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Modulating charge density and inelastic optical response in graphene by atmospheric pressure localized intercalation through wrinkles

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 Added by Johann Coraux
 Publication date 2013
  fields Physics
and research's language is English




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The intercalation of an oxide barrier between graphene and its metallic substrate for chem- ical vapor deposition is a contamination-free alternative to the transfer of graphene to dielectric supports, usually needed for the realization of electronic devices. Low-cost pro- cesses, especially at atmospheric pressure, are desirable but whether they are achievable remains an open question. Combining complementary microscopic analysis, providing structural, electronic, vibrational, and chemical information, we demonstrate the spontaneous reactive intercalation of 1.5 nm-thick oxide ribbons between graphene and an iridium substrate, at atmospheric pressure and room temperature. We discover that oxygen-containing molecules needed for forming the ribbons are supplied through the graphene wrinkles, which act as tunnels for the efficient diffusion of molecules entering their free end. The intercalated oxide ribbons are found to modify the graphene-support interaction, leading to the formation of quasi-free-standing high quality graphene whose charge density is modulated in few 10-100 nm-wide ribbons by a few 10^12 cm-2, where the inelastic optical response is changed, due to a softening of vibrational modes - red-shifts of Raman G and 2D bands by 6 and 10 cm-1, respectively.



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We present a study of quasi-free-standing monolayer graphene obtained by intercalation of Au atoms at the interface between the carbon buffer layer (Bu-L) and the silicon-terminated face (0001) of 4H-silicon carbide. Au intercalation is achieved by deposition of atomically thin Au on the Bu-L followed by annealing at 850 {deg}C in an Argon atmosphere. We explore the intercalation of Au and decoupling of the Bu-L into quasi-free-standing monolayer graphene by surface science characterizations and electron transport in top-gated electronic devices. By gate-dependent magnetotransport we find that the Au-intercalated buffer layer displays all properties of monolayer graphene, namely gate tunable ambipolar transport across the Dirac point, and n- or p-type doping depending on the Au content.
We present a method for decoupling epitaxial graphene grown on SiC(0001) by intercalation of a layer of fluorine at the interface. The fluorine atoms do not enter into a covalent bond with graphene, but rather saturate the substrate Si bonds. This configuration of the fluorine atoms induces a remarkably large hole density of p approx 4.5 times 1013 cm-2, equivalent to the location of the Fermi level at 0.79 eV above the Dirac point ED .
We present a study of charge transfer in Na-intercalated FeOCl and polyaniline-intercalated FeOCl using high-resolution x-ray absorption spectroscopy and resonant x-ray emission spectroscopy at the Fe-K edge. By comparing the experimental data with ab-initio simulations, we are able to unambiguously distinguish the spectral changes which appear due to intercalation into those of electronic origin and those of structural origin. For both systems, we find that about 25% of the Fe sites are reduced to Fe2+ via charge transfer between FeOCl and the intercalate. This is about twice as large as the Fe2+ fraction reported in studies using Mossbauer spectroscopy. This discrepancy is ascribed to the fact that the charge transfer occurs on the same time scale as the Mossbauer effect itself. Our result suggests that every intercalated atom or molecule is involved in the charge-transfer process, thus making this process a prerequisite for intercalation. The Fe2+ fraction is found to increase with pressure for polyaniline-FeOCl, hinting at an enhancement of the conductivity in the FeOCl intercalation compounds under pressure.
Two charge density wave transition can be detected in LaAu$_x$Sb$_2$ at ~ 110 and ~ 90 K by careful electrical transport measurements. Whereas control of the Au site occupancy in LaAu$_x$Sb$_2$ (for 0.9 < x < 1.0) can suppress each of these transitions by ~ 80 K, the application of hydrostatic pressure can completely suppress the lower transition by ~ 10 kbar and the upper transition by ~ 17 kbar. Clear anomalies in the resistance as well as the magnetoresistance are observed to coincide with the pressures at which the charge density wave transitions are driven to zero.
125 - C. Riedl , C. Coletti , T. Iwasaki 2009
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