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Irradiation-induced broadening of the Raman spectra in monolayer graphene

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 Added by Eugene Kogan
 Publication date 2019
  fields Physics
and research's language is English




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Broadening of the Raman scattering (RS) spectra was studied in monolayer graphene samples irradiated with various dose of ions followed by annealing of radiation damage at different temperatures. It is shown that the width {Gamma} (full width at half maximum, FWHM) of three main RS lines (G-, D-, and 2D) increases linearly with increase of the density of irradiation-induced point defects N d as {Delta}{Gamma} = m N d . The slope m of the linear dependencies is the same for one-phonon emitting G-line and D-line, and almost double for two-phonon emitting 2D-line. It is also shown that the width of D-line {Gamma} D for all samples is larger than one half of the width of 2D-line {Gamma} 2D , which shows that in the case of D-line, elastic electron scattering on point defects leads to an additional decreasing the lifetime of the emitted phonon. Theoretical model of the width of D-line in disordered graphene is developed which explains the experimental observations and allows to determine the numerical coefficient in the in-plane transverse optic phonon dispersion in graphene.



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97 - I. Shlimak , E. Zion , A. Butenko 2019
A brief review of experiments directed to study a gradual localization of charge carriers and metal-insulator transition in samples of disordered monolayer graphene is presented. Disorder was induced by irradiation with different doses of heavy and light ions. Degree of disorder was controlled by measurements of the Raman scattering spectra. The temperature dependences of conductivity and magnetoresistance (MR) showed that at low disorder, conductivity is governed by the weak localization and antilocalization regime. Further increase of disorder leads to strong localization of charge carriers, when the conductivity is described by the variable-range-hopping (VRH) mechanism. It was observed that MR in the VRH regime is negative in perpendicular fields and is positive in parallel magnetic fields which allowed to reveal different mechanisms of hopping MR. Theoretical analysis is in a good agreement with experimental data.
The Raman scattering spectra (RS) of two series of monolayer graphene samples irradiated with various doses of C$^{+}$ and Xe$^{+}$ ions were measured after annealing in high vacuum, and in forming gas (95%Ar+5%H$_{2}$). It was found that these methods of annealing have dramatically different influence on the RS lines. Annealing in vacuum below 500$^{circ}$C leads to significant decrease of both D-line, associated with defects, and 2D-line, associated with the intact lattice structure, which can be explained by annealing-induced enhanced doping. Further annealing in vacuum up to 1000$^{circ}$C leads to significant increase of 2D-line together with continuous decrease of D-line, which gives evidence of partial removal of defects and recovery of the damaged lattice. Annealing in forming gas is less effective in this sense. The blue shift of all lines is observed after annealing. It is shown that below 500$^{circ}$C, the unintentional doping is the main mechanism of shift, while at higher annealing temperatures, the lattice strain dominates due to mismatch of the thermal expansion coefficient of graphene and the SiO$_{2}$ substrate. Inhomogeneous distribution of stress and doping across the samples leads to the correlated variation of the amplitude and the peak position of RS lines.
113 - E. Zion , A.Haran , A. V. Butenko 2015
Gradual localization of charge carriers was studied in a series of micro-size samples of monolayer graphene fabricated on the common large scale film and irradiated by different doses of C$^+$ ions with energy 35 keV. Measurements of the temperature dependence of conductivity and magnetoresistance in fields up to 4 T showed that at low disorder, the samples are in the regime of weak localization and antilocalization. Further increase of disorder leads to strong localization regime, when conductivity is described by the variable-range-hopping (VRH) mechanism. A crossover from the Mott regime to the Efros-Shklovskii regime of VRH is observed with decreasing temperature. Theoretical analysis of conductivity in both regimes showed a remarkably good agreement with experimental data.
The influence of long-term ageing (about one year) on the Raman scattering (RS) spectra and the temperature dependence of conductivity has been studied in two series of monolayer graphene samples irradiated by different doses of C$^{+}$ and Xe$^{+}$ ions. It is shown that the main result of ageing consists of changes in the intensity and position of D- and G- and 2D-lines in RS spectra and in an increase of the conductivity. The observed effects are explained in terms of an increase of the radius of the textquotedblleft activatedtextquotedblright{} area around structural defects.
We calculate the double resonant (DR) Raman spectrum of graphene, and determine the lines associated to both phonon-defect processes, and two-phonons ones. Phonon and electronic dispersions reproduce calculations based on density functional theory corrected with GW. Electron-light, -phonon, and -defect scattering matrix elements and the electronic linewidth are explicitly calculated. Defect-induced processes are simulated by considering different kind of idealized defects. For an excitation energy of $epsilon_L=2.4$ eV, the agreement with measurements is very good and calculations reproduce: the relative intensities among phonon-defect or among two-phonon lines; the measured small widths of the D, $D$, 2D and $2D$ lines; the line shapes; the presence of small intensity lines in the 1800, 2000 cm$^{-1}$ range. We determine how the spectra depend on the excitation energy, on the light polarization, on the electronic linewidth, on the kind of defects and on their concentration. According to the present findings, the intensity ratio between the $2D$ and 2D lines can be used to determine experimentally the electronic linewidth. The intensity ratio between the $D$ and $D$ lines depends on the kind of model defect, suggesting that this ratio could possibly be used to identify the kind of defects present in actual samples. Charged impurities outside the graphene plane provide an almost undetectable contribution to the Raman signal.
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