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]. 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