Search

Resonantly enhanced multiphoton ionization (REMPI) and time-of-flight mass spectroscopy have been used to demonstrate that the reaction of Cl2 on the low work function Al(111) surface proceeds via a prompt vertical electron harpooning process. Sticking measurements were performed showing that Cl2 adsorbs via a direct chemisorption process at either high incident translation energy or high surface temperature. However, at glancing incident angles and low surface temperatures (100 K), a precursor-mediated channel predominates. REMPI studies show that fast abstracted Cl was produced via both channels: direct, remotely-dissociated incident Cl2, and indirect, precursor-mediated Cl2. For incident Cl2 of 0.11 and 0.27 eV at 40° incident angle and 100 K surface temperature, only the precursor-mediated channel was observed with atomic Cl abstracted product energies of 0.09–0.14 eV. At high surface temperature, 500 K, all incident translational energies and angles yield only the direct channel, with abstracted prod...

Nonresonant multiphoton ionization with time-of-flight mass spectrometry has been used to monitor the desorption of aluminum chloride (Al(x)Cl(y)) etch products from the Al(111) surface at 100 and 500 K during low-coverage (5% monolayer) monoenergetic Cl(2) (0.11-0.65 eV) dosing. The desorption products in this low-coverage range show predominantly hyperthermal exit velocities under all dosing conditions. For example, with 0.27 eV incident Cl(2), the etch product was found to have a most-probable velocity of 517+/-22 m/s at an Al(111) surface temperature of 100 K. This corresponds to 22 times the expected thermal desorption translational energy for AlCl(3). Cl(2) sticking probability measurements and Al(x)Cl(y) etch rate measurements show etching even at Cl(2) coverages of less than 5% monolayer at surface temperatures between 100 and 500 K. These experimental results are consistent with a combination of fast-time-scale surface diffusion and agglomeration of the adsorbed chlorine to form aluminum chlorides and the presence of activated AlCl(3) chemisorption states having potential energies above the vacuum level. Density functional theory calculations yield results that are consistent with both our experimental findings and mechanistic descriptions.

The NO chemisorption dynamics on ordered multilayer iron phthalocyanine (FePc) and quasiamorphous multilayer tetra-t-butyl FePc (ttbu-FePc) films on a Au(111) substrate was investigated using the King and Wells reflection technique. The NO zero coverage or initial sticking probabilities (S(0)) were measured as a function of sample temperature (T(s)) and beam energy (E(i)). The experimental results for both films show a monotonic decrease in S(0) with increasing T(s) and E(i) consistent with NO adsorption occurring via a multiple pathway precursor-mediated mechanism in which the adsorbate initially physisorbs to the FePc organics, diffuses, and chemisorbs to the Fe metal center. The saturation coverage is 3% for the multilayer FePc surface and only 2% for the multilayer ttbu-FePc surface consistent with NO chemisorption occurring only on the Fe metal, where NO chemisorbs to 100% of the surface Fe metal centers. The reduced saturation coverage in the ttbu-FePc film is attributed to fewer Fe metal centers in the less dense ttbu-FePc films. A comparison of NO sticking on a multilayer FePc/Au(111) film with NO sticking on a monolayer FePc/Au(111) film shows that S(0) is greater on the multilayer FePc film for all T(s) and E(i), consistent with an increase in collision inelasticity for NO/multilayer FePc/Au(111).

The gas-surface reaction dynamics of NO impinging on an iron(II) phthalocyanine (FePc) monolayer were investigated using King and Wells sticking measurements. The initial sticking probability was measured as a function of both incident molecular beam energy (0.09–0.4eV) and surface temperature (100–300K). NO adsorption onto FePc saturates at 3% of a monolayer for all incident beam energies and surface temperatures, suggesting that the final chemisorption site is confined to the Fe metal centers. At low surface temperature and low incident beam energy, the initial sticking probability is 40% and decreases linearly with increasing beam energy and surface temperature. The results are consistent with the NO molecule sticking onto the FePc molecules via physisorption to the aromatics followed by diffusion to the Fe metal center, or precursor-mediated chemisorption. The adsorption mechanism of NO onto FePc was confirmed by control studies of NO sticking onto metal-free H2Pc, inert Au(111), and reactive Al(111).