal objects without mutual disturbance. The graphene bilayer modulated with magnetic NPs is a non-trivial hybrid system that accommodates features of twist induced VHSs and PMFs in environs of giant classical spins., Comment: 6 figures, 13 pages

Methods for nanoscale material characterization are in ever-increasing demand, especially those that can provide a broader range of information at once. Near-field techniques based on combinations of scanning probe microscopy (SPM) and Raman or photoluminescence (PL) spectroscopy (tip-enhanced Raman spectroscopy [TERS] and/or tip-enhanced photoluminescence [TEPL]) are, thanks to their capabilities and fast development, strong candidates for becoming widespread across the scientific community as SPM and Raman microscopy did only a decade or two ago. Herein, a gap-less TEPL study is performed directly on as-grown MoS2 monolayer samples without any pretreatment or transfer, i.e., without the utilization of plasmonic substrate. Thanks to a mapping resolution as low as a few tens of nanometers, homogeneous layer interiors from defective edge fronts in the grown monolayers can be distinguished. With the aid of additional high-resolution SPM modes, like local surface potential and capacitance measurements, together with nanomechanical mapping, a combination of defects and a lack of substrate doping is suggested as being responsible for the observed PL behavior in the partially delaminated MoS2 layers. In contrast, mechanically exfoliated flakes show topography- and contamination-related heterogeneities in the whole flake area.

Controlled wrinkling of single-layer graphene (1-LG) at nanometer scale was achieved by introducing monodisperse nanoparticles (NPs), with size comparable to the strain coherence length, underneath the 1-LG. Typical fingerprint of the delaminated fraction of 1-LG is identified as substantial contribution to the principal Raman modes of the 1-LG. Correlation analysis of the Raman shift of the modes clearly resolved the 1-LG in contact and delaminated from the substrate, respectively. Intensity of Raman features of the delaminated 1-LG increases linearly with the amount of the wrinkles, determined by advanced processing of atomic force microscopy data. Our study thus offers universal approach for both fine tuning and facile quantification of the graphene topography up to ~ 60% of wrinkling.

Wrinkles in monolayer graphene (GN) affect the GN electronic and transport properties. Defined network of wrinkles can be reached by placing the GN on the substrate decorated with the nanoparticles (NPs). In order to explain mechanism behind the topographically induced changes of the GN electronic structure and to correlate it with the wrinkling, correct description of the GN morphology is of high demand. We demonstrate here how to determine from the atomic force microscopy (AFM) images whether the GN is in the contact with the substrate or it is delaminated, how is the wrinkling of the layer connected with the density of the NPs and if there is the preferential orientation of wrinkles. Also the relevance of detection of the NPs hidden beneath the GN layer is discussed. The study was done on nine samples of the GN on the top of Si-SiO2 substrate, decorated with the metal-oxide NPs of nominal diameter 6 and 10 nm. NP density varied in a range of 20 up to 470 NPs per um2. The projected area of wrinkles was increasing linearly with the increasing NP density, independently on the NP size., Comment: 2nd version: corrected references and text, updated co-authors

We present a comprehensive study of graphene grown by chemical vapor deposition on copper single crystals with exposed (100), (110) and (111) faces. Direct examination of the as-grown graphene by Raman spectroscopy using a range of visible excitation energies and microRaman mapping shows distinct strain and doping levels for individual Cu surfaces. Comparison of results from Raman mapping with X-ray diffraction techniques and Atomic Force Microscopy shows it is neither the crystal quality nor the surface topography responsible for the specific strain and doping values, but it is the Cu lattice orientation itself. We also report an exceptionally narrow Raman 2D band width caused by the interaction between graphene and metallic substrate. The appearance of this extremely narrow 2D band with full-width-at-half maximum (FWHM) as low as 16 cm-1 is correlated with flat and undoped regions on the Cu(100) and (110) surfaces. The generally compressed (~ 0.3% of strain) and n-doped (Fermi level shift of ~250 meV) graphene on Cu(111) shows the 2D band FWHM minimum of ~20 cm-1. In contrast, graphene grown on Cu foil under the same conditions reflects the heterogeneity of the polycrystalline surface and its 2D band is accordingly broader with FWHM > 24 cm-1., Comment: Manuscript 34 pages, 6 Figures; Supporting Information 12 pages, 14 Figures