[en] The detection limit for synchrotron radiation total reflection x-ray fluorescence (TXRF) that can routinely be achieved for transition metals is about 8E7 atoms/cm² for a standard 1000 second counting time. This high sensitivity can be further improved by using a pre-concentration process such as vapor phase decomposition (VPD). The sensitivity enhancement of VPD-TXRF over TXRF is usually estimated from the ratio of the total wafer surface area to the instrumental sampling area on the wafer. For example, a 200 mm wafer with a 5 mm edge exclusion has a total surface area of 283.5 cm². Assuming a sampling area of 0.126 cm² for the TXRF instrument at the Stanford Synchrotron Radiation Laboratory (SSRL) the gain in sensitivity for the VPD-TXRF technique will be 1 : 2250. This means, theoretically, that the TXRF detection limit of 8E7 atoms/cm² could be further reduced to 3.6 E4 atoms/cm² by applying this technique. During the VPD process, the contaminants on the wafer surface will be collected into a single droplet and dried on the wafer surface for TXRF analysis. However, impurities in the UPW (ultra pure water), chemicals or from handling cannot be ignored. Our investigation of wafers subjected, to different cleaning processes has revealed that background signals on the dry spot could arise from the VPD process itself. Therefore, the baseline determined by the purity of the UPW and starting chemicals limits the detection limits of VPD-SR-TXRF. (author)