HYPERSPECTRAL IMAGING WITH A SPATIAL HETERODYNE SPECTROMETER
20220397531 · 2022-12-15
Inventors
Cpc classification
G01J3/0205
PHYSICS
International classification
Abstract
A hyperspectral imaging apparatus based on a monolithic or free space optical spatial heterodyne spectrometer (SHS) design, array detector, electromagnetic radiation source, and optical collection element is described. The apparatus enables the simultaneous acquisition of spatially isolated Fizeau fringe patterns, each having an encoded light product that is decoded to produce a spectral fingerprint of the interrogated object. Features specific to the SHS, such as a large entrance aperture, large acceptance angle, and no moving parts, enable a variety of optical collection schemes including lens arrays, solid-core and hollow core waveguides, and others. In one example, a microlens array (MLA) is configured with the hyperspectral imaging apparatus to simultaneously image many hundred spatially isolated Fizeau fringe patterns while interrogating an object using an electromagnetic radiation source. Each Fizeau fringe pattern recorded by the array detector is decoded to produce a full Raman or laser-induced breakdown spectroscopy (LIBS) spectrum. Compared to prior art, the hyperspectral imaging apparatus overcomes the primary limitations of needing to trade time resolution for both spectral and spatial data density because the imaging apparatus simultaneously acquires both spectral and special information. Based on the selection and configuration of diffraction gratings, the grating aperture size, Littrow wavelength (i.e., heterodyne wavelength), and optical collection configuration, the apparatus can be tailored to produced low or high spectral resolution with a spectral bandpass that covers a portion or the entire Raman spectral range (up to 4200 cm.sup.−1) and for LIBS as well.
Claims
1. An optical apparatus for producing and simultaneously acquiring at least two spatially isolated Fizeau fringe patterns each having an encoded light product formed as a result of receiving a light product from at least one object, wherein said optical apparatus comprises: at least one spatial heterodyne spectrometer constructed to receive at least two light input beams and produce, from each said light input beam, two corresponding light output beams of said spatially isolated Fizeau fringe patterns; wherein the at least one spatial heterodyne spectrometer comprises a beam splitter for directing the light product and subsequently recombining, and one or more diffraction gratings, wherein the diffraction gratings are configured to adjust a wavelength of the light product; an optical element for receiving the light product from the at least one object and produce the at least two light input beams to the at least one spatial heterodyne spectrometer; a means for directing at least one excitation source to interact with the at least one object to produce the light product; and at least one detector array and at least one optical element for imaging the at least two spatially isolated Fizeau fringe patterns.
2. The apparatus of claim 1, wherein the at least one excitation source is a light emitting diode; a pulsed, continuous wave, or semi-continuous wave laser source; a coherent source; an incoherent source; or a combination thereof.
3. The apparatus of claim 1, wherein the optical element is a lens, an array of lenses, a microlens array, a multi-component lens, an optical fiber, an optical fiber bundle, a coherent fiber imaging bundle, a hollow fiber waveguide, a waveguide, a fiber conduit, a fiber faceplate, a mirror, a mirror array, a telescope, or a combination thereof.
4. The apparatus of claim 1, wherein the light product from the at least one object comprises Raman scattering wavelengths, atomic emission wavelengths, laser induced breakdown emission wavelengths, or a combination thereof.
5. The apparatus of claim 1, wherein the at least one detector array is a charge coupled device, an intensified charge coupled device, a frame transfer charge coupled device, an electron multiplying charge-coupled device, a complementary metal oxide semiconductor (CMOS) sensor, or a combination thereof, wherein the at least one detector array is configured to collect wavelengths.
6. The apparatus of claim 1, wherein the one or more diffraction gratings is configured to a predetermined Littrow angle to select a heterodyne wavelength.
7. The apparatus of claim 1, wherein the one or more diffraction gratings is configured to a predetermined rotation angle to adjust an angle of the at least two spatially isolated Fizeau fringe patterns.
8. The apparatus of claim 1, wherein the encoded light product comprises Raman wavelengths, emission wavelengths, or a combination thereof.
9. The apparatus of claim 8, wherein the at least one spatial heterodyne spectrometer is configured as a spatial heterodyne Raman spectrometer.
10. The apparatus of claim 9, wherein the spatial heterodyne Raman spectrometer is monolithic, free space optics, or a combination thereof.
11. The apparatus of claim 9, further comprising one or more blocking filters, one or more band pass filters, or a combination thereof, wherein the one or more blocking filters and the one or more band pass filters are configured to remove light outside of the Raman wavelengths.
12. The apparatus of claim 8, wherein the at least one spatial heterodyne spectrometer is configured as a spatial heterodyne laser-induced breakdown spectrometer, wherein the spatial heterodyne laser-induced breakdown spectrometer is monolithic, free space optics, or a combination thereof.
13. (canceled)
14. The apparatus of claim 12, further comprising one or more blocking filters, one or more band pass filters, or combination thereof, wherein the one or more blocking filters and the one or more band pass filters are configured to remove light outside of the emission wavelengths.
15. The apparatus of claim 1, wherein the at least one spatial heterodyne spectrometer is configured with one or more prisms to further increase an acceptance angle, or wherein at least one of the one or more diffraction gratings has a stepped configuration.
16. (canceled)
17. The apparatus of claim 1, further comprising a refractive corrective optic.
18. The apparatus of claim 1, wherein the encoded light product is decoded using a Fourier transform method or other decoding methods.
19. (canceled)
20. A device for imaging a sample comprising: an excitation source; a spatial heterodyne spectrometer; and a microlens array; wherein the microlens array and a surface of the sample to be imaged are arranged in parallel, and wherein the microlens array collects light from different regions of the surface of the sample.
21. The device of claim 20, wherein the excitation source is a light emitting diode, a laser source, a coherent source, an incoherent source, or a combination thereof, wherein the spatial heterodyne spectrometer is a laser-induced breakdown spectrometer, or wherein the spatial heterodyne spectrometer is configured to receive Raman wavelengths from the sample.
22-23. (canceled)
24. The device of claim 21, further comprising one or more band pass filters, the one or more band pass filters being configured to remove light outside of the Raman wavelengths.
25. The device of claim 20, further comprising one or more blocking filters, a charge-coupled device configured to collect Raman wavelengths, a diffraction grating or dispersive prism configured to adjust Raman wavelengths, or a combination thereof.
26-27. (canceled)
28. The device of claim 25, wherein a grating angle of the diffraction grating or the dispersive prism is adjustable, or wherein the spatial heterodyne spectrometer contains one or more simple wedge prisms to adjust an acceptance angle of light from the sample.
29. (canceled)
30. The device of claim 28, further comprising transfer optics comprised of one or more collection lenses or apertures for collimating the light from the microlens array to within the acceptance angle of the spatial heterodyne Raman spectrometer, further wherein a relay lens is positioned two focal lengths from the microlens array and two focal lengths from the aperture of the spatial heterodyne Raman spectrometer, wherein a center of the microlens array is aligned with a center of the relay lens.
31-44. (canceled)
45. A device comprising: an excitation source; a spatial heterodyne spectrometer comprised of a beam splitter and a pair of diffraction gratings; and one or more additional diffraction gratings.
46. The device of claim 45, wherein the excitation source is a light emitting diode, a laser source, a coherent source, an incoherent source, or a combination thereof, or wherein the spatial heterodyne spectrometer is a monolithic spatial heterodyne spectrometer.
47. (canceled)
48. The device of claim 45, wherein one or more additional diffraction gratings are stacked sequentially one above another, further wherein spacers are disposed between each of the additional diffraction gratings, further wherein a different Littrow wavelength for each of the additional diffraction gratings is selected by adjusting a grating angle of each of the additional diffraction gratings individually relative to each other and relative to the grating angle of the pair of diffraction gratings in the spatial heterodyne spectrometer.
49. (canceled)
50. The device of claim 48, wherein each of the additional diffraction gratings has a unique groove density relative to each other and relative to the groove density of the pair of diffraction gratings in the spatial heterodyne spectrometer.
51-55. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0048] A full and enabling disclosure of the present invention to one skilled in the art, including the best mode thereof, is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:
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DETAILED DESCRIPTION
[0072] Reference now will be made to the embodiments of the invention, one or more examples of which are set forth below. Each example is provided by way of an explanation of the invention, not as a limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as one embodiment can be used on another embodiment to yield still a further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the appended claims and their equivalents. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied exemplary constructions.
[0073] As used herein, the terms “about,” “approximately,” or “generally,” when used to modify a value, indicates that the value can be raised or lowered by 5% and remain within the disclosed embodiment.
[0074] The present invention greatly improves the usability and practicability of prior art spatial heterodyne spectrometers (SHSs) and, in particular, spatial heterodyne Raman spectrometers (SHRSs) and spatial heterodyne LIBS spectrometers (SHLSs) by first, enabling the equivalent approximate doubling of the spectral range using the new rotated grating approach versus the prior art tilted grating approach, thereby maintaining the equivalent SHS pathlength differences along the vertical (perpendicular to the grating dispersion) dimension to enable hyperspectral imaging preferably over the entire vertical dimension of the grating aperture of the SHS device. Second, the stepped grating SHS design approach disclosed herein maintains the equivalent SHS pathlength differences along the horizontal (parallel to the grating dispersion) dimension to enable hyperspectral imaging preferably over the entire horizontal dimension of the grating aperture of the SHS device. Third, when the stepped grating SHS design approach is combined with the rotated grating SHS design approach into a single SHS device, hyperspectral imaging is enabled preferably over the entire vertical and horizontal dimensions of the grating aperture of the SHS device while also enabling the approximate doubling of the spectral range.
[0075] The prior art for hyperspectral techniques has several limitations, in particular the need to trade time resolution for both spectral and spatial data density. The present invention overcomes the limitations of all prior art hyperspectral techniques by enabling simultaneous acquisition of hyperspectral images resulting in a complete Raman (or LIBS) spectrum at numerous spatially isolated object locations using a single acquisition or single laser pulse. This allows complete image acquisition with corresponding complete spectral information simultaneously. Furthermore, use of a single acquisition or single laser shot (e.g., laser pulse) mitigates degradation of the sample as might occur from repeated or prolonged exposure to intense laser light.
[0076] Specifically, the present invention enables encoding the light product received from an object in a single acquisition or single laser pulse to obtain low- or high-resolution spectra simultaneously at many spatially isolated locations on the sample. This is possible because the SHS has the unique property of allowing many spatially isolated beams of light to be simultaneously measured, by illuminating each beam of light onto a separate region of the SHS diffraction grating or gratings, or other alternate dispersive element, and onto separate regions of the CCD, ICCD, CMOS detector, or other type of array detector.
[0077] In one embodiment, we show that by using a microlens array (MLA) in combination with a SHS, the present invention can capture data for a plethora of points on the sample with a single acquisition or single laser shot. Furthermore, additional diffraction gratings can be added and imaged in order to enable hyperspectral imaging across an expanded portion of the SHS grating aperture by adjusting pathlength differences. Furthermore, one grating can be rotated about the grating normal, as opposed to tilting, to enable an approximate doubling of the spectral range. These improvements represent a significant advancement over all the prior art.
[0078] In an exemplary embodiment, the present invention contemplates the use of a (SHRS) (100), as depicted in
f=4(σ−σ.sub.L)tan θ.sub.L (1)
Ω.sub.max=2π/R (2)
θ.sub.L=arcsin(mλ.sub.L/2d)
[0079] According to Equation 1, emission lines above or below the Littrow wavelength may show identical fringe patterns and can lead to degenerate lines (i.e., line overlap). This degeneracy can be removed by tilting one of the gratings vertically, which induces a rotation to the interferogram (i.e., Fizeau fringe pattern), in opposite directions above and below Littrow. In this case, a 2D Fourier transform can be used to recover spectra above and below the Littrow wavelength unambiguously. This technique can be used to approximately double the spectral range of the SHRS.
[0080] In an alternative embodiment, the present invention utilizes a grating rotation, where the grooves of the grating are rotated with respect to the grooves on the other grating, which are vertical. While there are different ways to achieve this grating rotation—preinstalling the grating in the glass housing with the desired rotation or preinstalling the grating with vertical grooves and then rotating the glass housing—the key concept here is that one set of grooves are rotated (and not tilted) versus the other set of grooves.
[0081] The SHRS, like other Fourier transform interferometers, does not require a narrow slit to achieve high resolution as is common with dispersive spectrometers because there is only a weak dependence of resolution on entrance aperture width. This allows the SHRS to employ very large entrance apertures, greatly increasing the throughput of the system, which is advantageous when signal strength of the light product is low and also for imaging applications.
[0082] In the described embodiment of the SHRS (100), the resolving power is equal to the number of grating grooves illuminated, in this case R=10,800, giving a theoretical resolution of about 0.05 nm (1.7 cm.sup.−1) at 532 nm. The active area of the charge coupled device (CCD) detector (105) is about 16.2 mm or about 1200 pixels; therefore, the theoretical spectral range of the SHRS, based on the Nyquist criteria of 2 pixels per wavelength, is about 30 nm (1073 cm.sup.−1). The useful spectral range is only about ⅔ this value because the instrument response drops quickly at wavelengths far from the Littrow setting. This spectral range can be roughly doubled (to about 60 nm or 2145 cm.sup.−1) by tilting or by rotating one of the gratings slightly (with respect to the other grating) and using a 2D Fourier transform to recover wavelengths both above and below the Littrow wavelength, unambiguously. The maximum, resolution-limited solid angle field of view (FOV) of the SHRS is related to the resolving power by Equation 2 above. Thus, the solid angle FOV for an exemplary embodiment without field widening prisms is about 5.8×10.sup.−4 sr, and the full acceptance angle is about 1.4°. The addition of field widening prisms, another embodiment, offers several advantages including an increased acceptance angle.
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[0084] The present invention is shown in the system (200) in
[0085] It is critical that the light enters the SHRS (100) aperture (106) either collimated or within the acceptance angle of the SHRS (100). This can be achieved using a variety of different embodiments. In the demonstrated embodiment of
[0086] In one embodiment, shown in
[0087] As shown in
[0088] In an embodiment where optical fibers are used rather than an MLA, the range of individual fiber diameters could be from several micrometers (i.e., microns) to many hundreds of micrometers to a few millimeters. Of course, the size of the fiber diameter(s) used would limit, in part, the number of spatially isolated Fizeau fringe patterns obtained on the array detector.
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[0091] A method 300 for imaging a sample using the system 200 of the present invention is described in detail below with reference to
[0092] In an alternative embodiment, the spatial heterodyne spectrometer can be of a monolithic construction, as shown in
[0093] In yet another embodiment, shown in
[0094] In still another embodiment, rather than utilizing stepped diffraction gratings as in
[0095] The present invention may be better understood by reference to the following examples.
Example 1
[0096] A continuous 532 nm laser (MLL-FN-532-300 mW, OptoEngine, LLC) illuminated a 25 mm diameter, 550 nm longpass dichroic mirror (DMLP550, ThorLabs, Inc.), which directed the on-axis illumination beam through the MLA (MLA) (19-0055, SUSS MicroOptics), where each lenslet focused the laser to a spot on the sample. The surface of the sample was located 1.5 mm away at the focal point of the f/16 MLA. In this way, the sample was illuminated in epifluorescent geometry with an array of spots. The Airy disk diameter is 20 microns.
[0097] The fused silica MLA had a 4×4 mm overall size with 100-micron diameter circular lenslets packed in a square grid. The MLA had chromium apertures to block light between the lenslets and had an antireflective coating at 780 nm. Samples were illuminated with about 300 μW per lenslet.
[0098] Each individual MLA lenslet collected the signal from each illuminated spot. The relay lens, a Nikon™ AF NIKKOR 80-200 mm f/4.5-5.6, was used to image the back surface of the MLA onto the SHRS gratings. The placement and focal setting of the relay lens were changed depending on the desired resolving power per lenslet. For a fixed grating line density, the relay lens magnification dictated the lenslet beam size on the grating face, and therefore, the resolving power per lenslet. Magnifications of 8× and 10× were used. Using 300 lp/mm gratings for 10× magnification, the resolving power per lenslet was 594, which corresponds to about 32 cm.sup.−1 FWHM, and for 8× magnification, the resolving power per lenslet was 450, which corresponds to about 40 cm.sup.−1 FWHM. A spatial filter with 4 mm diameter was located at the focal point of the relay lens. This spatial filter isolates the lenslet beams from other background signals as described by Tiziani et. al.
[0099] The SHRS was equipped with a 25 mm N-BK7 non polarizing 50:50 cube beamsplitter (B5013, ThorLabs, Inc.) and a pair of 300 lp/mm gratings blazed at 500 nm (#64-403, Edmund Optics). An iris at the input aperture limited the size of the illuminated area on the gratings to 18 mm. The SHRS was equipped with four 532 nm longpass filters (LP03-532RE-25, Semrock RazorEdge®), a 550 nm longpass filter (FEL0550, ThorLabs, Inc.) and a 581 nm shortpass filter (581FD525, Knight Optical Ltd.) to remove strong Rayleigh scatter from the laser and to keep incoming signal within the SHRS spectral range. Inside the SHS, a fused silica f/4.5 lens with 105 mm focal length (UV-MICRO-APO 111032, Coastal Optical Systems, Inc.) imaged the interferogram with 1.2× magnification onto a thermoelectrically cooled back-illuminated UV-enhanced CCD detector with 2048×512, 13.5 μm pixels (PIXIS-2048 2KBUV, Teledyne Princeton Instruments). A spatial filter placed one focal length from the interferogram imaging lens was used to block higher grating orders. Images were acquired in Lightfield® 4.10 software with 100 kHz ADC gain high and in the low noise setting. The CCD was cooled to −70° C.
[0100] To obtain the spectra, the raw image was first imported into MATLAB® and the region of interest was selected. The columns of the selected region were summed in the vertical direction to give a raw interferogram superimposed on a background signal. To remove this background, a polynomial was fit and subtracted from the cross section. This corrected cross-section was then Fourier transformed to reveal the Raman spectrum. A 13 mm pellet die (#3619, Carver) was used to press a variety of heterogeneous pellet samples. All samples were prepared with the intention of keeping the constituents spatially separate. A diamond (Kit #458200, Ward's® Science) was pressed into a Potassium Perchlorate (#11630, 99% anhydrous, Alfa Aesar®) pellet.
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Example 2
[0103] Further using the operational setup shown in Example 1, a bilayer pellet of sodium sulfate and potassium perchlorate (239313, Sigma Aldrich) was sampled.
Example 3
[0104] Further, using the operational setup shown in Example 1, a bilayer pellet of sodium nitrate and potassium perchlorate (347663, Sigma Aldrich) was sampled.
Example 4
[0105] Further, using the operational setup shown in Example 1, a bilayer pellet of acetaminophen and ammonium nitrate (A7085 and 256064, Sigma Aldrich) was sampled. FIG. 11 shows an acetaminophen/ammonium nitrate bilayer pellet measured with the MLA-SHRS. The sample was illuminated with 300 μW/lenslet for 3 minutes. The raw interferogram image is labeled with the one-lenslet regions of interest and the corresponding spectra are below. The changing concentrations of acetaminophen and ammonium nitrate are seen across each lenslet of interest. Region A shows the acetaminophen Raman spectrum; regions B and C show the Raman bands of both acetaminophen and ammonium nitrate at different concentrations; and region D shows only the ammonium nitrate peak at 1043 cm.sup.−1. The resolving power per lenslet was 450, which corresponds to about 40 cm.sup.−1 FWHM.
[0106] Although the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims. All publications, patents, and patent applications mentioned in this specification are herein incorporated in their entirety by reference into the specification, to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated herein by reference. In addition, citation or identification of any reference in this application shall not be construed as an admission that such reference is available as prior art to the present invention.
Example 5
[0107] For Raman imaging measurements of an acetaminophen sample,