Field electron emission and field desorption of cesium from graphene

Field electron emission and field desorption of cesium ions from a monatomic graphene film on Ir and graphene clusters in amorphous carbon are investigated using field electron microscopy and continuous-mode field desorption microscopy. The deposition of cesium on amorphous carbon with graphite clusters leads to inversion of the emission (i.e., emission from the emission centers disappears against the back-ground of uniform emission from the previously nonemitting surface). In both systems, ion current pulses are observed during field desorption in a stationary electric field. During field desorption from the graphene film, current pulses of Cs⁺ ions with a duration shorter than 0.1 s appear from the plane faces of the iridium point. During desorption from graphite clusters, ion current pulses form a pattern of “collapsing rings” on the screen. Possible mechanisms of the observed processes are considered using the model of cesium intercalation by graphite and by the graphene layer and the desorption of Cs atoms under the action of the electric field, as well as the “flip” of the dipole moment during the cesium intercalation.     

Graphene traps for cesium atoms

A significant increase in the surface concentration of cesium atoms intercalated under graphene islands on rhodium has been revealed when annealing the adsorbed layer in a ultrahigh vacuum. Heating leads to a decrease in the area of graphene islands due to the solution of carbon atoms in the metal bulk. At the same time, the edge carbon atoms in the islands, which are coupled with the surface by chemisorptive forces, prevent the leakage of the alkali metal from under the islands. This leads to the significant compression of cesium and to an increase in its surface concentration under the islands by a factor of almost 10. The desorption of cesium is observed only after the complete thermal destruction of graphene islands.     

Intercalation of graphene on iridium with samarium atoms

Intercalation of graphene on Ir (111) with Sm atoms is studied by methods of thermal desorption spectroscopy and thermionic emission. It is shown that adsorption of samarium at T = 300 K on graphene to concentrations of N ≤ 6 × 10¹⁴ atoms cm^–2 followed by heating of the substrate leads to practically complete escape of adsorbate underneath the graphene layer. At N > 6 × 10¹⁴ atoms cm^–2 and increasing temperature, a fraction of adsorbate remains on graphene in the form of two-dimensional “gas” and samarium islands and are desorbed in the range of temperatures of 1000–1200 K. Samarium remaining under the graphene is desorbed from the surface in the temperature range 1200–2150 K. Model conceptions for the samarium–graphene–iridium system in a wide temperature range are developed.     

The nature of the adsorption bond between graphite islands and iridium surface

To reveal the nature of adsorption bonds between two-dimensional graphite islands and iridium (111) and (100) faces, a study has been made of the adsorption of potassium and cesium atoms on the surface of these systems, using thermal desorption and Auger electron spectroscopy, as well as surface ionization and thermionic emission techniques. The graphite islands are shown to be weakly bound to the iridium substrate by Van der Waals forces. The unsaturated valence bonds at the periphery of the graphite islands are “lowered down” on to the metal. The recess between the graphite layer and the metal is filled by adsorbing particles through defects in the graphite layer. The atoms can penetrate into the recess in two ways: at T > 1000 K directly from the flux incident on the surface, and at T < 1000 K also by migration from the graphite island surface. The adsorption capacity of this state is ～ (2?3) × 10¹⁴cm^-2. Thermal destruction of the islands at T > 1900 K liberates the potassium and cesium atoms from under the graphite islands. Our study suggests that the reason for the “raised” position of the islands lies in the valence bonds of the graphite layer being saturated, the valence bonds of the metal and its crystallographic orientation being less significant. Therefore one may expect the graphite layer to be raised also above other metals as well. The filling by cesium of the recess between the graphite layer and iridium and of the adsorption phase on the graphite surface, does not change the general “graphitic” shape of the carbon Auger peak. This cesium results, however, in a pronounced splitting of the negative spike on the carbon peak (which provides information on its location relative to the graphite layer) indicating the appearance in the valence band of graphite near the Fermi level of two narrow (～ 2?3 eV) regions with an enhanced density of states originating from the presence of the alkali metal.     

Studies of the desorption mechanism of O− by electron impact from oxygen covered metal surfaces

Electron-stimulated desorption of negative ions from oxygen covered tungsten and molybdenum has been investigated. The O^? desorption current as a function of incident electron energy was measured. The following results were observed: (1) the threshold of negative ion desorption is much lower than that of positive ions (20–25 eV for O⁺; 4–5 eV for O^?); (2) some resonant-like structures appear in the curves of desorption current as a function of electron energy in the low energy regions; these structures do not appear in the high energy regions; (3) these resonant-like structures are basically the same for O₂-W and O₂-Mo systems. Experimental results seem to indicate that the desorption of negative ions are essentially a feature of the absorbate and can be most readily explained based on potential energy curves for some electronic states of oxygen molecules and ions, and within the framework of the Franck-Condon principle.     

Umladung von H+ zu H− in Kaliumbzw. Cäsiumdampf im Energiebereich 0,5 bis 2 keV

For sources for polarized ions at a tandem accelerator the charge changing process from H⁺ to H^? in potassium and cesium metallic vapour is very favourable. The charge changing yield in potassium amounts to 10% at a proton energy of 0.5–1.5 keV, and to 15% in cesium at a proton energy of 0.5 keV.     

Thermally stimulated desorption of Na<Superscript>+</Superscript> and Cs<Superscript>+</Superscript> ions from a NaAu alloy film grown on Au

The formation of Na⁺ and Cs⁺ ions on and their thermal desorption from the surface of a NaAu alloy film grown on metallic gold are studied. It is shown that thermionic emission from insulator-coated metallic substrates is governed by a sequence of processes, such as diffusion of Na and Cs adatoms into the film, ionization of these atoms at the insulator-metal interface, diffusion of the resulting ions toward the surface, and desorption of the ions. The effect of weak electric fields on ion diffusion and desorption is investigated.     

Nonstationary processes in an electric field during coadsorption of gold and alkali metals on tungsten

The processes induced by a strong electric field in the “tungsten-gold-alkali metal” adsorption systems are studied. Field desorption of K⁺ and Cs⁺ ions initiates nonstationary processes involving ion current pulsations and periodic displacements of desorption regions under constant experimental conditions. The observed effects are explained as resulting from the processes of (i) formation of an alkali-metal-gold film exhibiting properties of a wide-band-gap semiconductor, (ii) breakdown and restoration of this film in an electric field, and (iii) accumulation and relaxation of the electric charge.     

Interaction of cesium and oxygen on W(110): I. Cesium adsorption on oxygenated and oxidized W(110)

Cesium adsorption on oxygenated and oxidized W(110) is studied by Auger electron spectroscopy, LEED, thermal desorption and work function measurements. For oxygen coverages up to 1.5 × 10¹⁵ cm^?2 (oxygenated surface), preadsorbed oxygen lowers the cesiated work function minimum, the lowest (～1 eV) being obtained on a two-dimensional oxide structure with 1.4 × 10¹⁵ oxygen atoms per cm². Thermal desorption spectra of neutral cesium show that the oxygen adlayer increases the cesium desorption energy in the limit of small cesium coverages, by the same amount as it increases the substrate work function. Cesium adsorption destroys the p(2 × 1) and p(2 × 2) oxygen structures, but the 2D-oxide structure is left nearly unchanged. Beyond 1.5 × 10¹⁵ cm^?2 (oxidized surface), the work function minimum rises very rapidly with the oxygen coverage, as tungsten oxides begin to form. On bulk tungsten oxide layers, cesium appears to diffuse into the oxide, possibly forming a cesium tungsten bronze, characterized by a new desorption state. The thermal stability of the 2D-oxide structure on W(110) and the facetting of less dense tungsten planes suggest a way to achieve stable low work functions of interest in thermionic energy conversion applications.     

Electron impact desorption of Xe from the tungsten (110) plane

The electron stimulated desorption of Xe adsorbed on the clean and on oxygen and CO covered tungsten (110) surfaces has been investigated. Only neutral Xe desorption was observed; for Xe on clean W a very small initial regime with cross section 10^?17cm² is followed by a slow decay with cross section 3×10^?19cm². The Xe yield varies nonlinearly with coverage, suggesting desorption from edges of islands or from sites with less than their full complement of nearest neighbor Xe atoms. Desorption from oxygen or CO covered surfaces results in an apparent desorption cross section identical to that of the underlying adsorbate. This results from a kicking off of Xe by electron desorbed O or CO. The true cross sections for these processes are ～10^?14cm² for Xe-0 and ～10^?15 cm² for Xe-CO. Some speculations about the mechanism, particularly the absence of ions are presented.     

Sodium Intercalation of Graphene Films on Re( $$10\bar 10$$ 10 1 ¯ 0 )

It is shown that during low-temperature (300–500 K) intercalation of sodium atoms into thin multilayer graphene and graphite films on rhenium the first graphene layer plays the role of a trap to which atoms coming on the surface diffuse through a graphite film. The intercalation phase of the interlayer space in the graphite bulk is actively filled at a sodium atoms concentration under the first graphene layer close to the maximum possible (2 ± 0.5) × 10¹⁴ cm^–2. This phase capacity is proportional to the graphite film thickness that can be varied in this work from one graphene layer to ~50 atomic layers. The diffusion energy E _d of Na atoms through the graphite film was estimated to be E _d ≈ 1.4 eV.

     

Resistance changes in thin metallic films under ion bombardment

Resistance changes in thin films of copper, aluminium and bismuth have been studied under the bombardment of nitrogen, carbon and argon ions. Variations in resistance with implantation dose have been observed upto doses of ∼ 3 × 10¹⁷ ions/cm² for ion energies in the range 40 to 120 keV. The results are discussed in terms of desorption of gases from the film and a composite action of sputter removal of the film and its structural changes upon ion bombardment. A simple theoretical model is discussed which can qualitatively explain the experimental observations.     

Silver sulphide growth on Ag(111): A medium energy ion scattering study

The interaction of S₂ with Ag(111) under ultra-high vacuum conditions has been investigated by medium energy ion scattering (MEIS). 100 keV He⁺ MEIS measurements provide a direct confirmation of a previous report, based on thermal desorption, that the growth of multilayer films of Ag₂S occurs through a continuous corrosion process. These films show a commensurate (√7 × √7)R19° unit mesh in low energy electron diffraction, consistent with the epitaxial growth of (111) layers of the high-temperature F-cubic phase of Ag₂S. The substantial range of co-existing film thicknesses found indicates that the growth must be in the form of variable-thickness islands. The use of 100 keV H⁺ incident ions leads to a very rapid decrease in the sulphide film thickness with increasing exposure that we attribute to an unusual chemical leaching, with implanted H atoms interacting with S atoms and desorption of H₂S from the surface.     

Influence of cesium atoms on the field electron emission from multi-walled carbon nanotubes

It has been shown that the deposition of cesium atoms on multi-wall carbon nanotubes abruptly increases the current of the field electron emission, decreases the threshold electric field by a factor of three (to 0.8 V/m), and decreases the work function to 2.1–2.3 eV. It has been found that the flowing of the large emission current I ≥ 2 × 10^?6 A leads to a change in the current-voltage characteristics and a decrease in the emission current. This effect has been explained by escape of cesium atoms from the tips of most nanotubes into the nanotube depth due to desorption or intercalation. At the same time, the low work function is retained for some nanotubes, probably, due to the stronger bonding of Cs atoms with these nanotubes.     

Paramagnetic Impurities in Graphene Oxide

We report on electron paramagnetic resonance and nuclear magnetic resonance study of graphene oxide produced by the Hummers method. We show that this compound reveals isolated Mn²⁺ ions, which originate from potassium permanganate used in the process of the sample preparation. These ions are likely anchored to the graphene oxide planes and contribute to the ¹H and ¹³C spin–lattice relaxation.     

Investigation of interaction between lithium and tantalum under a silicon film coating by electron-stimulated desorption technique

The electron-stimulated desorption of Li⁺ ions from lithium layers adsorbed on the tantalum surface coated with a silicon film has been investigated. The measurements are performed using a static magnetic mass spectrometer equipped with an electric field-retarding energy analyzer. The threshold of the electron-stimulated desorption of lithium ions is close to the ionization energy of the Li 1s level. The secondary thresholds are observed at energies of about 130 and 150 eV. The threshold at an energy of 130 eV is approximately 30 eV higher than the ionization energy of the Si 2p level and can be associated with the double ionization. The threshold at 150 eV can be caused by the ionization of the Si 2s level. It is demonstrated that the yield of Li⁺ ions does not correlate with the silicon amount in near-the-surface region of the tantalum ribbon and drastically increases at high annealing temperatures. The dependence of the current of Li⁺ desorption on the lithium concentration upon annealing of the tantalum ribbon at T>1800 K exhibits two maxima. The ions desorbed by electrons with energies higher than 130 and 150 eV make the largest contribution to the current of lithium ions after the annealing. The yield of lithium ions upon ionization of the Li 1s level at an energy of 55 eV is considerably lesser, but it is observed at higher concentrations of deposited lithium. The results obtained can be interpreted in the framework of the Auger-stimulated desorption model with allowance made for relaxation of the local surface field.     

Density functional theory study on the adsorption of alkali metal ions with pristine and defected graphene sheet

The graphene-based materials along with the adsorption of alkali metal ions are suitable for energy conversion and storage applications. Hence in the present work, we have investigated the structural and electronic properties of pristine and defected graphene sheet upon the adsorption of alkali metal ions (Li⁺, Na⁺, and K⁺) using density functional theory (DFT) calculations. The presence of vacancies or vacancy defects enhances the adsorption of alkali ions than the pristine sheet. From the obtained results, it is found that the adsorption energy of Li⁺ on the vacancies defected graphene sheet is higher (3.05?eV) than the pristine (2.41?eV) and Stone–Wales (2.50?eV) defected sheets. Moreover, the pore radius of the pristine and defected graphene sheets are less affected by metal ions adsorption. The increase in energy gap upon the adsorption of metal ions is found to be high in the vacancy defected graphene than that of other sheets. The metal ions adsorption in the defective vacancy sheets has high charge transfer from metal ions to the graphene sheet. The bonding characteristic between the metal ions and graphene sheet are analysed using QTAIM analysis. The influence of alkali ions on the electronic properties of the graphene sheet is examined from the Total Density of States (TDOS) and Partial Density of States (PDOS).     

Auger electron spectroscopy (AES) studies of argon ion induced desorption of carbon from tantalum

AES studies of argon ion induced desorption of carbon from tantalum were performed. The carbon adlayer was allowed to adsorb from a well characterized residual gas atmosphere, that was unvarying within 20%. The argon ions impact on the surface at an angle of 60° from the surface normal with energies between 0.2 to 1.0 keV. The total desorption cross section values measured under these conditions are 0.07–1.1 × 10^?15 cm².     

Magnetic resonance evidence of manganese–graphene complexes in reduced graphene oxide

We report on EPR and NMR study of reduced graphene oxide (RGO) produced by the Hummers method. We show that this RGO sample reveals isolated Mn²⁺ ions, which originate from potassium permanganate used in the process of the sample preparation. These ions form paramagnetic charge-transfer complexes with the graphene planes and contribute to the ¹³C spin–lattice relaxation.     

Molecular adsorbate detection using hyperthermal Cs+ surface scattering: chemisorbed water on Si(111)

Cs⁺ ion beams are scattered from an Si(111) surface chemisorbed with water. Scattering of Cs⁺ ions from the surface at the incidence energies of 10–;15 eV gives rise to reaction products CsOH⁺, CsOH⁺₂ and CsSiO⁺. We interpret that these cluster ions are formed by desorption of X (X = OH, H₂O and SiO), followed by Cs⁺X association and energy quenching near the surface. The Cs⁺ scattering method has potential advantages for adsorbate detection over desorption techniques, in particular for identification of molecular and thermally unstable species.