Earlier work by Bringansetal. [R. D. Bringans and M. A. Olmstead, J. Vac. Sci. Technol. B7, 1232 (1989); R. I. C. Uhrberg, R. D. Bringans, M. A. Olmstead, R. Z. Bachrach, and J. E. Northrup, Phys. Rev. B35, 3945 (1987)] and by Woolf [D. A. Woolf, D. I. Westwood, and R. H. Williams, Semicond. Sci. Technol.4, 1127 (1989)] has shown that molecular‐beam epitaxy deposition of arsenic may be used to provide a capping and passivation layer on clean silicon surfaces both to protect the clean surface and to allow the transport of samples between laboratories for characterization purposes. In the present work we have shown that it is also possible to carry out such capping by means of photoassisted metalorganic vapor phase epitaxy using excimer laser radiation to decompose arsine. Suitable control of the laser beam intensity allows the deposition of films varying in thickness from one monolayer to several hundreds of angstroms.