ABSTRACT
Fluorescence interference in Raman spectroscopy is a well-known problem and is especially significant in portable instruments where the availability of a variety of exciting wavelengths is unlikely. Several fluorescence avoidance and mitigation schemes are described in the literature, and implemented by Raman spectrometer manufacturers, but there is no standard method for evaluating the accuracy and repeatability of these schemes. Some test samples shown in instrument descriptions, such as "dark rum" and "sesame seed oil" are not reproducible. Therefore, we propose a set of colored LEGO blocks as "standard" samples for this purpose; they have the attractive properties of being very low cost, rugged, non-toxic, easy to transport and store, and appear to be manufactured using a standard process. This paper shows the Raman spectra of a set of these blocks at different excitation wavelengths, acquired on laboratory instruments, along with their visible-near-infrared spectra. The goal is to qualitatively understand the origins of the observed fluorescence and lay the groundwork for exploring the effectiveness of methods currently implemented on handheld Raman instruments.
ABSTRACT
The most common mid-infrared (MIR) attenuated total reflection (ATR) accessory has a nominal angle of incidence of 45° and does not have a polarizer. A spectrum recorded with such an accessory does not hold enough information for the sophisticated ATR correction of MIR spectra with strong peaks, which are often strongly affected by refractive index changes due to anomalous dispersion. Here we show that a 45° ATR spectrum recorded without a polarizer and the polarization angle for the same ATR Fourier transform infrared spectroscopy system provide enough information to determine the ATR s-polarized spectrum. Further analysis with an improved non-iterative Kramers-Kronig analysis immediately yields the complex refractive index function. The analysis is about two orders of magnitude faster than iterative formalism and runs within seconds on a typical office PC. The effectiveness of our advanced ATR correction formalism is showcased through its application to water, employing diamond, ZnSe, and Ge ATR crystals, along with two distinct ATR accessories. Additionally, the formalism is applied to octadecane spectra. Potential sources of errors such as incidence angle spread, dispersion of the polarization angle, and the influence of reflection at the air/ATR crystal interface are investigated by simulations.
