Ultra-sensitive Trace-Water Optical Sensor with In situ-synthesized Metal-Organic Framework in Glass Paper

Abstract

Monitoring of trace water in industrial gases is strongly recommended because contaminants cause serious problems during use, especially in the semiconductor industry. An ultra-sensitive trace-water sensor was developed with an in situ-synthesized metal-organic framework as the sensing material. The sample gas is passed through the sensing membrane and efficiently and rapidly collected by the sensing material in the newly designed gas collection/detection cell. The sensing membrane, glass paper impregnated with copper 1,3,5-benzenetricarboxylate (Cu-BTC), is also newly developed. The amount and density of the sensing material in the sensing membrane must be well balanced to achieve rapid and sensitive responses. In the present study, Cu-BTC was synthesized in situ in glass paper. The developed system gave high sensing performances with a limit of detection (signal/noise ratio = 3) of 9 parts per billion by volume (ppbv) H₂O and a 90% response time of 86 s for 200 ppbv H₂O. The reproducibility of the responses within and between lots had relative standard deviations for 500 ppbv H₂O of 0.8% (n = 10) and 1.5% (n = 3), respectively. The long-term (2 weeks) stability was 7.3% for 400 ppbv H₂O and one-year continuous monitoring test showed the sensitivity change of <~3% before and after the study. Furthermore, the system response was in good agreement with the response achieved in cavity ring-down spectroscopy. These performances are sufficient for monitoring trace water in industrial gases. The integrated system with light and gas transparent structure for gas collection/absorbance detection can also be used for other target gases, using specific metal-organic frameworks.