A method for the combined measurement of volatile and condensable organic AMC in semiconductor applications

Monitoring airborne molecular contamination (AMC) at the parts per trillion (ppt) level in cleanroom environments, scanner applications and compressed gas lines is essential for processes, equipment and yield-control. For the operation of EUV tools, in particular, volatile organic contamination is known to have as much impact as condensable organic compounds, which requires a suitable sampling and measurement methodology. Some of the current industry standards use sample traps comprised of porous 2,6-diphenylene-oxide polymer resin, such as Tenax®, for measuring volatile organic ( 6 C atoms, about toluene and higher) AMC. Inherent problems associated with these traps are a number of artifacts and chemical reactions that reduce accuracy of reported organic AMC concentrations. The break-down of the polymeric material forms false positive artifacts when used in the presence of reactive gases, such as nitrous acid and ozone, which attack and degrade the polymer to form detectable AMC. Most importantly, these traps have poor capture efficiency for volatile organic compounds (VOC). To address the disadvantages of polymer-based sample traps, we developed a method based on carbonaceous, multi-layered adsorbent traps to replace the 2,6-diphenylene-oxide polymer resin sample trap type. Along with the new trap’s ability to retain volatile organics, the trap was found to provide artifact-free results. With industry trends towards detecting more contaminants while continuously reducing required reporting limits for those compounds, artifact-free and accurate detection of AMC is needed at the parts per quadrillion (ppq) level. The proposed, multi-layered trap substantially increases laboratory productivity and reduces cost by eliminating the need to analyze condensable and volatile organic compounds in two separate methods. In our studies, even some organic compounds with six C-atoms, that are part of exposure tool OEM requirements, were not effectively retained by polymeric traps, but were fully retained on the multi-layered adsorbent trap. This demonstrates that the standard trap used in the industry will result in significantly underreporting actual AMC concentrations for volatile organic compounds, including some siloxanes (TMS, HMDSO, D3). Performance of the proposed trap was excellent at both zero and 50% relative humidity, an important metric, as the trap is used for AMC detection in dry supply gases and humidified environments. Retention of all organic compounds was quantitative for more than 30 liters of air, sufficient for ppq-level detection limits. Desorption efficiency was 94% for C26 compounds. Pressure drop through the new trap was comparable to that of polymer-based traps and much lower than other, commercially available carbonaceous traps. Precision of repeated analyses was 5%, a very good result. Resolution of IPA and acetone was complete and that of a mix of halogenated refrigerants was much improved over existing methods. We propose to adopt this methodology as a new industry standard to overcome widespread inaccuracy in the reporting of volatile organic AMC and false positive condensable AMC.