Photochemical routes to silicon epitaxy

The photochemistry of Si2H6 adsorbed on a hydrogen terminated silicon surface and the subsequentreactions of the photolysis products were investigated using high resolution electron energy lossspectroscopy and by measuring time-of-flight distributions with a mass spectrometer. The crackingpattern of the products ejected directly into the gas phase without colliding with either the surfaceor other molecules indicates that the primary photolysis channels yield mostly fragments thatcontain one silicon atom. It is likely that silicon is added to the surface by insertion of SiH2 radicalsinto Si–H bonds at the surface but there is little evidence for reactions that remove excess hydrogenfrom the surface at 110

Hydrogen adsorption on and desorption from Si: Considerations on the applicability of detailed balance

The translational energy of D2 desorbed from Si(100) and Si(111) surfaces was measured and found roughly equal to the thermal expectation at the surface temperature Ts. Combining these results with previously measured internal state distributions, the total energy of the desorbed molecules is approximately equal to the equilibrium expectation at Ts. Thus adsorption experiments, which suggest a large energetic barrier, are at variance with desorption experiments, which exhibit a trivial adsorption barrier, and the applicability of detailed balance for this system needs to be reexamined

The adsorbate state specific photochemistry of dioxygen on Pd(111)

The ultraviolet‐photochemistry of molecularly adsorbed oxygen on Pd(111) has been studied using pulsed laser light with 6.4 eV photon energy. Three processes occur upon irradiation: desorption of molecular oxygen, conversion between adsorption states, and dissociation to form adsorbed atomic oxygen. By using time‐of‐flight spectroscopy to detect the desorbing molecular oxygen and post‐irradiation thermal desorption spectroscopy (TDS) to characterize the adsorbate state, a detailed picture of the photochemical processes is obtained. The data indicate that the O2 molecules desorbing with low translational energies from the saturated surface as well as the conversion of adsorbed molecules between binding states are induced by the photoinduced build‐up of atomic oxygen on the surface. Analysis of a proposed reaction model reproduces the observed data and yields detailed rates. Polarization analysis indicates that the photochemical processes are initiated by electronic excitations of the substrate

Isotope and Quantum Effects in Vibrational State Distributions of Photodesorbed Ammonia

A marked quantum effect has been observed in the vibrational state distribution of photodesorbed ammonia. Namely, for quantum numbers larger than zero, symmetric and antisymmetric levels in the ν2 mode of the desorbed ammonia molecule are unequally populated. A strong propensity for symmetric levels is observed for NH3, whereas the reverse is found for ND3. Model calculations reproduce this effect. Moreover, it is found that the actual ratios probe the binding energy in the energetically less favorable inverted geometry with the H atoms pointing towards the surface

Cross sections and NO product state distributions resulting from substrate mediated photodissociation of NO₂ adsorbed on Pd(111)

Ultraviolet irradiation of NO2 adsorbed on top of a NO saturated Pd(111) surface causes the photodissociation of NO2/N2O4 and results in the desorption of NO molecules. This process has been studied using excitation energies between 3.5 and 6.4 eV. At a photon energy of 6.4 eV, a cross section of 3×10−18 cm2 is found. Using laser‐induced fluorescence to detect the desorbed NO molecules, fully state‐resolved data detailing the energy channeling into different degrees of freedom has been obtained. Two desorption channels are found, one characterized by nonthermal state populations, and one showing accommodation to the surface. The yield of the fast channel shows a marked increase above 4 eV photon energy. The slow channel is interpreted as being due to NO molecules which, after formation, undergo a trapping–desorption process. A polarization experiment indicates that the photodissociation is initiated by excitation of metal electrons rather than direct absorption by the adsorbate

Coupling of the rotational and translational degrees of freedom in molecular DIET: A classical trajectory study

Classical trajectories have been calculated to address recent observations in laser-induced desorption of molecules: in particular that the mean translational energy increases with rotational energy of the desorbed molecule. A model is discussed which explains rotational excitation on the basis of an anisotropic repulsive interaction in the excited state. The observed correlation is a consequence of the lifetime spread in the excited state resulting in the fact that for those molecules quenched later more potential energy is transferred into translational and rotational energy. Calculated rotational state and velocity distributions are in semiquantitative agreement with experimental findings

Mechanisms in photochemistry on metal surfaces

Fundamental mechanisms for photochemistry at metal surfaces are discussed. Experiments probing these mechanisms are presented for molecular oxygen adsorbed on palladium(111). In particular the dependence of these processes on photon energy and its relation to hot carrier dynamics is discussed

Photostimulated chemistry at the metal-adsorbate interface

The ultraviolet photochemistry of molecules adsorbed on metallic surfaces has been studied using excimer lasers as radiation source. Dissociation with the fragments either ejected into the gas phase or retained on the surface is one prominent channel. The other is photodesorption of intact molecules. The desorbing molecules are characterized by time-of-flight mass spectroscopy and laser spectroscopy. The state of the adsorbate after irradiation is characterized by thermal desorption spectroscopy and high resolution electron energy loss spectroscopy. The methods and fundamental characteristics are exemplified using results from three studied systems: O2, H2O, and N2O4 adsorbed on Pd(111)