The influence of laser dehydrogenation and crystallization of phosphorous-doped amorphous silicon (a-Si:H) on structural and hydrogen bonding configurations is investigated. After each crystallization step the samples were characterized using Raman spectroscopy measurement. The results show that in the first step of crystallization, a stratified structure is created with a polycrystalline silicon (poly-Si) layer at the top of an amorphous layer. The crystalline volume fraction is not influenced by the incorporation of phosphor. According to Raman measurements the amount of hydrogen accommodated in large clusters increases with increasing doping concentration and after laser crystallization.