Flow-through microfluidic photoionization detectors for rapid and highly sensitive vapor detection

A photoionization detector (PID) is well known for its high sensitivity, large dynamic range, and non-destructive vapor detection capability. However, due to its tardy response, which results from the relatively large ionization chamber and dead volume, the application of the PID in gas chromatography (GC) has been limited. Here, we developed a rapid, flow-through, and highly sensitive microfluidic PID that was microfabricated directly on a conductive silicon wafer. The microfluidic PID has a significantly reduced ionization chamber volume of only 1.3 μL, nearly 10 times smaller than that of state-of-the-art PIDs and over 100 times smaller than that of commercial PIDs. Moreover, it has virtually zero dead volume due to its flow-through design. Consequently, the response time of the microfluidic PID can be considerably shortened, ultimately limited by its residence time (7.8 ms for 10 mL min(-1) and 78 ms for 1 mL min(-1)). Experimentally, the response of the microfluidic PID was measured to be the same as that of the standard flame ionization detector with peak full-widths-at-half-maximum of 0.25 s and 0.085 s for flow rates of 2.3 mL min(-1) and 10 mL min(-1), respectively. Our studies further show that the microfluidic PID was able to detect analytes down to the picogram level (at 3σ of noise) and had a linear dynamic range of six orders of magnitude. Finally, because of the very short distance between the electrodes, low voltage (<10 VDC, over 10 times lower than that in a regular PID) can be used for microfluidic PID operation. This work will open a door to broad applications of PIDs in gas analyzers, in particular, micro-GC and multi-dimensional GC.