Methods and systems for estimating values of process parameters, structural parameters, or both, based on x-ray scatterometry measurements of high aspect ratio semiconductor structures are presented herein. X-ray scatterometry measurements are performed at one or more steps of a fabrication process flow. The measurements are performed quickly and with sufficient accuracy to enable yield improvement of an on-going semiconductor fabrication process flow. Process corrections are determined based on the measured values of parameters of interest and the corrections are communicated to the process tool to change one or more process control parameters of the process tool. In some examples, measurements are performed while the wafer is being processed to control the on-going fabrication process step. In some examples, X-ray scatterometry measurements are performed after a particular process step and process control parameters are updated for processing of future devices.