Soft x-ray photochemistry in solid surfaces

Resent studies on photochemistry using synchrotron soft x-rays in solid surfaces are reviewed. A type of site-selective chemical reaction induced by inner-shell excitation is classified into two model systems that are referred to as 'Element-specific fragmentation' and 'Bonding-site-specific dissociation.' The former system uses difference of core-binding-energies in different elements and the latter is based on the existence of plural unoccupied molecular orbitals with different antibonding character. The selectivity of the reaction in respective systems is discussed in terms of mass-patterns of desorbed fragment-ions and photon-energy dependence of the ion yields. Also discussed are the fragmentation and desorption mechanisms which include intrinsic direct photofragmentation and indirect channels induced by secondary electrons. The latter process reduces the selectivity of the reaction. Furthermore, two experimental approaches, which have recently been performed to estimate the relative magnitude of contribution in the direct and indirect processes to the total yields, are described: (1) the layer-thickness dependence and (2) polarization-angle dependence in the photofragmentation. (author)