Trace Analysis of Gases and Liquids with Spontaneous Raman Scattering Based on the Integrating Sphere Principle

Spontaneous Raman scattering is an attractive optical technique for the analysis of gases and liquids; however, their low densities and notoriously weak scattering cross sections demand an enhancement of the spontaneous Raman scattering signal for detection. Here, we have developed a simple but highly effective and fast technique to enhance the signal of spontaneous Raman scattering from gases and liquids. The technique is developed based on the principle of an integrating sphere, which realizes the multiple pass actions of low-energy pump light and the collection of all Raman scattered light for a sample volume of 2 mL. By measuring the ambient air sample with an exposure time of 180 s, we found the experimental detection limit of our spontaneous Raman scattering setup can reach 3 ppm. CH4 (<2 ppm) in air can be also examined by increasing the exposure time to 300 s. The performance of our setup used for the analysis of trace gases is further illustrated by characterizing ethane, propane, butane, and pentane in methane as well as isotopes of carbon dioxide. The results reveal that the detection limit of our setup for liquids can be improved by nearly 4 orders of magnitude compared to that of confocal Raman scattering spectroscopy with the same experimental conditions.

Automated summary

In this study, a simple and effective method was developed to enhance the signal of spontaneous Raman scattering from gases and liquids. By utilizing the principle of an integrating sphere, multiple pass actions of low-energy pump light and the collection of all Raman scattered light were achieved. The experimental results showed that our setup can significantly improve the detection limit for liquids compared to confocal Raman scattering spectroscopy.