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Raman spectroscopy as probe of nanometer-scale strain variations in graphene

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 Added by Christoph Neumann
 Publication date 2014
  fields Physics
and research's language is English




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Confocal Raman spectroscopy is a versatile, non-invasive investigation tool and a major workhorse for graphene characterization. Here we show that the experimentally observed Raman 2D line width is a measure of nanometer-scale strain variations in graphene. By investigating the relation between the G and 2D line at high magnetic fields we find that the 2D line width contains valuable information on nanometer-scale flatness and lattice deformations of graphene, making it a good quantity for classifying the structural quality of graphene even at zero magnetic field.



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We present a molecular modeling study analyzing nanometer-scale strain variations in graphene as a function of externally applied tensile strain. We consider two different mechanisms that could underlie nanometer-scale strain variations: static perturbations from lattice imperfections of an underlying substrate and thermal fluctuations. For both cases we observe a decrease in the out-of-plane atomic displacements with increasing strain, which is accompanied by an increase in the in-plane displacements. Reflecting the non-linear elastic properties of graphene, both trends together yield a non-monotonic variation of the total displacements with increasing tensile strain. This variation allows to test the role of nanometer-scale strain variations in limiting the carrier mobility of high-quality graphene samples.
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The equilibrium optical phonons of graphene are well characterized in terms of anharmonicity and electron-phonon interactions, however their non-equilibrium properties in the presence of hot charge carriers are still not fully explored. Here we study the Raman spectrum of graphene under ultrafast laser excitation with 3ps pulses, which trade off between impulsive stimulation and spectral resolution. We localize energy into hot carriers, generating non-equilibrium temperatures in the ~1700-3100K range, far exceeding that of the phonon bath, while simultaneously detecting the Raman response. The linewidth of both G and 2D peaks show an increase as function of the electronic temperature. We explain this as a result of the Dirac cones broadening and electron-phonon scattering in the highly excited transient regime, important for the emerging field of graphene-based photonics and optoelectronics.
Raman spectroscopy is a powerful tool for characterizing the local properties of graphene. Here, we introduce a method for evaluating unknown strain configurations and simultaneous doping. It relies on separating the effects of hydrostatic strain (peak shift) and shear strain (peak splitting) on the Raman spectrum of graphene. The peak shifts from hydrostatic strain and doping are separated with a correlation analysis of the 2D and G frequencies. This enables us to obtain the local hydrostatic strain, shear strain and doping without any assumption on the strain configuration prior to the analysis. We demonstrate our approach for two model cases: Graphene under uniaxial stress on a PMMA substrate and graphene suspended on nanostructures that induce an unknown strain configuration. We measured $omega_mathrm{2D}/omega_mathrm{G} = 2.21 pm 0.05$ for pure hydrostatic strain. Raman scattering with circular corotating polarization is ideal for analyzing strain and doping, especially for weak strain when the peak splitting by shear strain cannot be resolved.
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