Abstract: For small angles that are near critical angle, a primary incident X-ray beam has excellent depth resolution. A series of X-ray fluorescence measurements are performed at varying small angles and analyzed for depth profiling of elements within a substrate. One highly useful application of the X-ray fluorescence measurements is depth profiling of a dopant used in semiconductor manufacturing such as arsenic, phosphorus, and boron. In one example, angles are be varied from 0.01° to 0.20° and measurements made to profile arsenic distribution within a semiconductor wafer. In one embodiment, measurements are acquired using a total reflection X-ray fluorescence (TXRF) type system for both known and unknown profile distribution samples. The fluorescence measurements are denominated in counts/second terms and formed as ratios comparing the known and unknown sample results. The count ratios are compared to ratios of known to unknown samples that are acquired using a control analytical measurement technique.