We report the observation of an unusual hexagonal (4H) phase in silver nano
particles deposited by high-pressure de magnetron sputtering. X-ray-diffrac
tion and transmission electron microscopy studies clearly reveal the presen
ce of a hexagonal 4H phase in the silver nanoparticles in addition to the c
ubic 3C phase-which is the equilibrium crystal structure for bulk silver. T
he smaller the average particle size, the larger was the volume fraction of
the 4H phase. The hexagonal phase can be made to revert to the usual cubic
structure by heating the nanocrystalline sample and allowing the grains to
grow. This rare hexagonal phase had previously been observed only in certa
in mineral deposits. We show that there is a size-induced stabilization of
this phase in nanocrystalline silver below approximate to 30 nm.