The present invention relates broadly to a spectrometer for detecting an electromagnetic (EM) wave spectrum having one or more wavelength components within a spectral band of interest, a method of detecting an electromagnetic (EM) wave spectrum having one or more wavelength components within a spectral band of interest, and a method of fabricating the spectrometer. In a non-limiting example embodiment, the present invention can be applied to Raman spectroscopy.
Any mention and/or discussion of prior art throughout the specification should not be considered, in any way, as an admission that this prior art is well known or forms part of common general knowledge in the field.
As shown schematically in
Amongst optical spectroscopy techniques, Raman spectroscopy is a powerful technology for label-free detection and analysis of biological and biochemical molecules. However, the Achilles' heel of conventional Raman technology is the laser induced sample fluorescence emission, which is several orders of magnitude higher in intensity than that of the Raman scattering, thereby drowning out the desired Raman signals. To overcome this problem, time-gated (TG) Raman spectroscopy with a pulsed laser has been proposed, which utilizes the fact that Raman scattering is ultrafast and almost instantaneous with the laser pulses and yet the fluorescent emission is relatively slow and has a time delay at nano-second scale after the laser pulses. As shown schematically in
A schematic of a TG Raman spectroscopy setup is shown in
Embodiments of the present invention seek to address at least one of the above problems.
In accordance with a first aspect of the present invention, there is provided a spectrometer for detecting an electromagnetic (EM) wave spectrum having one or more wavelength components within a spectral band of interest, comprising:
In accordance with a second aspect of the present invention, there is provided a method of detecting an electromagnetic (EM) wave spectrum having one or more wavelength components within a spectral band of interest, the method comprising the steps of:
In accordance with a third aspect of the present invention, there is provided a method of constructing the spectrometer of the first aspect.
Embodiments of the invention will be better understood and readily apparent to one of ordinary skill in the art from the following written description, by way of example only, and in conjunction with the drawings, in which:
It has been recognized by the present inventor that the high-throughput spectrometer designs in WO 2021/029827 are optimized if the illumination on the spectrometer entrance aperture is uniform. Any non-uniformity illumination would translate into system noises and thus could reduce SNR of the spectrometer. This uniform illumination requirement can also complicate the spectrometer fore-optics design and potentially increase the cost of the fore-optics. An example embodiment of the present invention can provide an apparatus and method of removing the uniform illumination limitation so that the spectrometer can have a better SNR and be more robust in operation. An example embodiment of the present invention can also provide an apparatus and the method of applying single-pixel high-throughput spectrometers in time-gated or time-resolved Raman spectroscopy systems.
In an example embodiment a type of high throughput single-pixel spectrometer is provided, which is enhanced by employing a unique design to remove the limitation of uniform illumination on the entrance aperture. As a result, an example embodiment of the present invention can greatly simplify the sampling optics or fore optics design, thus making the sampling process for spectroscopic detection and chemical/biochemical analysis easier, more robust, and more convenient for field uses. An example embodiment of the present invention can also have all of the distinct advantages that it (1) is not based on optical interferometers hence is more robust and less sensitive to external disturbances; (2) has an enlarged entrance aperture thus allowing a significantly enhanced light-gathering power, and hence is capable of detection of very weak signals; (3) uses single-pixel photodetector hence can be cost-effectively operated in applications where image sensors/detector arrays are expensive; (4) has the multiplexing advantage hence supporting high SNR detection.
An example embodiment for high throughput single-pixel spectrometers can be implemented in a Raman spectroscopy system. The advantages of using an example embodiment of the present invention in a Raman system include: (1) extremely large spectrometer throughput allowing easier detection of weak Raman scattered signals; (2) can use lasers that are not focused, hence leading to low power density on sample thus less harmful to delicate samples; (3) removing the requirement for precise focusing of laser spot on sample also enhances the robustness of the equipment and facilitates field application, (3) laser illumination on the sample can have a large area (e.g. millimeter by millimeter) allowing faster and easier detection for inhomogeneous samples like powders and pills owing to integrated averaging effect. (4) single-pixel detection makes it easier and cost-effective to implement time-gated or time-resolved Raman spectroscopy to suppress fluorescence background.
It is noted that an example embodiment of the present invention can be used in IR and Raman spectroscopic sensing in various application domains such as in food and beverage quality assessment, gas sensing, environmental monitoring, precision agriculture, industrial process control, internet of things, biomedical point of care testing, drug screening, and many others.
A schematic of a spectrometer 600 according to an example embodiment is shown in
Slight modification to the system shown in
The incident EM radiation contains N number of spectral components λ1, λ2, . . . , λi, . . . , λN (i=1˜N) within the spectral range of interest [λmin, λmax] of the spectrometer 600. If the EM radiation has a broader spectral range than the range of interest, a bandpass filter can be inserted in the spectrometer 600 to cut-off all components outside of [λmin, λmax]. The shape of the radiation spectrum is represented by a column vector X′=[x1′ x2′ . . . xi′ . . . xN′]T, where xi′ is the relative intensity of radiation at wavelength λi. It is noted that the relative value of xi′ with respect to those at other wavelengths is important to the shape of the spectrum, while the absolute value of xi′ is not.
Firstly, a single encoded slit 606 is considered for simplicity. The slit 606 is encoded by a total number of K pixels along its length direction. The EM radiation from a sample is directed to the entrance slit 606 of the spectrometer 600, where the illumination along the slit 606 length direction might not be uniform due to a number of factors including the uniformity of the light source, conditions of optical alignment and focusing, and homogeneity of the sample. On the other hand, for spectroscopy applications, the input radiation spectrum at each encoding pixel along the slit 606 should be the same. Therefore, the total radiation intensity at the kth encoding pixel can be written as Ik′(Σi−1Nxi′), where Ik′ is a scaling factor to reflect the nonuniform illumination along the slit.
At jth measurement (j=1˜M), an encoding pattern is set at the slit 606, where the weightage of the kth encoding pixel is denoted as αjk (with αjk−1 for a transparent pixel or ajk=0 for an opaque pixel). As shown in
where ηi is the efficiency of detection at the wavelength λi. And, ηi might include a number of factors including 0th order diffraction efficiency from the grating, optical losses along the 0th order path, and photodetector efficiency at wavelength λi. It should be noted that in above equation the term (Σi=1Nxi′ηi) has a value independent of the encoding process, and this term is defined as a coefficient c1. Next, a new vector is defined to represent the spectrum without changing its shape:
and a new scaling factor Ik=c1Ik′. With these definitions and after a complete cycle of encoding process from j=1 to M, the Eq. (1) can be written into a matrix form.
where U is a M×1 measurement vector, A is a M×K encoding matrix, and I is a K×1 vector representing intensity scaling at each pixel. It is understood that the vector I can be solved using the following:
It is noted that the total radiation intensity at a given pixel number k can be written either as Ik′(Σi=1Nxi′) or lk(Σi=1Nxi), and they are equal. Consequently, the overall radiation intensity incident onto the spectrometer slit is given by:
It is also noted that the spectrum X by its definition in Eq. (2) is normalised by the following equation:
Hence, in some spectroscopy sensing cases where comparing spectra is necessary for example obtaining an absorption spectrum by comparing the spectra of the light source and the light transmitted through the sample, the spectrum X need to be scaled by a factor of (Σk=1KIk) to reflect the actual amount of total radiation intensity falling onto the entrance slit 606.
Next, the measurement of the spectrum X is considered. As shown in
As shown in
where bki is the weight (or portion) of the light intensity at wavelength λi from kth pixel on the entrance slit that can pass through the 2nd encoder and ξi is the efficiency of detection at the wavelength λi at the 2nd detector. Again, ξi might include a number of factors including 1st order diffraction efficiency from the grating, optical losses along the 1st order path, as well as the photodetector efficiency at wavelength λi. It is important to note that ξi is a system parameter that remains constant once the spectrometer 600 is constructed and thus can be readily calibrated with lasers with known wavelengths and intensities. With this in mind, it is defined:
Consequently, the Eq. (6) can be rewritten in a matrix form:
After a complete set of measurement from j=1 to M, the above equation can be written in a matrix form:
where V is a M×1 measure vector, A is the 1st encoding matrix of dimension M×K, O is a diagonal matrix of dimension K×K and contains the scaling factor Ik obtained from Eq. (3), B is the 2nd encoding matrix of dimension K×N, and Y is a N×1 column vector containing spectrum of the radiation, respectively. In the above equation, the matrices A and B are known by the spectrometer encoder designs and the matrix O can be obtained by measuring the 0th order diffraction using the 1st detector 613. Then, the above linear equations can be solved for Y when a sufficient number of measurements are made. Depending on the total number of measurements M and the number of unknown spectral components N (i.e. whether M=N, M<N, or M>N), a number of methods can be used for obtaining the solution, which include matrix inversion, generalised inversion, compressed sensing, regression, and generalised regression with regularisation. Once the vector Y is solved, the radiation spectrum X can be obtained using Eq. (7).
In the following description M=N is set as an example. It is also important to note that (AOB) is a M×N matrix and its rank is also affected by the total number of encoding pixels K on the entrance slit. To maximise the rank of (AOB), the number K should be equal to or greater than N. In the following description we will set K=N.
In Eq. (9), A matrix is determined by the 1st encoding pattern design that is precisely decided by the programmable encoder at the slit, and this matrix is known and accurate. The scaling factor matrix O is determined by measuring the 0th order diffracted light using the 1st detector and obtained using a computational algorithm such as compressed sensing. This matrix is also relatively accurate. However, the B matrix is affected by the aberrations of the spectrometer optics as well as alignment errors especially between the encoded slit and the 2nd encoding mask, and thus may contain large errors that could affect the spectrum reconstruction results. Fortunately, the errors in B matrix are systematic, which means that they can be calibrated and removed through proper calibration methods provided that the spectrometer optics once constructed is unchanged.
One possible calibration procedure can be as follows. (1) Use a tunable laser as the spectrometer input, and set the laser wavelength to λi (i=1, 2, . . . , N) and its intensity to 1. (2) Record the measurements Zi for a complete set of encoding patterns. Then, we have:
During the calibration process, one can use the method of averaging to suppress the detector noise by repeating the step (2) for a number of times. Then, from the above equation, the ith column of the B matrix can be easily obtained through the following equation:
(3) Repeat the steps (1) and (2) for a new wavelength λi+1, until all columns of the B matrix are calibrated. It is also noted that the B matrix can also be calibrated using other methods. For example, by feeding the spectrometer with a series of input EM waves with known spectra, and then employ machine learning algorithms to calibrate the B matrix by minimising the errors between the reconstruct spectra and know spectra. Once B is calibrated, one can then proceed to measure unknown EM spectra with enhanced accuracy and SNR using Eqs. (3) and (9).
Next, it is considered that the entrance aperture now contains a total number of Ns encoded slits. One can treat each individual slit using the method described above. Considering the fact that the 1st detector receives the 0th order diffracted light from all the slits, the Eq. (3) now becomes:
where Al and Il denote the encoding matrix and intensity scaling vector for the lth slit, respectively. This equation can be further casted into a block matrix form.
with the measurement vector U and encoding matrix Ā know, the vector Ī or I1, I2, . . . , INs can be solved. It is noted that the vector Ī now contains N×Ns unknowns, it may take a long time to complete N×Ns measurements. In this case, a smaller number of measurements can be conducted, and compressed sensing algorithms can be used to find the Ī. This procedure is usually accurate, because the intensity distribution at the entrance aperture is indeed slowly varying and hence the vector Ī is sparse in some basis.
As shown in
where V is the measurement vector, Al, Ol and Bl respectively denote the 1st encoding matrix, intensity scaling matrix, and 2nd encoding matrix for the lth slit, and Y is a vector contains the spectrum X. Again, this equation can be further casted into a block matrix form.
In the above equation, the matrix
In summary, the spectrometer according to an example embodiment works in the following way. At least one encoded slit in the spectrometer entrance aperture plane are used to generate a series of encoding patterns to encode the incident EM wave. For each encoding pattern, a 1st detector 613 is used to record the total intensity of the 0th order diffracted wave, and a 2nd detector 622 is used to record the total intensity of a non-zeroth order diffracted wave (usually +1 or −1 order) that pass through the 2nd encoder. After a sufficient number of measurements are recorded, the spectrum of the EM wave can be reconstructed by solving the Eqs. (13) and (15) using a number of methods including matrix inversion, generalised inversion, regression, and regression with regularisation.
The key advantages of the spectrometer according to an example embodiment include: (1) can conveniently operate at any EM wavelength band including near IR, mid IR, far IR, as well as UV, and DUV owing to the low-cost single-pixel photodetectors used to record the total intensity of the diffracted wave; (2) has multiplexing advantage resulting in high SNR; (3) has an extremely high throughput owing to the large entrance aperture used, thus enabling the detection of very weak EM wave signals; (4) removes the requirement for uniform illumination of the entrance aperture, thus greatly simplifying the spectrometer fore optics design and making sampling process for spectroscopic sensing easier and more convenient for field uses.
Particularly for Raman spectroscopy, the spectrometer according to an example embodiment has the following significant advantages: (1) extremely large spectrometer throughput allowing easier detection of weak Raman scattered signals; (2) can use lasers that are not focused, hence leading to low power density on sample thus less harmful to delicate samples; (3) removing the requirement for precise focusing of laser spot on sample also enhances the robustness of the equipment and facilitate field application. (3) laser illumination on sample can have a large area (millimeter by millimeter) allowing faster and easier detection for inhomogeneous samples like powders and pills owing to integrated averaging effect. (4) single-pixel detector(s) make it easier and cost-effective to implement time-gated or time-resolved Raman spectroscopy to suppress fluorescence background.
An example embodiment of a spectrometer 1000 is shown in
Another example embodiment of a spectrometer 1100 is shown in
In the above example embodiments, detectors (613, 622, D1 and D2) can be single-pixel detectors such as photodiodes, avalanche photodiodes (APDs), single-photon avalanche diodes (SPADs), photon multiplier tubes (PMTs) and many others. In some applications when the light spot on a detector is larger than its photosensitive area, cascading using multiple single-pixel detectors can be used in an example embodiment, as shown in
Next, the use of an example embodiment of a high-throughput spectrometer in time-resolved (TR) Raman spectroscopy applications will be described. As shown schematically in
A TR Raman system 1400 according to an example embodiment is shown in
It is noted that for TR Raman system according to an example embodiment and using a visible pulsed laser, the detector D1 in the high throughput spectrometer 1408 shown in
With single-pixel detectors used in the Raman system according to an example embodiment, time correlated single photon counting (TCSPC) technology can be directly applied to obtain the TR Raman spectrum. As shown in
To further illustrate the data processing algorithm according to an example embodiment, the D2 histogram 1512 is used as an example. During operation, the high-throughput spectrometer according to an example embodiment generates a series of encoding patterns at its entrance aperture, and at each encoding pattern a histogram is produced with the hardware discussed in
The key advantages of a spectrometer according to an example embodiment include that it: (1) can conveniently operate at any EM wavelength band including near IR, mid IR, far IR, as well as UV, and DUV owing to the low-cost single-pixel photodetectors used; (2) has multiplexing advantage resulting in high SNR; (3) has an extremely high throughput owing to the large entrance aperture used, thus enabling the detection of very weak EM wave signals; (4) removes the requirement for uniform illumination of the entrance aperture, thus greatly simplifying the spectrometer foreoptics design and making sampling process for spectroscopic sensing easier and more convenient for field uses.
Particularly for Raman spectroscopy, a spectrometer according to an example embodiment can have the following significant advantages: (1) extremely large spectrometer throughput allowing easier detection of weak Raman scattered signals; (2) can use lasers that are not focused, hence leading to low power density on sample thus less harmful to delicate samples; (3) removing the requirement for precise focusing of laser spot on sample also enhances the robustness of the equipment and facilitate field application; (3) laser illumination on sample can have a large area (millimetre by millimetre) allowing faster and easier detection for inhomogeneous samples like powders and pills owing to integrated averaging effect; (4) single-pixel make it easier and cost-effective to implement time-gated or time-resolved Raman spectroscopy to suppress fluorescence background; (5) Combination of TCSPC with MEMS-micromirror-based encoded entrance aperture makes high sensitive TG/TR Raman detection with essentially no mechanical moving parts.
{The following is a usual “repetition” of the claim language in the description.}
In one embodiment, a spectrometer for detecting an electromagnetic (EM) wave spectrum having one or more wavelength components within a spectral band of interest is provided, comprising an entrance aperture; an exit aperture; a dispersion and imaging optics configured to create dispersed images of the entrance aperture on a plane of the exit aperture, such that respective images at the different wavelength components are offset by different amounts of displacements along a direction of dispersion; at least one single-pixel detector, each single-pixel detector sensitive to one or more of the wavelength components; an EM detector; a first collection optics configured to gather a first EM wave energy incident on the entrance aperture to the EM detector; a second collection optics configured to gather a second EM wave energy that exits the exit aperture to the at least one single-pixel detector; and a measurement unit configured to measure the output of the EM detector and the output of the at least one single pixel detector for reconstructing the EM wave spectrum taking into account an intensity distribution of an incident EM wave on the entrance aperture.
The entrance aperture may comprise at least one entrance slit that is spatially encoded along a direction substantially transverse to the direction of dispersion.
The exit aperture may comprise a plurality of exit slits arranged in the direction of dispersion, where each exit slit is spatially encoded along a direction substantially transverse to the direction of dispersion.
An encoding pattern of the at least one entrance slits and/or an encoding pattern of the plurality of exit slits may be adjustable and configured to be changed for a number of times.
The first collection optics may be configured to gather the first EM wave energy from the zeroth order diffraction from a dispersion element of the dispersion and imaging optics.
The first collection optics may be configured to gather the first EM wave energy from a beam splitter element disposed near the entrance aperture.
The EM detector may comprise a single-pixel detector or an imaging camera.
The spectrometer may comprise a bandpass filter for filtering the spectral band of interest from the incident EM wave.
The spectrometer may comprise a first field lens configured for pupil matching with a fore optics, for disposal near the entrance aperture.
The spectrometer may comprise a second field lens configured for pupil matching with the second collection optics, for disposal near the exit aperture.
The second collection optics may comprise a dispersion element to remove the dispersion effects from the dispersion and imaging optics.
Adjustable encoding patterns of at least one of the entrance slit and/or the exit slit, respectively, may be implemented using microelectromechanical systems (MEMS) technology or using MEMS micromirror arrays.
Adjustable encoding patterns of at least one of the entrance slit and/or the exit slit, respectively, may be implemented using a movable mask placed in the vicinity of a fixed aperture opening.
The spectrometer may be configured as a Raman spectroscopy system. The spectrometer may be configured for time-gate and/or time-resolved Raman spectroscopy.
The measurement unit may be configured for using time correlated single photon counting (TCSPC), wherein 3D histogram data cubes are constructed with the EM detector and the at least the single-pixel detector. The measurement unit may be configured to slice the 3D histogram data cubes at various time delays, each time delay slice representing a complete set of encoded intensity measurements for reconstructing the Raman spectrum at that corresponding time delay. The measurement unit may be configured such that time-resolved Raman shift spectra are reconstructed at various time delays.
The method may comprise spatially encoding at least one entrance slit of the entrance aperture along a direction substantially transverse to the direction of dispersion.
The method may comprise spatially encoding a plurality of exit slits of the exit aperture along a direction substantially transverse to the direction of dispersion.
The method may comprise changing an encoding pattern of the at least one entrance slits and/or an encoding pattern of the plurality of exit slits for a number of times.
The first EM wave energy may be gathered from the zeroth order diffraction from a dispersion element.
The first EM wave energy may be gathered from a beam splitter element disposed near the entrance aperture.
The EM detector may comprise a single-pixel detector or an imaging camera.
The method may comprise filtering the spectral band of interest from the incident EM wave.
The method may comprise pupil matching with a fore optics.
The method may comprise pupil matching during gathering of the second EM wave energy to the at least one single-pixel detector.
The method may comprise removing dispersion effects from the creating of the dispersed images of the entrance aperture on the plane of an exit aperture.
Adjustable encoding patterns of at least one of the entrance slit and/or the exit slit, respectively, may be implemented using microelectromechanical systems (MEMS) technology or using MEMS micromirror arrays.
Adjustable encoding patterns of at least one of the entrance slit and/or the exit slit, respectively, may be implemented using a movable mask placed in the vicinity of a fixed aperture opening.
The method may be used for performing Raman spectroscopy. The method may be used for performing time-gate and/or time-resolved Raman spectroscopy.
The method may comprise using time correlated single photon counting (TCSPC), wherein 3D histogram data cubes are constructed with the EM detector and the at least the single-pixel detector. The method may comprise slicing the 3D histogram data cubes at various time delays, each time delay slice representing a complete set of encoded intensity measurements for reconstructing the Raman spectrum at that corresponding time delay. The method may comprise reconstructing time-resolved Raman shift spectra at various time delays.
In one embodiment, a method of constructing the spectrometer of any one of the example embodiments is provided.
Industrial applications of embodiments of the present invention include that the technology could be used to develop IR and/or Raman spectrometers with high throughput and high spectral resolution for field uses in a range of applications which include, but are not limited to, gas sensing, materials identification and verification, environment monitoring, sensors for internet of things (IoTs), biological science, food and beverage quality assessment, forensics and law enforcement, as well as pharmaceutical research and drug development.
Embodiments of the present invention can have one or more of the following features and associated benefits/advantages:
Aspects of the systems and methods described herein may be implemented as functionality programmed into any of a variety of circuitry, including programmable logic devices (PLDs), such as field programmable gate arrays (FPGAs), programmable array logic (PAL) devices, electrically programmable logic and memory devices and standard cell-based devices, as well as application specific integrated circuits (ASICs). Some other possibilities for implementing aspects of the system include: microcontrollers with memory (such as electronically erasable programmable read only memory (EEPROM)), embedded microprocessors, firmware, software, etc. Furthermore, aspects of the system may be embodied in microprocessors having software-based circuit emulation, discrete logic (sequential and combinatorial), custom devices, fuzzy (neural) logic, quantum devices, and hybrids of any of the above device types. Of course the underlying device technologies may be provided in a variety of component types, e.g., metal-oxide semiconductor field-effect transistor (MOSFET) technologies like complementary metal-oxide semiconductor (CMOS), bipolar technologies like emitter-coupled logic (ECL), polymer technologies (e.g., silicon-conjugated polymer and metal-conjugated polymer-metal structures), mixed analog and digital, etc.
The various functions or processes disclosed herein may be described as data and/or instructions embodied in various computer-readable media, in terms of their behavioral, register transfer, logic component, transistor, layout geometries, and/or other characteristics. Computer-readable media in which such formatted data and/or instructions may be embodied include, but are not limited to, non-volatile storage media in various forms (e.g., optical, magnetic or semiconductor storage media) and carrier waves that may be used to transfer such formatted data and/or instructions through wireless, optical, or wired signaling media or any combination thereof. When received into any of a variety of circuitry (e.g. a computer), such data and/or instruction may be processed by a processing entity (e.g., one or more processors).
The above description of illustrated embodiments of the systems and methods is not intended to be exhaustive or to limit the systems and methods to the precise forms disclosed. While specific embodiments of, and examples for, the systems components and methods are described herein for illustrative purposes, various equivalent modifications are possible within the scope of the systems, components and methods, as those skilled in the relevant art will recognize. The teachings of the systems and methods provided herein can be applied to other processing systems and methods, not only for the systems and methods described above.
It will be appreciated by a person skilled in the art that numerous variations and/or modifications may be made to the present invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects to be illustrative and not restrictive. Also, the invention includes any combination of features described for different embodiments, including in the summary section, even if the feature or combination of features is not explicitly specified in the claims or the detailed description of the present embodiments.
In general, in the following claims, the terms used should not be construed to limit the systems and methods to the specific embodiments disclosed in the specification and the claims, but should be construed to include all processing systems that operate under the claims. Accordingly, the systems and methods are not limited by the disclosure, but instead the scope of the systems and methods is to be determined entirely by the claims.
Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise,” “comprising,” and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in a sense of “including, but not limited to.” Words using the singular or plural number also include the plural or singular number respectively. Additionally, the words “herein,” “hereunder,” “above,” “below,” and words of similar import refer to this application as a whole and not to any particular portions of this application. When the word “or” is used in reference to a list of two or more items, that word covers all of the following interpretations of the word: any of the items in the list, all of the items in the list and any combination of the items in the list.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10202109715X | Sep 2021 | SG | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/SG2022/050637 | 9/1/2022 | WO |