Use of an Internal Mercury-Argon Lamp for the Calibration of Raman Frequency in Large Raman Images of Astromaterials

Raman imaging is an emerging tool for the analysis of meteorites, as it is capable of describing mineralogy, carbon composition/speciation, and crystal orientation all within a petrographic context. Adequately examining the heterogeneous composition of a meteorite, while maintaining low laser powers needed to prevent damage to meteorite mineralogy and organics, often requires the collection of large Raman images with long collection times on the timescale of days. However, the frequency calibration of the Raman instrument/spectrometer drifts on long timescales resulting in low frequency precision for the Raman spectra comprising a large Raman image. This decrease in frequency precision can compromise the analysis of geological markers that can provide important information on a meteorite sample. We examine, in detail, the change in bandwidth and frequency of the Raman bands and Hg-Ar emission lines in our Raman images as a function of time and laboratory temperature. To overcome the drift in calibration, we utilize a commercial WITec Raman instrument with an internal Hg-Ar calibration lamp to individually calibrate each spectrum in the Raman image. Our instrument, known as “Ratatoskr”, uses a beam splitter in place of the customary mirror to facilitate collection of Hg-Ar calibration lines concurrent with Raman spectra. We show that using the internal calibration we can improve the frequency precision for the spectra in our Raman images from ~±0.15 cm(exp -1) to ~±0.05 cm(exp -1) for Raman spectra collected over multiple days. This is important as it improves measurements of mineral chemistry, latent strain, and other features that are dependent upon accurate peak position determination. We also examine the spectral signal-to-noise ratio needed to minimize the frequency error when fitting bands to Gaussian/Lorentzian profiles. We then use our results to suggest a general method for calibrating the frequency of Raman spectra in large Raman images.