Characterization of Raman Spectroscopy System Transfer Functions in Intensity, Wavelength, and Time

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Characterization of Raman Spectroscopy System Transfer Functions in Intensity, Wavelength, and Time instruments Article Characterization of Raman Spectroscopy System Transfer Functions in Intensity, Wavelength, and Time Yu-Chung Lin and Joseph V. Sinfield * Lyles School of Civil Engineering, Purdue University, West Lafayette, IN 47907, USA; [email protected] * Correspondence: [email protected] Received: 30 June 2020; Accepted: 29 July 2020; Published: 5 August 2020 Abstract: The emergence of a wide variety of relatively low-cost compact spectrometers has led to an increase in the use of spectroscopic techniques by researchers in a broad array of fields beyond those that have traditionally employed these analytical methods. While the fundamental elements and functions of Raman systems are generally consistent, the specific components that compose a system may vary in number, design, and configuration, and researchers often modify off-the-shelf spectrometers for unique applications. Understanding the effect of instrument design and components on acquired information is thus crucial and provides the prospect to optimize the system to individual needs and to properly compare results obtained with different systems while also reducing the potential for unintended misinterpretation of data. This paper provides a practical treatment of the influences in a typical compact spectroscopy system that can impact the extent to which the output of the system is representative of the observed environment, a relationship that in measurement science is classically termed the system transfer function. For clarity, the transfer function is developed in terms of traditional Raman output parameters, namely intensity, wavelength, and time. Keywords: system; transfer function; Raman spectroscopy; intensity; wavelength; time 1. Introduction Raman spectroscopy is named after physicist C.V. Raman, who discovered the instantaneous inelastic light scattering phenomenon in 1928 [1]. The technique provides rich information to identify and characterize materials and has gained popularity because of both its simplicity and diverse range of applications. In this method, a monochromatic light source, usually a laser, is directed toward the target sample. Interaction between the incident photons and molecules of the sample scatter the incident light. While the majority of these scattered photons leave the sample at the same frequency at which they arrived (referred to as elastic or Rayleigh scattering), a small fraction of the photons may exchange energy with the molecules, leading to inelastic, or Raman scattering. In this latter case, individual incident photons may either lose energy (Stokes-shift; most common) or gain energy (anti-stokes-shift). For any given scattered photon, the amount of energy transferred is indicative of a vibrational and/or rotational energy state of the target molecule bonds and thus offers insight into the composition of the sample. To obtain this information, scattered photons are collected and guided to an instrument that separates spectral constituents. A light-sensitive detector is then used to assess the intensity of the scattered returns as a function of frequency to develop a Raman spectrum that reflects the molecular composition and structure of the sample. The rapid advance of Raman spectroscopy has been driven significantly by innovation in the underlying technologies that compose Raman systems. Developments in semiconductors have fostered the advent of compact, low-cost lasers across a wide range of operating frequencies. Advances in optics production, optical coatings, and fiber optics have enabled greater flexibility and customization in system designs. Developments in light detection and data acquisition have improved Raman Instruments 2020, 4, 22; doi:10.3390/instruments4030022 www.mdpi.com/journal/instruments Instruments 2020, 4, x 2 of 57 Advances in optics production, optical coatings, and fiber optics have enabled greater flexibility and Instruments 2020 4 customization, ,in 22 system designs. Developments in light detection and data acquisition 2have of 52 improved Raman system sensitivity and speed. Collectively, these advances have helped make the systemRaman sensitivityspectroscopic and speed.technique Collectively, more prevalent these advances in both have laboratory helped make and the Ramanfield settings, spectroscopic with techniqueparticularly more strong prevalent growth in in both the laboratory use of compac and fieldt Raman settings, spectroscopy with particularly systems strong and even growth portable in the useinstruments of compact for Ramanchemical spectroscopy analysis in applications systems and such even as portable food security instruments [2,3], art for examination chemical analysis [4–6], in applicationssitu mineral suchdetection as food [7], security explosive [2, 3detection], art examination [8], product [4–6 quality], in situ control mineral [9], detection forensic [ 7science], explosive [10], detectionand environmental [8], product monitoring quality control [11,12]. [9 ], forensic science [10], and environmental monitoring [11,12]. Due to thethe broadbroad arrayarray ofof applicationsapplications forfor whichwhich RamanRaman spectroscopyspectroscopy isis employed,employed, RamanRaman spectroscopic instruments may may encompass encompass a a variety variety of of context-specific context-specific components. components. It Itis isessential essential to toknow know how how each each of ofthese these components components contributes contributes to to variations variations in in the the properties properties of of the optical and electrical signals propagated inin the system and to evaluate and understand the possible output of the system beforebefore interpretinginterpreting results results derived derived from from its it use.s use. One One should should also also understand understand the the significance significance of theseof these possible possible variations variations before before comparing comparing the results the ofresults different of researchers.different researchers. With these perspectivesWith these inperspectives mind, this in paper mind, develops this paper the develops generalized the gene transferralized function transfer of afunction Raman of spectroscopic a Raman spectroscopic system for thesystem parameters for the ofparameters intensity, wavelength,of intensity, andwavele timength, and thenand appliestime and the then generalized applies formulationthe generalized to a specificformulation Raman to a spectroscopic specific Raman system spectroscopic as an example. system as an example. This paper first first introduces introduces several several general general components components in ina Raman a Raman system system and and provides provides an anoverview overview of how of howthe Raman the Raman phenomenon phenomenon is indu isced induced and observed and observed in a typical ina system. typical Transfer system. Transferfunctions functions for output for characterizing output characterizing quantitiesquantities of intensity, of wavelength, intensity, wavelength, and time are and then time developed are then developedby following by the following sequence the of sequencelight propagation of light propagationthrough a system, through from a system,the laser fromsource the to laser the sample, source toand the to sample,the detector and and to thedata detector acquisition and electronics. data acquisition For the electronics. intensity analysis, For the energy intensity losses analysis, when energylight propagates losses when through light different propagates components through in di thfferente system components are of greatest in the concern. system The are wavelength of greatest concern.analysis Thehighlights wavelength changes analysis in the highlights wavelengths changes managed in the wavelengths and/or observed managed as light and/or traverses observed the as lightsystem. traverses Lastly, thethe system. time delay Lastly, analysis the time draws delay attention analysis to draws group attention delay and to signal group spreading delay and which signal spreadingmay occur whichin fiber may optic occur and inelectronic fiber optic components, and electronic respectively. components, respectively. 2. The Components in a Raman System A Raman spectroscopy system requires a coherent optical source (usually a laser), a device to selectively examine bands of optical wavelengths composing the scattered return, and a detector to assess the scattering. In a typica typicall lab benchtop Raman spectroscopicspectroscopic system, there are also usually optics to collect, collect, direct, direct, and and focus focus the the light; light; to to elim eliminateinate unwanted unwanted frequencies; frequencies; or to or divert to divert part part of the of thelight light (for (forexample example as a trigger as a trigger for data for acquisition). data acquisition). There is There also usually is also usuallya sample a holder sample that holder contains that containsthe sample the of sample interest of (often interest a cuvette). (often a cuvette).In a portable In a Raman portable system, Raman the system, device the may device directly may focus directly on focusthe environment on the environment of interest of without interest a without container a containerto hold the to target. hold the No target. matter No what matter kind whatof Raman kind ofspectroscopic Raman spectroscopic system, all system, components all components along the along inbound the inboundand return and light return paths light as paths well as as well all asconnections all connections and conduits and conduits between
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