# US 11,307,092 B2 · Swept-source Raman spectroscopy systems and methods

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- Number: US 11,307,092 B2
- Document ID: US11307092B2
- Status: Granted
- Kind: B2
- Application number: 16/853,811
- Filed: 2020-04-21
- Published: 2021-04-22
- Granted: 2022-04-19
- Earliest claimed: 2017-12-22
- Assignees: Massachusetts Institute of Technology
- Applicants: Massachusetts Institute of Technology
- Inventors: Amir H. Atabaki; Rajeev J. Ram; William F. Herrington
- Web page: https://patentgrep.com/patent/US11307092B2

## CPC

- G01J 3/0229: {using masks, aperture plates, spatial light modulators or spatial filters, e.g. reflective filters}
- G01J 1/4257: {applied to monitoring the characteristics of a beam, e.g. laser beam, headlamp beam (monitoring arrangements for lasers in general H01S3/0014)}
- G01J 3/0297: {Constructional arrangements for removing other types of optical noise or for performing calibration}
- G01J 3/10: Arrangements of light sources specially adapted for spectrometry or colorimetry
- G01J 3/18: using diffraction elements, e.g. grating (gratings per se G02B)
- G01J 3/2803: {using photoelectric array detector}
- G01J 3/433: Modulation spectrometry; Derivative spectrometry
- G01J 3/44: Raman spectrometry; Scattering spectrometry {; Fluorescence spectrometry}
- G01N 21/65: Raman scattering
- G01N 21/95684: {Patterns showing highly reflecting parts, e.g. metallic elements}
- G01J 2003/4334: {by modulation of source, e.g. current modulation}
- G01N 2201/0221: Portable; cableless; compact; hand-held
- G01N 2201/06113: Coherent sources; lasers
- G01N 2201/0635: Structured illumination, e.g. with grating
- G01N 2201/0638: Refractive parts
- G02B 6/29343: {Cascade of loop resonators}
- G02B 6/29395: {configurable, e.g. tunable or reconfigurable (switching G02B6/35)}
- G01J: MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY (light sources F21, H01J, H01K, H05B; investigating properties of materials by optical means G01N)
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS

## Abstract

In swept source Raman (SSR) spectroscopy, a swept laser beam illuminates a sample, which inelastically scatters some of the incident light. This inelastically scattered light is shifted in wavelength by an amount called the Raman shift. The Raman-shifted light can be measured with a fixed spectrally selective filter and a detector. The Raman spectrum can be obtained by sweeping the wavelength of the excitation source and, therefore, the Raman shift. The resolution of the Raman spectrum is determined by the filter bandwidth and the frequency resolution of the swept source. An SSR spectrometer can be smaller, more sensitive, and less expensive than a conventional Raman spectrometer because it uses a tunable laser and a fixed filter instead of free-space propagation for spectral separation. Its sensitivity depends on the size of the collection optics. And it can use a nonlinearly swept laser beam thanks to a wavemeter that measures the beam's absolute wavelength during Raman spectrum acquisition.

## Claims

### Claim 1

A system comprising:
a tunable laser to emit a tunable excitation beam with a wavelength tuning range of 50 nm or less;
a wavelength sensor, in optical communication with the tunable laser, to measure a wavelength of the tunable excitation beam;
a band-edge filter, in optical communication with the tunable laser, to reject at least a portion of amplified spontaneous emission from the tunable laser, wherein a passband of the band-edge filter overlaps with the wavelength tuning range of the tunable laser;
a spectrally selective detector to detect a Raman signal emitted by a sample in response to excitation with the tunable excitation beam; and
a processor, operably coupled to the wavelength sensor and the spectrally selective detector, to determine a Raman spectrum of the sample based on the Raman signal and the wavelength of the tunable excitation beam.

### Claim 2 (depends on 1)

The system of claim 1, wherein the wavelength tuning range is at most 35 nm, and a center wavelength of the tunable excitation beam is an ultraviolet (UV) wavelength.

### Claim 3 (depends on 2)

The system of claim 2, wherein the processor is further configured to determine the Raman spectrum with a Raman shift of up to 4000 cm−1.

### Claim 4 (depends on 1)

The system of claim 1, wherein a center wavelength of the tunable excitation beam is a visible light wavelength.

### Claim 5 (depends on 1)

The system of claim 1, wherein the processor is further configured to determine the Raman spectrum with a resolution finer than 1 nm.

### Claim 6 (depends on 1)

The system of claim 1, wherein the tunable laser is configured to tune the tunable excitation beam across the wavelength tuning range in less than one second.

### Claim 7

A method of detecting a target substance with a known Raman spectral response in a sample, the method comprising:
emitting a tunable excitation beam with a wavelength tuning range of 50 nm or less, the wavelength tuning range selected based on the known Raman spectral response;
applying the tunable excitation beam to the sample while measuring a wavelength of the tunable excitation beam;
detecting a Raman signal emitted by the sample in response to the tunable excitation beam;
determining a Raman spectrum of the sample based on the Raman signal and the wavelength of the tunable excitation beam; and
determining a presence or an absence of the target substance in the sample based on the Raman spectrum.

### Claim 8 (depends on 7)

The method of claim 7, wherein the emitting includes emitting the tunable excitation beam with a center wavelength selected from an ultraviolet (UV) wavelength and a visible light wavelength.

### Claim 9 (depends on 8)

The method of claim 8, wherein the wavelength tuning range is at most 35 nm, and wherein the determining the Raman spectrum includes determining the Raman spectrum with a Raman shift of up to 4000 cm′.

### Claim 10 (depends on 7)

The method of claim 7, wherein the determining the Raman spectrum includes determining the Raman spectrum with a resolution finer than 1 nm.

### Claim 11

A method of measuring a Raman spectrum of a sample, the method comprising:
emitting a swept laser beam from a tunable laser towards a sample;
collecting Raman light emitted by the sample in response to the nonlinearly swept laser beam;
transmitting the Raman light through a filter having a transmission that varies in wavelength as a function of an incidence angle of the Raman light on the filter;
detecting, with a detector, a spatial distribution of the Raman light; and
estimating the Raman spectrum of the sample based on the spatial distribution of the Raman light.

### Claim 12 (depends on 11)

The method of claim 11, wherein a passband of the filter shifts to shorter wavelengths at larger values of the incidence angle.

### Claim 13 (depends on 11)

The method of claim 11, wherein the transmission of the filter varies nonlinearly with the incidence angle.

### Claim 14 (depends on 11)

The method of claim 11, wherein the filter is a photonic crystal filter.

### Claim 15 (depends on 11)

The method of claim 11, wherein the emitting includes sweeping the laser beam over a set of excitation wavelengths,
wherein the detecting includes, for each excitation wavelength of the set of excitation wavelengths, detecting the spatial distribution of the Raman light emitted by the sample in response to that excitation wavelength to detect a set of spatial distributions of the Raman light, and
wherein estimating the Raman spectrum includes reconstructing the Raman spectrum based on the set of spatial distributions of the Raman light.

### Claim 16 (depends on 11)

The method of claim 11, wherein the incidence angle is a first incidence angle of a set of incidence angles defined by the Raman light on the filter,
wherein the transmission of the filter is different for each incidence angle of the set of incidence angles, and
wherein the spatial distribution of the Raman light is a wavelength distribution that maps to the transmission of the filter.

### Claim 17

A system, comprising:
a tunable laser to emit a swept laser beam towards a sample along a first axis;
a filter having a transmission that varies in wavelength as a function of an incidence angle of the Raman light on the filter, to receive and filter the Raman light;
a detector to receive the Raman light from the filter and to detect a spatial distribution of the Raman light; and
a processor, operably coupled to the detector, to estimate a Raman spectrum of the sample based on the spatial distribution of the Raman light.

### Claim 18 (depends on 17)

The system of claim 17, wherein the transmission of the filter varies nonlinearly with the incidence angle.

### Claim 19 (depends on 17)

The system of claim 17, wherein the tunable laser is further configured to emit the laser beam by sweeping the laser beam over a set of excitation wavelengths,
wherein the detector is further configured to detect the spatial distribution by detecting, for each excitation wavelength of the set of excitation wavelengths, the spatial distribution of the Raman light emitted by the sample in response to that excitation wavelength to detect a set of spatial distributions of the Raman light, and
wherein the processor is further configured to estimate the Raman spectrum by reconstructing the Raman spectrum based on the set of spatial distributions of the Raman light.

### Claim 20 (depends on 17)

The method of claim 17, wherein the incidence angle is a first incidence angle of a set of incidence angles defined by the Raman light on the filter,
wherein the transmission of the filter is different for each incidence angle of the set of incidence angles, and
wherein the spatial distribution of the Raman light is a wavelength distribution that maps to the transmission of the filter.