The structural properties and hydrogen bonding of undoped and phosphorous doped polycrystalline silicon produced by step-by-step laser dehydrogenation and crystallization technique were investigated using Raman spectroscopy and hydrogen effusion measurements. At low laser fluences, E-L, a two-layer system is created. This is accompanied by the change in hydrogen bonding. The intensity of the Si-H vibration mode at 2000 decreases faster than the one at 2100 cm(-1). This is even more pronounced in phosphorous-doped specimens. The laser crystallization results in an increase of the hydrogen binding energy by approximately 0.2-0.3 eV compared to the amorphous starting materials. (c) 2006 Elsevier B.V. All rights reserved.