Depth-resolved analysis of subsurface hydrogen absorbed by Pd(100)

The adsorption and initial absorption of hydrogen (H-2) by Pd(1 0 0) at T = 100 - 160 K are investigated by thermal desorption spectroscopy (TDS) and nuclear reaction analysis, which enables a depth-resolved determination of the hydrogen concentration at and below the Pd surface. Under 3 x 10(8) mba r H-2 and T < 130 K hydrogen is first chemisorbed at the surface and the co verage saturates at 1.0 ML. A small fraction of further dosed hydrogen pene trates the surface and accumulates in a region of up to approximate to4 nm depth, contrasting previous assignments of a corresponding 'alpha (1)'-TDS peak at 180 K to exclusive occupation of first-layer subsurface sites. At T > 130 K H-migration from such a nearsurface hydride phase to the deeper bu lk of the metal occurs and a solution of H in Pd is formed by means of faci le diffusion. This bulk dissolved hydrogen emerges as a broad structure in TDS at T = 200-260 K exhibiting a tailing at high temperatures characterist ic of diffusion-controlled desorption kinetics. (C) 2001 Elsevier Science B .V. All rights reserved.