An X-ray photoelectron spectroscopic study of the adsorption of N2, NH3, NO,and N2O on dysprosium

The adsorption of N₂, NH₃, NO, and N₂O onto clean polycrystalline dysprosium at 300 and 115 K and the changes undergone by the adsorbed species upon heating from 115 K have been investigated using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). At 115 K, N₂ adsorbs dissociatively, vielding two peaks in the N 1s region at 396.2 and 398.2 eV corresponding respectively to a nitride and to chemisorbed nitrogen N(a). No peaks corresponding to molecularly adsorbed N₂ (BE 400.2 eV [10]) were observed. Upon heating the sample the N(a) is converted into the nitride species, as evidenced by a decrease in the 398.2 eV peak and a corresponding increase in the 396.2 eV peak. At a warm-up temperature of 300 K, the N(a) species accounts for only ～10% of the total nitrogen on the surface. Ammonia adsorbed at 115 K shows three distinct peaks, at 401.7, 399.3 and 396.2 eV, corresponding to molecular, partly dissociated, and completely dissociated (nitride) ammonia. Upon heating multilayer ammonia to 175 K, it desorbs to leave predominantly the peak corresponding to the partly dissociated species. Upon further heating the molecular and partly dissociated ammonia is converted into the nitride species. At 400 K only nitride-type nitrogen remains on the surface. The adsorption of NO and N₂O at 115 K is predominantly dissociative. NO has N 1s peaks at 403.1 and 396.3 eV corresponding possibly to molecularly adsorbed NO, and to nitride species. After N₂O adsorption there is very little nitrogen on the surface. Adsorption of N₂ and NO at 300 K yields only the peak at 396.2 eV, whereas NH₃ yields, in addition to this peak, a small intensity (～20%) of the peak at 398.2 eV (partly dissociated ammonia).     

A photoelectron spectroscopic observation of iron surfaces exposed to N2, N2O,NO, NO2 and air at 200 torr or 1 atm

Photoelectron spectra from core levels are presented for adsorption of nitrogen-containing gases at 200 torr or 1 atm on iron surfaces. Assignments of each band and the adsorption process are discussed. On the substrate at normal temperature, each gas forms nitride and nitrogen oxide groups (NO, NO₂ and NO₃) which appear at 398.6, 400.0, 404.5 and 407.1 eV, respectively. The relative intensifies of each species depend on the gases adsorbed. NO and NO₂ are considered to dissociate on the surface and the oxygen atom adsorb preferentially. The oxygen on the surface can be considered to contribute to the formation of each surface ligand.     

Adsorption of nitrogen and ammonia by polycrystalline iron surfaces in the temperature range 80–290 K studied by electron spectroscopy

X-ray and uv induced photoelectron spectroscopy have provided information on the various molecular states of nitrogen formed on polycrystalline iron surfaces from dinitrogen and ammonia. At 85 K two distinct states are observed with N₂(g) which have N(1s) binding energy values of 405.3 and 400.2 eV. These are in equilibrium with N₂(g), are weakly held, and are desorbed on warming to 290 K leaving a nitrogen free surface. The two states are assigned to a molecularly adsorbed

and linear

species the former characterised by an N(1s) value of 400.2 eV and the latter by 405.3 eV. At 290 K nitrogen is adsorbed with a very low sticking probability (?10^?6) giving rise to an N(1s) value of 397.2 eV. This is undoubtedly the dissociatively chemisorbed

species. At a nitrogen pressure of l Torr adsorption is “instantaneous” and the N(1s) value is 397 eV. No evidence for the unstable bridged and linear forms of nitrogen is obtained at 290 K although they may well be precursors to the formation of the strongly chemisorbed nitrogen species. Shifts in the N(1s) binding energy induced by subsequent oxygen adsorption are discussed briefly. At 85 K ammonia adsorbs largely in the molecular form with a broad N(1s) peak centred at about 400 eV but on warming to 290 K this splits to give two peaks one at 397 eV and the other at 400 eV. Interaction at 290 K leads to a dominant peak at 397.2 eV and a subidiary one at 400 eV. Helium (1) spectra support the assignment of the 397.2 eV peak to dissociated species (N, NH) and the 400 eV peak to molecular adsorption. The conclusions with N₂ and NH₃ are substantiated further by comparing the data with results for nitric oxide. The concentration of nitrogen adatom species formed from NO at 290 K and 10^?6 Torr is some ten times that formed from N₂ at 1 Torr and three times that from NH₃ at 10^?6 Torr and the same temperature.     

Adsorption and decomposition of ammonia on W(100); XPS and UPS studies

The adsorption and decomposition of ammonia on a clean and c(2 × 2)-N ordered W(100) surface has been studied by photoemission spectroscopy (XPS and UPS). At 120 K molecularly adsorbed ammonia was identified by N(1s) core level emission at 400.9 eV and the valence emissions at 7.6 and 11.7 eV. By heating the sample stepwise the N(1s) core level shifted to lower binding energy. In the valence region, the corresponding spectral changes were obtained, where the dependence of the peak intensity on photon energy was observed. These observations were interpreted to demonstrate that adsorbed ammonia dissociates its hydrogen successively to form NH_x(a) and finally to atomic nitrogen. On the other hand, ammonia was molecularly adsorbed on a c(2 × 2)-N ordered surface even at temperatures as high as 300 K, although the spectra at 400 K or above were very similar to those under a steady state flow condition, where the tungsten surface was mostly covered by atomic nitrogen. At higher ammonia pressure up to about 100 Pa thicker nitride layers were formed at 700 K, which were characterized by the N(1s) core level at 397.3 eV and a broad emission around 6 eV in the valence level.     

Coordination of acetonitrile (CH3CN) to platinum (111): Evidence for an η2(C,N) species

Acetonitrile (CH₃CN) coordination to a Pt(111) surface has been studied with electron energy loss vibrational spectroscopy (EELS), XPS, thermal desorption and work function measurements. We compare data for the surface states with known acetonitrile coordination complexes. For CH₃CN adsorbed on Pt(111) at 100 K, the molecule is rehybridized and adsorbs with the CN bond parallel or slightly inclined to the surface plane in an η²(C, N) configuration. The ν(CN) frequency is 1615 cm^?1 and the C ls and N ls binding energies are 284.6 eV and 397.2 eV respectively. By contrast, weakly adsorbed multilayer acetonitrile exhibits a ν(CN) vibrational frequency of 2270 cm^?1, and C ls and N ls binding energies of 286.9 eV and 400.1 eV respectively. Both the EELS and XPS results are consistent with rehybridization of the CN triple bond to a double bond with both C and N atoms of the CN group attached to the surface. In addition to this majority η²(C, N) monolayer state, evidence is found for a second, more strongly bound minority molecular state in thermal desorption spectra. As a result of the low coverage of this state, EELS was unable to spectroscopically identify it and we tentatively assign it as an η⁴(C, N) species associated with accidental step sites. By contrast to the surface complexes, almost all of the known platinum-nitrile coordination complexes are end-bonded via the N lone-pair orbital. Several cases of side-on bonding are known, however, and we compare the results with the known complex Fe₃(η²-NCCH₃)(CO)₉. The difference in the coordinative properties of a Pt(111) surface versus a single Pt atom must be due to the increased ability of multi-atom arrays to back-donate electrons into the π¹ system of acetonitrile. Previously published EELS and XPS results for monolayer acetonitrile on Ni(111) and polycrystalline films are almost identical to the present results on Pt(111). We believe that the monolayer of $\text{CH}{}_3\text{CN}\text{Ni}\text{(111)}$ is also an η²(C, N) species, not an end-bonded species previously proposed by Friend, Muetterties and Gland.     

The adsorption of SO2 on iron surfaces studied by x-ray photoelectron spectroscopy

The interaction of SO₂ with evaporated iron surfaces in the temperature range 80–450 K was investigated by using X-ray photoelectron spectroscopy. At 300 K, SO₂ decomposed at the initial stage of the interaction and gave adsorbed S with the S2p peak at 161.9 eV and adsorbed O with the O1s at 530.0 eV. Further exposure of SO₂ gave adsorbed SO₄ with S2p at 166.8 eV O1s at 531.3 eV, being different in binding energies from ionic SO₄^2?. This indicates the two stage reaction Of SO₂ with iron surface; SO₂(gas) → S(ads) + 20(ads), SO₂(gas) + 2O(ads) → SO₄(ads). The first reaction did not occur at low temperature or in the presence of adsorbed O. The adsorbed SO₄ formed at 80 K showed a quantitative decomposition reaction into S(ads) and O(ads) in the temperature range 200–350 K.     

Coadsorption of CN and O on Cu (1 0 0) surface: A density functional study

The adsorption of cyanide (CN) or oxygen atom, as well as the coadsorption of CN + O on Cu (1 0 0) surface is studied by using density functional theory (DFT) and the cluster model method. Cu₁₄ cluster is used to simulate the surface. Perpendicular and parallel bonding geometries of CN adsorbed on Cu (1 0 0) surface are considered, respectively. The present calculations show that the CN may be absorbed on top and bridge sites by carbon atom of cyanide (C-down), and C-down on top site is the most favorable. The adsorbed C-N stretch frequencies compared with that of the gaseous CN species are all red-shifted, except the C-down on top site. The charge transfer from the surface to the CN species leads to an increase in work function for the Cu surface. The oxygen atom adsorbed on the four-fold hollow site of Cu (1 0 0) is the most favorable, and is consistent with the experimental study. The coadsorption of O at a four-fold hollow site tends to block adsorption of CN at the nearby sites. If O coverage increases, the CN may be adsorbed on the top and bridges sites with the C-down model. The reaction CN + O → OCN on the Cu (1 0 0) is predicted to be exothermic, and formed OCN species may be stably absorbed on the Cu (1 0 0).     

Cyanide chemistry of rubidium-dosed silver and the use of cyanogen as a titrant for surface alkali

The presence of adsorbed rubidium induces dissociation of cyanogen during chemisorption and leads to a mixed adiayer containing two kinds of cyanide surface species. One of these is weakly bound in an undissociated state and desorbs as (CN)₂ (E_d ? 100 k J mole^?1). A second species is the result of dissociation to CN_adsand appears to be closely associated with the Rb adatoms. This species desorbs exclusively as RbCN (E_d ~ 165 kJ mole^?1) with a kinetic order of between zero and unity depending on the surface coverage. This behaviour, together with the electron impact properties of the Rb + CN overlayer suggest that nucleation and island growth of RbCN occurs above a certain critical coverage. This model can account for the way in which the initially large ESD cross-section for CN loss (~3.5 × 10^?18 cm²) rapidly decreases towards zero with decreasing coverage. It is demonstrated that the special properties of the Ag-(CN)₂-Rb system permit (CN)₂ to be used as a specific titrant for surface alkali, and the technique is used to obtain a value for the activation energy (30 kJ mole^?1) for surface → bulk diffusion of Rb in Ag, as well as the above cross-section to ESD.     

Adsorption of hydrazine and ammonia on aluminium

The adsorption and decomposition of hydrazine and ammonia by clean polycrystalline aluminium surfaces have been studied by X-ray photoelectron spectroscopy. At 85 K both ammonia and hydrazine are adsorbed molecularly, with N(1s) peaks at 400.5 eV. At 290 K hydrazine is initially adsorbed to give an N(1s) peak at about 399 eV, but with time (and further exposure) the position of the peak maximum drift to lower N(1s) values, finally approaching 397 eV after heating the ad-layer to 390 K. These observations are interpreted in terms of a slow dissociative chemisorption process: N₂H₄(a) → NH₂(a) → NH(a) → N(a). There is no doubt that the NN bond in hydrazine is broken and that hydrogen ad-atoms formed inhibit the subsequent adsorption of N₂H₄ at 290 K. Ammonia dissociates more slowly than hydrazine to give mainly amine (NH₂) species at 290 K.     

Resonances in the cesium atom yield in electron-stimulated desorption from tungsten coated with a germanium monolayer

The yield and energy distributions of Cs atoms emerging from cesium layers, which are adsorbed on tungsten coated with a thin germanium film (1-to 2-monolayers thick), have been measured as a function of the incident electron energy, the amount of adsorbed cesium, and the substrate temperature. The measurements were performed by the time-of-flight technique with a surface ionization detector. At low cesium coverages (Θ < 0.1), the Cs atom appearance threshold at a substrate temperature T = 160 K is ～24 eV, which correlates with the Cs 5s-level ionization energy. As the electron energy is increased, the yield passes through a broad plateau and reaches saturation. The signal intensity in the plateau region decreases gradually with increasing cesium coverage and tends to zero for Θ > 0.14. For Θ ≥ 0.15, the cesium atom appearance threshold shifts to ～30 eV, which corresponds to the Ge 3d-level ionization energy and the plateau is replaced by a resonance peak at ～38 eV, which can be identified with the ionization energy of the W 5p _3/2 level. This peak is observed only for Θ < 0.3 and T = 160 K. For Θ ≥ 0.3, there appears a resonance peak at ～50 eV, and for Θ ≥ 0.5, another resonance peak appears at ～80 eV. These peak positions correlate with the ionization energies of the W 5p _1/2 and W 5s levels, and their intensity is maximum at Θ = 1. The Cs atom energy distributions for Θ < 0.15 consist of a bell-shaped peak with a maximum at ～0.55 eV, and those for Θ ≥ 0.15 contain two nearly resolved maxima, a broad one peaking at ～0.5 eV and a narrow one at ～0.35 eV. The above results argue for the existence of three channels of Cs atom desorption. One channel involves reverse motion of the Cs²⁺ ion; another channel, neutralization of the adsorbed Cs⁺ ion following the Auger decay of a vacancy in the Ge atom; and the third channel involves desorption of a CsGe molecule as it is repelled from a W core exciton.     

Low voltage electrodeposition of CNx films and study of the effect of the deposition voltage on bonding configurations

Carbon nitride (CN_x) films were deposited from acetonitrile at low voltage (150-450 V) through electrodeposition. The films were characterized by atomic force microscopy (AFM), Raman spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. AFM investigations revealed that the grain size was ∼200 nm and roughness was ∼10 nm. The films were found to be continuous and close packed. IR spectra revealed existence of strong sp³, sp² type bonding and weak sp type carbon nitrogen bonds and these bonds were found to increase with voltage. The fraction of sp³-bonded species in the sample increased in low voltage range and after reaching maximum at 350 V, decreased for higher voltages. However, the concentration of sp² CN ring structures in the film increased with increasing voltage. Also, the peak width decreased at low voltages reaching a minimum and increased thereafter. It was observed that the voltage dependent increase in the concentration of polymeric type sp² CN (chain) structures was much more pronounced than that of graphitic type sp² CN (ring) structures. Raman spectra showed the presence of both the D and G bands. The shift in the G band indicated the presence of nitrogen in the film. The I_D/I_G ratio was found to increase with the incorporation of nitrogen. Auger electron spectroscopy (AES) showed a clear increase in the nitrogen content with increase in the voltage. The formation of the film could be explained on the basis of dissociation of electrolyte under applied voltage.     

NO adsorption on the Rh(110) surface: kinetics and composition of the adlayer studied by fast XPS

The adsorption and dissociation of NO on the Rh(110) surface were studied by synchrotron radiation X-ray photoemission spectroscopy at temperatures in the range 210–370 K. The O 1s or N 1s spectra were collected every 14 s while the surface was continuously exposed to a steady NO gas pressure. The difference in the binding energies for the atomic oxygen (O 1s ≤530.2 eV), atomic nitrogen (N 1s 397.2 eV) and molecular upright bonded NO molecules (O 1s ≥531.0 eV and N 1s 400 eV) allowed us to distinguish these surface species and to follow the evolution of the adsorbate layer. In addition to these dominating surface species a new species, characterized by O 1s binding energy of 530.7 eV and N 1s binding energy similar to that of the atomic nitrogen, was detected within a narrow coverage range. This state is tentatively assigned to a “lying down” NO bonding configuration, detectable at the timescale of the measurements. The uptake plots, constructed using the integrated intensity of the deconvoluted O 1s and N 1s spectra, are used to elucidate the effect of the reaction temperature and surface coverage and composition on the kinetics of dissociative and molecular NO adsorption of Rh(110).     

The impact of ultra thin silicon nitride buffer layer on GaN growth on Si (1 1 1) by RF-MBE

Ultra thin films of pure silicon nitride were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma with a high content of nitrogen atoms. The effect of annealing of silicon nitride surface was investigated with core-level photoelectron spectroscopy. The Si 2p photoelectron spectra reveals a characteristic series of components for the Si species, not only in stoichiometric Si₃N₄ (Si⁴⁺) but also in the intermediate nitridation states with one (Si¹⁺) or three (Si³⁺) nitrogen nearest neighbors. The Si 2p core-level shifts for the Si¹⁺, Si³⁺, and Si⁴⁺ components are determined to be 0.64, 2.20, and 3.05 eV, respectively. In annealed sample it has been observed that the Si⁴⁺ component in the Si 2p spectra is significantly improved, which clearly indicates the crystalline nature of silicon nitride. The high resolution X-ray diffraction (HRXRD), scanning electron microscopy (SEM) and photoluminescence (PL) studies showed a significant improvement of the crystalline qualities and enhancement of the optical properties of GaN grown on the stoichiometric Si₃N₄ by molecular beam epitaxy (MBE).     

Experimental and theoretical studies of Si-CN bonds to eliminate interface states at Si/SiO2 interface

Cyanide treatment, which includes the immersion of Si in KCN solutions followed by a rinse, effectively passivates interface states at Si/SiO₂ interfaces by the reaction of CN⁻ ions with interface states to form Si-CN bonds. X-ray photoelectron spectroscopy (XPS) measurements show that the concentration of the CN species in the surface region after the cyanide treatment is ∼0.25 at.%. Take-off angle-dependent measurements of the XPS spectra indicate that the concentration of the CN species increases with the depth from the Si/SiO₂ interface at least up to ∼2 nm when ultrathin SiO₂ layers are formed at 450 °C after the cyanide treatment. When the cyanide treatment is applied to metal-oxide-semiconductor (MOS) solar cells with 〈ITO/SiO₂/n-Si〉 structure, the photovoltage greatly increases, leading to a high conversion efficiency of 16.2% in spite of the simple cell structure with no pn-junction. Si-CN bonds are not ruptured by air mass 1.5 100 mW cm⁻² irradiation for 1000 h, and consequently the solar cells show no degradation. Neither are Si-CN bonds broken by heat treatment at 800 °C performed after the cyanide treatment. The thermal and irradiation stability of the cyanide treatment is attributable to strong Si-CN bonds, whose bond energy is calculated to be 1 eV higher than that of the Si-H bond energy using a density functional method.     

Photoemission of adsorbed CO and H2O on Pt: Valence band studies

In this paper, using monochromatic He and Ne discharge lines, we report the ultraviolet photoemission results for CO and H₂O adsorbed on a Pt crystal. For chemisorbed CO, we use the energy dependence of the photoionization cross section to deduce that the 5σ?1π splitting is approximately 1 eV and that the 5σ is located at about ?8.1 eV while the 1π is at ?9.1 eV. The distribution of metal electrons changes in two ways upon CO chemisorption: a d character peak is found at ?4 to ?5 eV and emission at E_f is strongly depleted. For the weakly adsorbed water molecule, we find preferential attenuation of Pt states near E_f that has heretofore been observed for strongly chemisorbed systems.     

Nitridation of iron by the mixing technology with laser and plasma beams

Iron nitride (Fe_xN) is obtained by the mixing technology with laser and plasma beams coaxially on the surface of pure iron in atmosphere. In this technology, laser and plasma provide heat source and nitrogen ion source, respectively, easily to nitriding the sample. The feasibility of the method is analyzed in theory. Small-angle X-ray diffraction measurements reveal formation of iron nitride in the as-treated sample, and scanning tunneling microscope measurements describe the surface profiles of the irradiated area, at different laser energy densities or different scanning velocities.     

Subthreshold sputtering at high temperatures

The sputtering of tungsten from a target at a temperature of 1470 K during irradiation by 5-eV deuterium ions in a steady-state dense plasma is discovered. The literature values of the threshold for the sputtering of tungsten by deuterium ions are 160–200 eV. The tungsten sputtering coefficient measured by the loss of weight is found to be 1.5×10^?4 atom/ion at a deuterium ion energy of 5 eV. Previously, such a sputtering coefficient was usually observed at energies of 250 eV. The sputtering is accompanied by a change in the target surface relief, i.e., by the etching of the grain boundaries and the formation of a wavy structure on the tungsten surface. The subthreshold sputtering at a high temperature is explained by the possible sputtering of adsorbed tungsten atoms that are released from the traps around the interstitial atoms and come to the target surface from the space between the grains. The wavy structure on the surface results from the merging of adsorbed atoms into ordered clusters.     

An investigation of the adsorption of oxygen and oxygen containing species on platinum by photoelectron spectroscopy

It is shown that XPS can detect 0.01 monolayers of adsorbed carbon or oxygen and can identify the chemical state of the adsorbed atom(s). Two states of adsorbed oxygen were resolved by thermal desorption spectroscopy and by XPS. The O 1s binding energies (^FE_B) were 530.2 and 533 eV below the platinum Fermi level for the strongly and weakly adsorbed states respectively. (^FE_B) did not vary with coverage. The resulting apparent variation of (^VE_B), the vacuum level referenced value, is discussed in terms of a simple model for the work function Φ which was measured in situ. UPS indicated that the weakly adsorbed state is probably molecular, with levels at 6.1, 9.3, 10.4 and l2.4 eV below the Fermi level. The main change in the UPS spectra produced by the strongly adsorbed state was a reduction of a peak close to the Fermi level.     

Evolution of the phase-structure state during annealing of Fe-ZrN films grown by magnetron sputtering

The evolution of the phase-structure state of Fe-ZrN films grown by RF magnetron sputtering and annealed at T = 200–650°C has been studied by transmission electron microscopy, high-resolution electron microscopy, and X-ray diffraction analysis. It has been found that the initial state of the film contains 1- to 5-nm crystallites of α-Fe-based solid solution supersaturated with nitrogen. The number of such crystallites increases, the concentration of nitrogen in them decreases and 2- to 10-nm nanocrystallites of ZrN and Fe2N nitride phases appear after annealing. The formation of zirconium nitride at the first stage (200–500°C) is associated with a decrease in the degree of supersaturation of the α-Fe lattice with nitrogen. At a higher annealing temperature (650°C), a decrease in the nitrogen concentration in the lattices of both the bcc Fe and zirconium nitride phase leads to the formation of iron nitride crystallites.     

Color center formation by synchrotron radiation in the Na6Al6Si6O24(Nal)1.6 optical ceramic

The spectrum of F-center excitation by 5-to 27-eV photons in the Na₆Al₆Si₆O₂₄(NaI)_2x sodalite optical ceramic (x=0.8) was measured at 80 K by high-sensitivity photoexcited luminescence techniques. The F-centers are created by photons with an energy of 5.6-to 8.5 eV through the excitation and ionization of iodine centers of two types; in the 8.2-to 27-eV region, through the generation of electronic excitations in the aluminosilicate framework of alternating Al³⁺ and Si⁴⁺ ions, each coordinated tetrahedrally by oxygen ions. At the low irradiation doses used, the F centers are created primarily through photoelectron capture by the iodine vacancies which exist before irradiation. In the 23-to 25-eV region, the efficiency of F-center formation doubles as a result of the multiplication of electron-hole pairs.