Quote: Originally posted by radagast | Assuming that fluorescence doesn't increase equally across the wavelength range while cranking up the laser's power (and I don't see why it would),
this might account for the background hump. | Fluorescence is the absorption and re-emission of photons, so
its emission spectrum is generally independent of the pumping energy. Emission lines are doppler-broadened for each transition, so with (a) a
room-temperature sample and (b) a spectrometer that doesn't discriminate with really fine resolution and (c) a laser with a broad emission spectrum
and (d) and an organic sample with lots of transitions, you'll end up with a big hump like you're seeing. (a), (b), and (c) each contribute their own
convolution width, and (d) means you're summing more than one Gaussian together.
What to do about it is another thing entirely. In the time-resolution paper I posted up-thread, they're using extraordinary sharp pulses and using a
photomultiplier tube in single-photon mode to count. They're not doing simultaneous measurements at different frequencies; they're scanning. So that's
not the easiest way to improve fluorescence rejection.
Other than improving the quality of all the components, the easiest thing to me seems to take advantage of the different ways that Raman scattering
and fluorescence behave with respect to frequency. The Raman spectrum will be shifted when you change pump frequency (by rotating the prism); the
fluorescence spectrum won't be. Some signal processing allows nulling out the bulk of the fluorescence. You can take spectra at different frequencies
by monochromating the laser. Run the beam through a prism to disperse the green beam. Use a lens to put the rays parallel again after you've got
enough separation. Then use a slit to select a pump frequency.
To estimate how well this might work, compute the wavenumber shift for ( 532 +/- 3 ) nm. That's what you can reasonable get out of a laser with an 8 nm emission width. That number is around 212
cm-1. At +/- 2 nm, it's 141 cm-1. At +/- 1nm, it's 71 cm-1. (Note that this is roughly 35 cm-1 per nm of
pump wavelength difference.) The broadest peaks are aroung 50 cm-1 (roughly), so even a fairly small pump wavelength difference would
suffice to get good peak separation. |