Penetration of alkali atoms throughout graphene membrane: theoretical modeling

Theoretical studies of penetration of various alkali atoms (Li, Na, Rb, Cs) throughout graphene membrane grown on silicon carbide substrate are reported and compared with recent experimental results. Results of first principles modeling demonstrate rather low (about 0.8 eV) energy barrier for the formation of temporary defects in carbon layer required for the penetration of Li at high concentration of adatoms, higher (about 2 eV) barrier for Na, and barriers above 4 eV for Rb and Cs. Experiments prove migration of lithium adatoms from graphene surface to the buffer layer and SiC substrate at room temperature, sodium at 100{\deg}C and impenetrability of graphene membrane for Rb and Cs. Differences between epitaxial and free standing graphene for the penetration of alkali ions are also discussed.Comment: 16 pages, 3 figure, accepted to Nanoscal

Structure of Self-Assembled Monolayers on Gold Studied by NEXAFS and Photoelectron Spectroscopy

Self-assembled monolayers (SAMs) provide well-defined and ordered films of molecules spontaneously chemisorbed on a surface. By designing molecules with desired functionalities, such molecular film can be interesting for a range of applications from molecular electronics to catalysis. Important parameters for SAM applications are the film structure and quality, which are dependent on the structure of molecular constituents, the substrate, and the self-assembly process. In this work, SAMs on Au(111) of a variety of functionalized molecules, with thiol and silane headgroups, have been studied using high-resolution X-ray photoemission spectroscopy (HRXPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, Infrared reflection absorption spectroscopy (IRRAS), contact angle measurements and Kelvin probe measurements. In particular, the effects of varying the size of the backbone, varying the headgroup, inclusion of a porphyrin tailgroup, different ways of deprotection of the headgroups, and mixed molecular layers have been investigated. The first part of thesis work is focused on SAMs of oligo(phenyleneethynylene) (OPE) derivatives. First the effect of the extent of the conjugated system on the structure of SAM was investigated. As the lateral π-system in the OPE backbone increases, molecular surface densities become lower and molecular inclinations larger. Subsequently, a bulky porphyrin tailgroup was added onto the OPE molecule. Porphyrin-functionalized OPE with several headgroups were compared and the thioacetyl anchor group was found to form a high quality SAM. In the second part of the work, the molecular orientation of thiol-derivatized tetraphenylporphyrin layers was studied. The geometry of the molecular layer and the number of linkers that bind to the gold surface depend strongly on preparation schemes, i.e. whether or not the acetyl protection groups on the thiol were removed before adsorption. Finally, mixed SAMs of a ferrocene-terminated alkanethiol and alkanethiols were studied. By diluting the ferrocene-functionalized molecules in unfunctionalized alkanethiols, the orientational order and the packing density improved. The geometrical structure and the fraction of the ferrocene-terminated molecules can be tuned by controlling the parameters in the preparation scheme

Characterization of Self-Assembled Monolayers of Oligo(phenyleneethynylene) Derivatives on Gold

Oligo(phenyleneethynylene) (OPE) molecules are a class of fully conjugated aromatic molecules, that attract attention for their application as “molecular wires” in molecular electronic devices. In this thesis work, self-assembled monolayers (SAMs) formed from a variety of OPE derivatives have been studied. The chemical properties, structure, and packing density of the SAMs have been characterized utilizing techniques such as high-resolution X-ray photoemission spectroscopy (HRXPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), Infrared reflection absorption spectroscopy (IRRAS), contact angle measurements, and atomic force microscopy (AFM). In a first study, three OPE-derivatives, with benzene, naphthalene and anthracene, respectively, inserted into the backbone, and an acetyl-protected thiophenol binding group were found to form SAMs on Au(111) substrates with lower molecular surface densities and larger molecular inclination as the lateral π-system increases. In a second study, porphyrin was introduced as the end group to a wire-like molecule such as OPE. The purpose was to obtain well-organized and functionalized surfaces with optical and redox properties. Three porphyrin-functionalized OPEs had different binding groups, an acetyl-protected thiophenol, a benzylic thiol, and a trimethylsilylethynylene group, and were found to form SAMs on gold surfaces with difference in structure and degree of order. The molecules with the acetyl-protected thiophenol binding group were found to form a high quality SAM compared to the other two. This SAM exhibits a well-ordered and densely packed layer. This study gives rise to a better understanding of SAM formation of OPE derivatives, and will form a base for further investigations of charge transport properties of these molecular films, which is of interest for applications in molecular electronic devices

Studies of Li intercalation of hydrogenated graphene on SiC(0001)

The effects of Li deposition on hydrogenated bilayer graphene on SiC(0001) samples, i.e. on quasi-freestanding bilayer graphene samples, are studied using low energy electron microscopy, micro-low-energy electron diffraction and photoelectron spectroscopy. After deposition, some Li atoms form islands on the surface creating defects that are observed to disappear after annealing. Some other Li atoms are found to penetrate through the bilayer graphene sample and into the interface where H already resides. This is revealed by the existence of shifted components, related to H–SiC and Li–SiC bonding, in recorded core level spectra. The Dirac point is found to exhibit a rigid shift to about 1.25 eV below the Fermi level, indicating strong electron doping of the graphene by the deposited Li. After annealing the sample at 300–400 °C formation of LiH at the interface is suggested from the observed change of the dipole layer at the interface. Annealing at 600 °C or higher removes both Li and H from the sample and a monolayer graphene sample is re-established. The Li thus promotes the removal of H from the interface at a considerably lower temperature than after pure H intercalation

Studies of Li intercalation of hydrogenated graphene on SiC(0001)

The effects of Li deposition on hydrogenated bilayer graphene on SiC(0001) samples, i.e. on quasi-freestanding bilayer graphene samples, are studied using low energy electron microscopy, micro-low-energy electron diffraction and photoelectron spectroscopy. After deposition, some Li atoms form islands on the surface creating defects that are observed to disappear after annealing. Some other Li atoms are found to penetrate through the bilayer graphene sample and into the interface where H already resides. This is revealed by the existence of shifted components, related to H–SiC and Li–SiC bonding, in recorded core level spectra. The Dirac point is found to exhibit a rigid shift to about 1.25 eV below the Fermi level, indicating strong electron doping of the graphene by the deposited Li. After annealing the sample at 300–400 °C formation of LiH at the interface is suggested from the observed change of the dipole layer at the interface. Annealing at 600 °C or higher removes both Li and H from the sample and a monolayer graphene sample is re-established. The Li thus promotes the removal of H from the interface at a considerably lower temperature than after pure H intercalation

Nanoscale 3-D (E, k(x), k(y)) band structure imaging on graphene and intercalated graphene

An x-ray photoemission electron microscope (X-PEEM) equipped with a hemispherical energy analyzer is capable of fast acquisition of momentum-resolved photoelectron angular distribution patterns in a complete cone. We have applied this technique to observe the 3-D (E, k(x), k(y)) electronic band structure of zero-, one-, and two-monolayer (ML) graphene grown ex situ on 6H-SiC(0001) substrates where a carbon buffer layer (zero ML) forms underneath the graphene layer(s). We demonstrate that the interfacial buffer layer can be converted into quasi-free-standing graphene upon intercalation of Li atoms at the interface and that such a graphene is structurally and electronically decoupled from the SiC substrate. High energy and momentum resolution of the X-PEEM, along with short data acquisition times from submicrometer areas on the surface demonstrates the uniqueness and the versatility of the technique and broadens its impact and applicability within surface science and nanotechnology

Changes in structural and electronic properties of graphene grown on 6H-SiC(0001) induced by Na deposition

The effects of Na deposited on monolayer graphene on SiC(001) were investigated by synchrotron-based photoelectron spectroscopy and angle resolved photoelectron spectroscopy. The experimental results show that Na prefers to adsorb on the graphene layer after deposition at room temperature. Nonetheless, part of the Na atoms are able to intercalate in between the graphene and the buffer layer and some go even further into the substrate interface as indicated by the shift of the bulk SiC component in the C 1s and Si 2p core level spectra. The ARPES spectrum exhibits a lowering of the Dirac point indicating increased n-type doping of the monolayer graphene induced by the deposited Na atoms. Upon subsequently heating the sample, we found that a slightly elevated temperature is essential in order to promote Na intercalation. A fully Na intercalation at the graphene-SiC interface is obtained after heating at a temperature of about 75 degrees C. The intercalated Na decouples the buffer layer and transforms it into a second graphene layer so two pi-bands are observed in the ARPES spectra. Interestingly, the two bands show different locations of the Dirac point but both exhibit linear dispersion in the vicinity of the (K) over bar point and not the hyperbolic dispersion observed for AB stacked bi-layer graphene. When heating the sample to about 125 degrees C or higher, Na is found to leave the interface and the second graphene layer is transformed back to the carbon buffer layer.Funding Agencies|EU|

Epitaxial graphene on 6H-SiC and Li intercalation

The influence of lithium (Li) exposures on monolayer graphene grown on the silicon-terminated SiC(0001) surface is investigated using low-energy electron microscopy, photoelectron spectroscopy, and micro-low-energy electron diffraction. After Li deposition, islands or Li droplets are observed on the surface, and are found to coalesce together with time. Formation of a dipole layer at the interface, interpreted to originate from Li-Si bonding, is observed directly after Li deposition, and manifested by a 2 eV shift of the C 1s and Si 2p bulk SiC peaks. This indicates that Li atoms penetrate through the graphene and carbon buffer layer directly after deposition at room temperature since three pi bands are then moreover observed at the K point, instead of the single pi band for monolayer graphene. The existence of three pi bands is interpreted as a mixture of bilayer and monolayer graphene plus a difference in doping levels due to an uneven distribution of Li atoms. Li gives rise to electron doping of the graphene and results in a lowering of the Dirac point. After annealing to a few hundred degrees Celsius, a more even Li distribution and intercalation is obtained since then two distinct pi bands appear at the K point.Original Publication:Chariya Virojanadara, Somsakul Watcharinyanon, A A Zakharov and Leif I Johansson, Epitaxial graphene on 6H-SiC and Li intercalation, 2010, PHYSICAL REVIEW B, (82), 20, 205402.http://dx.doi.org/10.1103/PhysRevB.82.205402Copyright: American Physical Societyhttp://www.aps.org