Spectrofluorimetry with attomole sensitivity in photonic crystal fibres

We report the use of photonic crystal fibres (PCF) as spectrofluorimetric systems in which sample solutions are excited within the microstructure of the fibre. The use of intra-fibre excitation has several advantages that combine to enable highly sensitive measurements of fluorescence spectra and lifetimes: long path-lengths are achieved by the efficient guidance of the fundamental mode; sample volumes contained within the micron-scale structure are very small, only a few nanolitres per cm of path; collection and guidance of the emitted fluorescence is efficient and the fluorescence lifetime is unperturbed. Fluorophores in bulk solution can be studied in hollow core PCF, whereas the use of PCF with a suspended, solid core enables selective excitation of molecules in close proximity to the silica surface, through interaction with the evanescent field. We demonstrate the measurement of fluorescence spectra and fluorescence lifetimes in each of these excitation regimes and report the detection of attomole quantities of fluorescein.