Single-Grating Monolithic Spatial Heterodyne Raman Spectrometer: An Investigation on the Effects of Detector Selection.

Spatial heterodyne Raman spectrometers (SHRSs) are modified forms of Michelson interferometers, except the mirrors in a Michelson interferometer are replaced with stationary diffraction gratings. This design removes the need for an entrance slit, as is the case in a dispersive spectrometer, and removes the need to scan the spectrum by using a moving mirror in a modern Michelson interferometer. In previous studies, various SHRS variants, such as free-standing two-grating SHRS, single-grating SHRS (1g-SHRS), monolithic SHRS (mSHRS), and single-grating mSHRS (1g-mSHRS), have been evaluated. However, the present study exclusively focuses on the 1g-mSHRS configuration. The 1g-mSHRS and 1g-SHRS increase the spectral range at fixed grating line density while trading off spectral resolution and resolving power. The mSHRS benefits from increased rigidity, lack of moving parts, and reduced footprint. In this study, we investigate how the choice of detector impacts the performance of the 1g-mSHRS system, with a specific focus on evaluating the performance of three types of cameras: charged-coupled device (CCD), intensified CCD (ICCD), and complementary metal-oxide-semiconductor (CMOS) cameras. These systems were evaluated using geological, organic, and inorganic samples using a 532 nm continuous wave laser for the CMOS and CCD cameras, and a 532 nm neodymium-doped yttrium aluminum garnet pulsed laser for the ICCD camera. The footprint of the 1g-mSHRS was 3.5 × 3.5 × 2.5 cm3 with a mass of 272 g or 80 g, depending on whether the monolith housing is included or not. We found that increasing the number of pixels utilized along the x-axis of the camera increases fringe visibility (FV) and optimizes the resolution (by capturing the entirety of the grating and magnifying the fringes). The number of pixels utilized in the y-axis, chip size, and dimensions, affect the signal-to-noise ratio of the systems. Additionally, we discuss the effect of pixel pitch on the recovery of Fizeau fringes, including the relationship between the Nyquist frequency, aliasing, and FV.

Remote Raman Sensing Using a Single-Grating Monolithic Spatial Heterodyne Raman Spectrometer: A Potential Tool for Planetary Exploration.

Advances in Raman instrumentation have led to the implementation of a remote dispersive Raman spectrometer on the Perseverance rover on Mars, which is used for remote sensing. For remote applications, dispersive spectrometers suffer from a few setbacks such as relatively larger sizes, low light throughput, limited spectral ranges, relatively low resolutions for small devices, and high sensitivity to misalignment. A spatial heterodyne Raman spectrometer (SHRS), which is a fixed grating interferometer, helps overcome some of these problems. Most SHRS devices that have been described use two fixed diffraction gratings, but a variance of the SHRS called the one-grating SHRS (1g-SHRS) replaces one of the gratings with a mirror, which makes it more compact. In a recent paper we described monolithic two-gratings SHRS, and in this paper, we investigate a single-grating monolithic SHRS (1g-mSHRS), which combines the 1g-SHRS with a monolithic setup previously tested at the University of South Carolina. This setup integrates the beamsplitter, grating, and mirror into a single monolithic device. This reduces the number of adjustable components, allows for easier alignment, and reduces the footprint of the device (35 × 35 × 25 mm with a weight of 80 g). This instrument provides a high spectral resolution (∼9 cm-1) and large spectral range (7327 cm-1) while decreasing the sensitivity to alignment with a field of view of 5.61 mm at 3m. We discuss the characteristics of the 1g-mSHRS by measuring the time-resolved remote Raman spectra of a few inorganic salts, organics, and minerals at 3 m. The 1g-mSHRS makes a good candidate for planetary exploration because of its large spectral range, greater sensitivity, competitively higher spectral resolution, low alignment sensitivity, and high light throughput in a compact easily aligned system with no moving parts.

Compositionally and density stratified igneous terrain in Jezero crater, Mars.

Before Perseverance, Jezero crater's floor was variably hypothesized to have a lacustrine, lava, volcanic airfall, or aeolian origin. SuperCam observations in the first 286 Mars days on Mars revealed a volcanic and intrusive terrain with compositional and density stratification. The dominant lithology along the traverse is basaltic, with plagioclase enrichment in stratigraphically higher locations. Stratigraphically lower, layered rocks are richer in normative pyroxene. The lowest observed unit has the highest inferred density and is olivine-rich with coarse (1.5 millimeters) euhedral, relatively unweathered grains, suggesting a cumulate origin. This is the first martian cumulate and shows similarities to martian meteorites, which also express olivine disequilibrium. Alteration materials including carbonates, sulfates, perchlorates, hydrated silicates, and iron oxides are pervasive but low in abundance, suggesting relatively brief lacustrine conditions. Orbital observations link the Jezero floor lithology to the broader Nili-Syrtis region, suggesting that density-driven compositional stratification is a regional characteristic.

Suppressing the Multiplex Disadvantage in Photon-Noise Limited Interferometry Using Cross-Dispersed Spatial Heterodyne Spectrometry.

Spatial heterodyne spectrometers are members of the static Fourier transform class of spectrometers, well-regarded for their ability to acquire high-resolution, high wavelength precision emission spectra in compact, light footprint packages. In a spatial heterodyne spectrometer experiment, a Fizeau fringe is generated for every spectral feature in a given spectrum, and spatial heterodyne spectrometer records the superposition of all Fizeau fringes in the spectrum on a detector. Hence, the sensitivity of spatial heterodyne spectrometers is constrained by uncorrelated, multiplicative photon noise that limits the detection of spectral features to those that are more luminous than the square root of the total incident flux onto the detector. In essence, powerful spectral features create a rising floor of noise that wash out less luminous features. In the present work, we introduce a novel spectrometer coupling, that being an Amici prism spectrometer in series with spatial heterodyne spectrometer, that correlates photon shot noise along one axis of a detector that in turn suppresses multiplicative photon noise within each row of the interferogram image. We demonstrate that this spectrometer pairing facilitates the measurement of weak Raman spectral features that, in a traditional spatial heterodyne spectrometer measurement, would be washed out by multiplicative photon noise.

A Monolithic Spatial Heterodyne Raman Spectrometer: Initial Tests.

A monolithic spatial heterodyne Raman spectrometer (mSHRS) is described, where the optical components of the spectrometer are bonded to make a small, stable, one-piece structure. This builds on previous work, where we described bench top spatial heterodyne Raman spectrometers (SHRS), developed for planetary spacecraft and rovers. The SHRS is based on a fixed grating spatial heterodyne spectrometer (SHS) that offers high spectral resolution and high light throughput in a small footprint. The resolution of the SHS is not dependent on a slit, and high resolution can be realized without using long focal length dispersing optics since it is not a dispersive device. Thus, the SHS can be used as a component in a compact Raman spectrometer with high spectral resolution and a large spectral range using a standard 1024 element charge-coupled device. Since the resolution of the SHRS is not dependent on a long optical path, it is amenable to the use of monolithic construction techniques to make a compact and robust device. In this paper, we describe the use of two different monolithic SHSs (mSHSs), with Littrow wavelengths of 531.6 nm and 541.05 nm, each about 3.5 × 3.5 × 2.5 cm in size and weighing about 80 g, in a Raman spectrometer that provides ∼3500 cm-1 spectral range with 4-5 cm-1 and 8-9 cm-1 resolution, for 600 grooves/mm and 150 grooves/mm grating-based mSHS devices, respectively. In this proof of concept paper, the stability, spectral resolution, spectral range, and signal-to-noise ratio of the mSHRS spectrometers are compared to our bench top SHRS that uses free-standing optics, and signal to noise comparisons are also made to a Kaiser Holospec f/1.8 Raman spectrometer.

Spatial Heterodyne Raman Spectrometer (SHRS) for In Situ Chemical Sensing Using Sapphire and Silica Optical Fiber Raman Probes.

A spatial heterodyne Raman spectrometer (SHRS), constructed using a modular optical cage and lens tube system, is described for use with a commercial silica and a custom single-crystal (SC) sapphire fiber Raman probe. The utility of these fiber-coupled SHRS chemical sensors is demonstrated using 532 nm laser excitation for acquiring Raman measurements of solid (sulfur) and liquid (cyclohexane) Raman standards as well as real-world, plastic-bonded explosives (PBX) comprising 1,3,5- triamino- 2,4,6- trinitrobenzene (TATB) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) energetic materials. The SHRS is a fixed grating-based dispersive interferometer equipped with an array detector. Each Raman spectrum was extracted from its corresponding fringe image (i.e., interferogram) using a Fourier transform method. Raman measurements were acquired with the SHRS Littrow wavelength set at the laser excitation wavelength over a spectral range of ∼1750 cm-1 with a spectral resolution of ∼8 cm-1 for sapphire and ∼10 cm-1 for silica fiber probes. The large aperture of the SHRS allows much larger fiber diameters to be used without degrading spectral resolution as demonstrated with the larger sapphire collection fiber diameter (330 µm) compared to the silica fiber (100 µm). Unlike the dual silica fiber Raman probe, the dual sapphire fiber Raman probe did not include filtering at the fiber probe tip nearest the sample. Even so, SC sapphire fiber probe measurements produced less background than silica fibers allowing Raman measurements as close as ∼85 cm-1 to the excitation laser. Despite the short lengths of sapphire fiber used to construct the sapphire probe, well-defined, sharp sapphire Raman bands at 420, 580, and 750 cm-1 were observed in the SHRS spectra of cyclohexane and the highly fluorescent HMX-based PBX. SHRS measurements of the latter produced low background interference in the extracted Raman spectrum because the broad band fluorescence (i.e., a direct current, or DC, component) does not contribute to the interferogram intensity (i.e., the alternating current, or AC, component). SHRS spectral resolution, throughput, and signal-to-noise ratio are also discussed along with the merits of using sapphire Raman bands as internal performance references and as internal wavelength calibration standards in Raman measurements.

Optimizing Data Reduction Procedures in Spatial Heterodyne Raman Spectroscopy with Applications to Planetary Surface Analogs.

A spatial heterodyne Raman spectrometer (SHRS) is a variant of a Michelson interferometer in which the mirrors of a Michelson are replaced with two stationary diffraction gratings. When light enters the SHRS, it is reflected off of diffraction gratings at frequency-dependent angles that produce crossed wavefronts in space that can be imaged using a plane array detector. The crossed wavefronts, which represent a superposition of interference fringes, are converted to a Raman spectrum upon applying a Fourier transform. In this work, a new approach to intensity calibration is discussed that originates from modeling the shot noise produced by the SHRS and converting the real noise to idealized white noise as predicted by theory. This procedure has two effects. First, the technique produces Raman spectra with white noise. Second, when the mean of the noise is normalized to one, the technique produces Raman spectra where the intensity axis is equivalent to signal-to-noise ratio. The data reduction technique is then applied to the measurement of materials of interest to the planetary science community, including minerals and inorganic salts, at a distance of 5 m from the collecting optic.

Standoff Laser-Induced Breakdown Spectroscopy (LIBS) Using a Miniature Wide Field of View Spatial Heterodyne Spectrometer with Sub-Microsteradian Collection Optics.

A spatial heterodyne spectrometer (SHS) is described for standoff laser-induced breakdown spectroscopy (LIBS) measurements. The spatial heterodyne LIBS spectrometer (SHLS) is a diffraction grating based interferometer with no moving parts that offers a very large field of view, high light throughput, and high spectral resolution in a small package. The field of view of the SHLS spectrometer is shown to be ∼1° in standoff LIBS measurements. In the SHLS system described here, the collection aperture was defined by the 10 mm diffraction gratings in the SHS and standoff LIBS measurements were made up to 20 m with no additional collection optics, corresponding to a collection solid angle of 0.2 µsr, or f/2000, and also using a small telescope to increase the collection efficiency. The use of a microphone was demonstrated to rapidly optimize laser focus for 20 m standoff LIBS measurements.

Transmission Raman Measurements Using a Spatial Heterodyne Raman Spectrometer (SHRS).

A spatial heterodyne Raman spectrometer (SHRS) was used to measure transmission Raman spectra of highly scattering compounds. Transmission Raman spectral intensities of ibuprofen were only 2.4 times lower in intensity than backscatter Raman spectra. The throughput was about eight times higher than an f/1.8 dispersive spectrometer, and the width of the area viewed was found to be seven to nine times higher, using 50.8 mm and 250 mm focal length collection lenses. However, the signal-to-noise (S/N) ratio was two times lower for the SHRS than the f/1.8 dispersive spectrometer, apparently due to high levels of stray light.

Miniature Spatial Heterodyne Raman Spectrometer with a Cell Phone Camera Detector.

A spatial heterodyne Raman spectrometer (SHRS) with millimeter-sized optics has been coupled with a standard cell phone camera as a detector for Raman measurements. The SHRS is a dispersive-based interferometer with no moving parts and the design is amenable to miniaturization while maintaining high resolution and large spectral range. In this paper, a SHRS with 2.5 mm diffraction gratings has been developed with 17.5 cm-1 theoretical spectral resolution. The footprint of the SHRS is orders of magnitude smaller than the footprint of charge-coupled device (CCD) detectors typically employed in Raman spectrometers, thus smaller detectors are being explored to shrink the entire spectrometer package. This paper describes the performance of a SHRS with 2.5 mm wide diffraction gratings and a cell phone camera detector, using only the cell phone's built-in optics to couple the output of the SHRS to the sensor. Raman spectra of a variety of samples measured with the cell phone are compared to measurements made using the same miniature SHRS with high-quality imaging optics and a high-quality, scientific-grade, thermoelectrically cooled CCD.

Improving Spectral Results Using Row-by-Row Fourier Transform of Spatial Heterodyne Raman Spectrometer Interferogram.

This work describes a method of applying the Fourier transform to the two-dimensional Fizeau fringe patterns generated by the spatial heterodyne Raman spectrometer (SHRS), a dispersive interferometer, to correct the effects of certain types of optical alignment errors. In the SHRS, certain types of optical misalignments result in wavelength-dependent and wavelength-independent rotations of the fringe pattern on the detector. We describe here a simple correction technique that can be used in post-processing, by applying the Fourier transform in a row-by-row manner. This allows the user to be more forgiving of fringe alignment and allows for a reduction in the mechanical complexity of the SHRS.

Performance Assessment of a Plate Beam Splitter for Deep-Ultraviolet Raman Measurements with a Spatial Heterodyne Raman Spectrometer.

In earlier works, we demonstrated a high-resolution spatial heterodyne Raman spectrometer (SHRS) for deep-ultraviolet (UV) Raman measurements, and showed its ability to measure UV light-sensitive compounds using a large laser spot size. We recently modified the SHRS by replacing the cube beam splitter (BS) with a custom plate beam splitter with higher light transmission, an optimized reflectance/transmission ratio, higher surface flatness, and better refractive index homogeneity than the cube beam splitter. Ultraviolet Raman measurements were performed using a SHRS modified to use the plate beam splitter and a matching compensator plate and compared to the previously described cube beam splitter setup. Raman spectra obtained using the modified SHRS exhibit much higher signals and signal-to-noise (S/N) ratio and show fewer spectral artifacts. In this paper, we discuss the plate beam splitter SHRS design features, the advantages over previous designs, and discuss some general SHRS issues such as spectral bandwidth, S/N ratio characteristics, and optical efficiency.

Ultraviolet Stand-off Raman Measurements Using a Gated Spatial Heterodyne Raman Spectrometer.

A spatial heterodyne Raman spectrometer (SHRS) is evaluated for stand-off Raman measurements in ambient light conditions using both ultraviolet (UV) and visible pulsed lasers with a gated ICCD detector. The wide acceptance angle of the SHRS simplifies optical coupling of the spectrometer to the telescope and does not require precise laser focusing or positioning of the laser on the sample. If the laser beam wanders or loses focus on the sample, as long as it is in the field of view of the SHRS, the Raman signal will still be collected. The SHRS is not overly susceptible to vibrations, and a vibration isolated optical table was not necessary for these measurements. The system performance was assessed by measuring stand-off UV and visible Raman spectra of a wide variety of materials at distances up to 18 m, using 266 nm and 532 nm pulsed lasers, with 12.4 in. and 3.8 in. aperture telescopes, respectively.

Deep-Ultraviolet Raman Measurements Using a Spatial Heterodyne Raman Spectrometer (SHRS).

A deep-ultraviolet (UV) 244 nm excitation spatial heterodyne Raman spectrometer (SHRS) is demonstrated for the first time. The deep-UV SHRS has no moving parts, and even though it is small for a deep-UV Raman spectrometer, the spectral resolution is shown to be about 4 cm(-1). The deep-UV SHRS also has a large input aperture and acceptance angle, and the resulting large field of view is shown to be useful to avoid laser-induced sample degradation. In this feasibility study, Raman spectra of several compounds are measured to demonstrate the spectral resolution and range of the system. A photosensitive compound is also measured to demonstrate the use of a large laser spot to minimize UV-laser-induced sample degradation.

Direct measurements of sample heating by a laser-induced air plasma in pre-ablation spark dual-pulse laser-induced breakdown spectroscopy (LIBS).

Direct measurements of temperature changes were made using small thermocouples (TC), placed near a laser-induced air plasma. Temperature changes up to ~500 °C were observed. From the measured temperature changes, estimates were made of the amount of heat absorbed per unit area. This allowed calculations to be made of the surface temperature, as a function of time, of a sample heated by the air plasma that is generated during orthogonal pre-ablation spark dual-pulse (DP) LIBS measurements. In separate experiments, single-pulse (SP) LIBS emission and sample ablation rate measurements were performed on nickel at sample temperatures ranging from room temperature to the maximum surface temperature that was calculated using the TC measurement results (500 °C). A small, but real sample temperature-dependent increase in both SP LIBS emission and the rate of sample ablation was found for nickel samples heated up to 500 °C. Comparison of DP LIBS emission enhancement values for bulk nickel samples at room temperature versus the enhanced SP LIBS emission and sample ablation rates observed as a function of increasing sample temperature suggests that sample heating by the laser-induced air plasma plays only a minor role in DP LIBS emission enhancement.

Remote Raman spectroscopy for planetary exploration: a review.

In this review, we discuss the current state of standoff Raman spectroscopy as it applies to remote planetary applications, including standoff instrumentation, the technique's ability to identify biologically and geologically important analytes, and the feasibility to make standoff Raman measurements under various planetary conditions. This is not intended to be an exhaustive review of standoff Raman and many excellent papers are not mentioned. Rather it is intended to give the reader a quick review of the types of standoff Raman systems that are being developed and that might be suitable for astrospectroscopy, a look at specific analytes that are of interest for planetary applications, planetary measurement opportunities and challenges that need to be solved, and a brief discussion of the feasibility of making surface and plume planetary Raman measurements from an orbiting spacecraft.

Raman spectroscopy using a spatial heterodyne spectrometer: proof of concept.

The use of a spatial heterodyne interferometer-based spectrometer (SHS) for Raman spectroscopy is described. The motivation for this work is to develop a small, rugged, high-resolution ultraviolet (UV) Raman spectrometer that is compatible with pulsed laser sources and that is suitable for planetary space missions. UV Raman is a particular technical challenge for space applications because dispersive (grating) approaches require large spectrographs and very narrow slits to achieve the spectral resolution required to maximize the potential of Raman spectroscopy. The heterodyne approach of the SHS has only a weak coupling of resolution and throughput, so a high-resolution UV SHS can both be small and employ a wide slit to maximize throughput. The SHS measures all optical path differences in its interferogram simultaneously with a detector array, so the technique is compatible with gated detection using pulsed lasers, important to reject ambient background and mitigate fluorescence (already low in the UV) that might be encountered on a planetary surface where samples are uncontrolled. The SHS has no moving parts, and as the spectrum is heterodyned around the laser wavelength, it is particularly suitable for Raman measurements. In this preliminary report we demonstrate the ability to measure visible wavelength Raman spectra of liquid and solid materials using an SHS Raman spectrometer and a visible laser. Spectral resolution and bandpass are also discussed. Separation of anti-Stokes and Stokes Raman bands is demonstrated using two different approaches. Finally spectral bandpass doubling is demonstrated by forming an interference pattern in both directions on the ICCD detector followed by analysis using a two-dimensional Fourier transform.

Trace molecular detection via surface-enhanced Raman scattering and surface-enhanced resonance Raman scattering at a distance of 15 meters.

We report the first demonstration of surface-enhanced Raman spectroscopy (SERS) detection of para-mercapto benzoic acid (pMBA) and surface-enhanced resonance Raman spectroscopy (SERRS) detection of brilliant cresyl blue (BCB) and cresyl violet perchlorate (CVP) with continuous-wave excitation from a stand-off distance of 15 meters. We further report the first stand-off SERRS detection of BCB and CVP at that same distance in the presence of ambient fluorescent and incandescent/blackbody background light. These preliminary results suggest that it is possible to detect sub-nanomole amounts of material at reasonable distances with eye-safe laser powers using stand-off SERRS and serve as proof-of-concept highlighting the potential extension of stand-off Raman spectroscopy to include SERS and SERRS for remote, eye-safe chemical detection, analysis, and imaging in the presence of ambient background light.

Analysis of titanium dioxide in synthetic fibers using Raman microspectroscopy.

The ability of Raman microspectroscopy to distinguish between rutile and anatase forms of the inorganic pigment titanium dioxide (TiO(2)) and to make quantitative measurements of titania loading in fibers is demonstrated. Issues that affect the validity of the Raman measurements include the spatial heterogeneity of TiO(2) in the fiber, the polarization of the laser beam, and the polarizing properties of the fiber itself. The amount of titanium dioxide in single delustered polyamide fibers was quantitated at concentration levels ranging from 0 to 7.1% TiO(2). Fiber polarization and orientation effects were shown to be minimized by scrambling the polarization of the laser.

Characterization of the Ag mediated surface-enhanced Raman spectroscopy of saxitoxin.

The rapid detection and quantification of saxitoxin (STX) is reported using surface-enhanced Raman spectroscopy (SERS) with a colloidal hydrosol of silver nanoparticles. Under the conditions of our experiments, the limit of detection (LD) for STX using SERS is 3 nM, with a limit of quantification (LQ) of 20 nM. It is shown that the SERS method is rapid, with spectra being collected in as little as 5 seconds total integration time for a 40 nM STX sample. In order to improve the signal-to-noise ratio, SERS spectra were generally collected with a total integration time of 1 minute (6 accumulations of 10 seconds each), with no need for extensive sample work-up or substrate preparation. Based on these results, the SERS technique shows great promise for the future detection and quantification of STX molecules in aqueous solutions.