Methods and systems for performing optical measurements of geometric structures filled with an adsorbate by a gaseous adsorption process are presented herein. Measurements are performed while the metrology target under measurement is treated with a flow of purge gas that includes a controlled amount of fill material. A portion of the fill material adsorbs onto the structures under measurement and fills openings in the structural features, spaces between structural features, small volumes such as notches, trenches, slits, contact holes, etc. In one aspect, the desired degree of saturation of vaporized material in the gaseous flow is determined based on the maximum feature size to be filled. In one aspect, measurement data is collected when a structure is unfilled and when the structure is filled by gaseous adsorption. The collected data is combined in a multi-target model based measurement to reduce parameter correlations and improve measurement performance.