IN a colloidal suspension containing particles of two different sizes,
there is an attractive force between the larger particles. This attra
ction is due to the extra volume that becomes available to the smaller
particles when the larger particles approach one another, thus increa
sing the entropy of the system. Entropic 'excluded-volume' effects of
this type have been studied previously in colloids and emulsions, in t
he context of phase-separation phenomena in the bulk(1-15) and at flat
surfaces(2,16). Here we show how similar effects can be used to posit
ion the larger particles of a binary mixture on a substrate, or to mov
e them in a predetermined way. Our experiments demonstrate the entropi
cally driven repulsion of a colloidal sphere (in a suspension of small
er spheres) from the edge of a step; the magnitude of the entropic bar
rier felt by the sphere is approximately twice its mean thermal energy
. These results indicate that passive structures etched into the walls
of a container create localized entropic force fields which can trap,
repel or induce the controlled drift of particles. Manipulation techn
iques based on these effects should be useful for making the highly or
dered particle arrays required for structures with photonic band gaps(
17,18), microelectronic mask materials(19), and materials for clinical
assays(20).