A method of determining temperatures at localized regions of a substrate during processing of the substrate in a photolithography process includes the following steps: independently illuminating a photoresist layer including a photoresist pattern at a plurality of locations on the substrate with a light source, so that light is diffracted off the plurality of locations of the photoresist pattern; measuring the diffracted light from the plurality of locations to determine measured diffracted values associated with respective locations from the plurality of locations; and comparing the measured diffracted values against a library to determine a pre-illumination process temperature of the photoresist layer at the plurality of locations.