Neutron reflectometry is used to study photomechanical effects in thin films of azobenzene polymer cast onto silicon substrates. A significant photoexpansion effect, up to 17%, is observed at 25 degrees C, due to the free volume requirement of the azobenzene chromophore photoisomerization. Above a distinct crossover temperature of similar to 50 degrees C, the material response is inverted and instead photocontraction effects, of more than -15%, are observed. In this case the combined photomotion and thermal mobility enables aggregation and crystallization of the azobenzene dipoles. The photomechanical effects, which can be reversed, occur readily using a variety of irradiation powers, incident polarizations, and film thickness values. This photomechanical behavior, which appears to be general to all azo materials, is likely the origin for a wide variety of curious photomotions observed in these systems, including macroscopic bending of samples and micron-scale surface mass transport.