Abstract:
A double-pass fiber-optic based spectroscopic gas sensor delivers Raman excitation light and infrared light to a hollow structure, such as a hollow fiber waveguide, that contains a gas sample of interest. A retro-reflector is placed at the end of this hollow structure to send the light back through the waveguide where the light is detected at the same end as the light source. This double pass retro reflector design increases the interaction path length of the light and the gas sample, and also reduces the form factor of the hollow structure.

Description:
This application claims priority to provisional application No. 61/090,662, titled: “A Combined Raman and IR Fiber-Based Sensor for Gas Detection” filed Aug. 21, 2008. 
    
    
     The United States Government has rights in this invention pursuant to Contract No. DE-AC52-07NA27344 between the United States Department of Energy and Lawrence Livermore National Security, LLC. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to gas analysis via spectroscopy, and more specifically, it relates to the use of infrared absorption and Raman scattering spectroscopy and assays for the qualitative and quantitative analysis of gases. 
     2. Description of Related Art 
     Gas detection utilizing Raman spectroscopy has previously been demonstrated using a solid-core optical fiber probe, typically comprised of one or more optical fibers for excitation and signal collection. These probes provide a conduit (e.g., light pipe) for exciting a gas or a gas mixture under test with an excitation wavelength(s) of light that generates Stokes and/or anti-Stokes scattering, part of which is collected by a signal collection fiber(s) and provided to a spectrometer. Wavelength cross-sections for gas species have been documented. The main technical problem with this approach is the low signals that are generated from the gas analyte because of the low Raman scattering cross-sections and potential background interferences. This severely limits the sensitivity level, making gas detection at low ppm levels difficult. Studies have used a multi-pass cell or cavity, as well as optical fiber multi-pass cells, to increase the interaction path length between the gas molecules and excitation photons, which improves the limits of detection. However, implementing this cavity design in the field for gas detection is difficult because it requires delicate and precise alignment, a small size, and lacks long-term robustness and rigidity. 
     Chemical detection using optical spectroscopic techniques frequently requires significant enhancement of the signals in order to achieve detection limits of parts per million (ppm) levels. As mentioned above, one standard approach is the use of multi-pass cavities that maximize the interaction length between the chemical analyte and the excitation light. The cavity usually consists of two mirrors that reflect the light back and forth. Two parabolic mirrors can be used to focus multiple reflections to the same point. Field deployment of these devices is difficult because of the sensitivity of their optical alignment. Due to the limitations and difficulties of using multi-pass configurations in the field, utilizing optical fiber is frequently more suitable under these conditions. Work in this area has largely focused on solid-core optical fiber probes (such as e.g. Raman gas sensing with fiber optic probes). Fiber based IR absorption spectroscopy for trace gas detection has previously been demonstrated. As in the Raman techniques described above, the fiber geometries used for IR absorption spectroscopy are likewise usually solid core based. 
     SUMMARY OF THE INVENTION 
     Objects of the present invention include providing improved techniques for performing integrated IR and Raman spectroscopic measurements on a gas sample located within a confined volume, extending the path length of a hollow gas sampling structure thereby providing a capability for sensing a broader range of gas species, obtaining complimentary spectroscopic gas species information, reducing the device form factor and increasing the measurement sensitivity. 
     These and other objects will be apparent based on the disclosure herein. 
     The present invention provides embodiments of an optical design and device that combines Raman scattering and infrared (IR) absorption spectroscopy for gas detection. This combination offers a broader sensing capability (both Raman and IR spectroscopy) than prior art systems. The complementary spectra enable detection and identification of unknown gas species, which is a significant advancement in the field of gas sensors. 
     Embodiments of the present invention include a hollow fiber waveguide (HFW) and a metal coated capillary, each possibly but not necessarily in combination with a solid core optical fiber probe which provides robust field deployment. The optical fiber probe may also encompass an optical filter(s). The hollow gas sampling structure embodiment, e.g., acts as an extended optical path length or multi-pass cell that does not require sensitive alignment. The embodiments using a retro-reflection optical design enhance sensitivity by extending the optical interaction path length of the Raman excitation light and the IR light with the gas sample and by increasing the number of Raman and IR product (e.g. photons) collected. 
     The hollow structures of the present invention function as a fiber optic-based multi-pass optical cavity to increase the light (e.g. photon)/gas interaction path length and as a cylindrical gas cell to confine the gaseous analyte during the measurement to a known volume essential to quantitative measurements. Both functions combined enable low detection limits to be reached in a continuous measurement scenario. A variety of spectroscopic techniques can be used with this hollow cylindrical structure in parallel, but not limited to, Infrared and Raman spectroscopy by coupling of light of differing wavelengths. In addition, the inner surface of the hollow structure can be coated with a single or multiple optical coatings (e.g., (but not limited to) reflective metallic and dielectric layers) optimized to achieve higher throughput and sensitivity. 
     In an embodiment of the present invention, IR light is delivered to a hollow gas sampling structure that contains the gas analyte, and attenuation of the light intensity as a result of selective absorption by the molecules is detected at the distal end of the waveguide as the light exits the fiber. Using a broadband IR radiation source, usually a frequency resolved spectrum is recorded, while a configuration using and IR laser radiation source may record simply attenuation of the radiation intensity. The gas molecule can be introduced into the core of the hollow structure, e.g., at either or both ends of the structure. For situations, where only one access port is allowed for the sensor, the light delivery and collection can be performed at the same end of the fiber. There is also a need to reduce the weight and size of these sensors for miniaturization. If a particular application requires that tight connections must be made at both ends of the hollow structure for collection of optical signals, gas molecules may be restricted from entering the core on either end. The present invention is designed to resolve all of these issues. 
     This invention combines Raman and IR spectroscopy in a single fiber-based gas sensor device for the purpose of detecting, identifying, and quantifying low concentration levels of individual gases and gas mixtures. This combination of both Raman scattering and IR absorption spectroscopy in a single optical design produces complementary spectra that function as molecular-level fingerprints of the gaseous species being probed. Together, these signatures enable the identification of unknown gas species. An essential component of embodiments of this invention include a hollow gas sampling structure in which the gas analytes are confined to a predetermined volume and for increasing the interaction path length between the (excitation) light and the gas molecules. This enables detection limits down to the parts-per-million (ppm) and parts-per-billion (ppb) levels to be reached. Also important to some embodiments is the choice of coatings (e.g., (but not limited to) aluminum, silver, dielectric, etc.) at the inside of the hollow fiber to minimize optical losses. Coupling of a solid core probe or optical fiber, which delivers excitation light to the hollow structure, is provided by a novel fiber geometry. Important for a remote sensing geometry is a double pass arrangement using a retro reflector to direct the scattered light (Raman) or to further increase the absorption path length of light (IR) traveling back through the hollow structure and into the solid core fiber probe, enabling detection of the signals at the same side as the excitation. 
     The spectroscopic techniques usable in the present invention include absorption, photo-acoustics, Raman, fluorescence, surface-enhanced Raman, surface-enhanced infrared, and/or coherent anti-Stokes Raman scattering spectroscopy. The hollow structure functions as a confined volume gas sampling structure in which photons from a light source interact with the gas sample to be detected, and which is present inside the hollow structure. The sample can either be in aqueous or gaseous phase, and can be delivered into the structure by either directly pumping or flowing it into the volume, or by natural diffusion, convection, etc. The molecules can be introduced through the ends of the hollow structure, which are open to the surrounding environment. Another embodiment provides porous structures either at specific locations or along the entire hollow gas sampling structure. Some of the hollow structures usable in the invention are cylindrical in shape and have a diameter ranging from hundreds of microns to several millimeters and its length can be up to meters long. The inside of the structure can be coated with a light guiding and/or reflecting layer, e.g., (but not limited to) a metallic or dielectric layer, to enable light to be guided down the length of the hollow structure. The coating also serves to guide the analytical signal (e.g., scatterings). The layer can also be functionalized for directly targeting and/or recognizing molecules, or roughened to enable surface-enhancement features. Light, from a source such, but not limited to, as a quantum cascade laser, diode laser, or a broadband source is efficiently coupled into the hollow structure using, e.g., a focusing lens, micro-optics, fiber optic components, or combinations thereof. 
     The invention can be used in weapons sensors for continuous monitoring and detection of gases, gas mixtures, and identifying unknown gas species. It can be used for quantification of gas species, environmental, monitoring, as a hand held first responder device to identify and locate victims following a natural disaster or terrorist attack based on molecules generated by a victim (e.g., CO2), for homeland security, e.g., as a breath analysis tool for detection of low concentration levels of high explosives handled and inhaled by suspect persons, for breath analysis for radiological exposure assessment, breath analysis for detecting diseases in-vivo (e.g., cancer) and may generally be used as a chemical sensor/detector. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The accompanying drawings, which are incorporated into and form a part of the disclosure, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. 
         FIG. 1A  shows a present invention embodiment and components of a combined Raman scattering and IR absorption spectroscopy hollow gas sampling structure-based gas sensor. 
         FIG. 1B  shows an enlarged view of the distal end of the solid core optical fiber probe with attached hollow gas sampling structure of  FIG. 1A . 
         FIG. 2  is a present invention design and dimensions of a hollow cylindrical structure for gas analysis. 
         FIG. 3A  is a present invention schematic of the coupling of light into a hollow gas sampling structure using a focusing lens. 
         FIG. 3B  is a present invention schematic of the coupling of light into a hollow gas sampling structure using at least one optical fiber. 
         FIG. 4  illustrates a present invention roughened metal coating on the interior of a glass hollow waveguide where the adsorption of molecules to the surface for surface enhanced Raman or IR spectroscopy. 
         FIG. 5  is a present invention schematic of an optical configuration of a double pass IR gas sensor. 
         FIG. 6  is a present invention optical design of a solid core fiber probe connected to a hollow gas sampling structure with retro reflector at the HFW end. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       FIG. 1A  illustrates as an example of a present invention design of a gas sensor that combines both Raman scattering and IR absorption spectroscopy for gas detection. Components in this design include a Raman excitation light source  10 , an IR illumination light source  12 , an optional solid core optical fiber probe  14  (which can consist of fiber optics  1 - 4 , each having a termination. The distal ends of fibers  1 - 4  may but do not have to terminate into a fiber bundle which delivers light to a hollow structure  16  with optional coatings and filtering as described herein. A retro reflector  18  provides a second pass of light through the hollow gas sampling structure and directs light to, a Raman signal detector  20  and an IR signal detector  22 .  FIG. 1B  shows an enlarged view of the distal end of the solid core optical fiber probe of  FIG. 1A . The figure shows a center fiber  23  that can be used to deliver the Raman excitation light. One or more of the surrounding fibers  24  can be used to deliver the IR light. Some or all of the fibers  25  that surround fibers  24  can be used to collect the Raman signal and/or the IR light. The figure further shows a portion of the hollow gas sampling structure  16 . 
     Raman excitation light source  10  can be a laser that emits monochromatic light. The wavelength of the light can range, e.g., (but not limited to) from the UV to the near infrared spectral region (for example, 200 nm-785 nm). The laser power can be, e.g., in the milliwatt range (e.g., about 500 mW). In the exemplary embodiment, monochromatic light is coupled into solid core optical fiber probe termination  1 . The fiber in the center ( FIG. 1B ) delivers the monochromatic laser light while the surrounding fibers are used for collection of Raman and IR light. Optional bandpass and longpass optical filters placed at the fiber ends and also in the spectrometer serve to reduce undesired signals that may interfere with the Raman signal of the gas analyte. Example undesired signals may include residual lines from the excitation laser beam, Rayleigh scattered light, and Raman signals from the fiber material (e.g., (but not limited to) silica Raman scattered light, etc.). The solid core fiber probe can consist of various combinations of fiber bundles (e.g., 1 around 6), 2-fiber, and 24-around-1) with, e.g., one fiber delivering the light and the remaining fibers collecting the Raman signal and IR signals. This solid core fiber bundle is coupled to a hollow gas sampling structure (HFW)  16 , which can have a diameter of, e.g., about 1 mm and an internal metal coating (e.g., silver, aluminum). The proper choice of coating can be selected based on the wavelength(s) of the excitation light provided by Raman source  10  and/or IR source  12 . The hollow gas sampling structure may contain a gas analyte of interest, which can enter the hollow structure by diffusion through openings in the structure. It is within the hollow structure that the laser beam interacts with the gas sample to generate the Raman scattering and IR light signals. The hollow gas sampling structure functions as a type of multi-pass cell to increase the interaction path length between photons and the gas molecules. The length of the fiber can be varied to optimize this interaction. An exemplary length is 1-2 ft. The retro reflector  18  (e.g., mirror or reflective coating) is used to reflect the excitation light (from source  10  and/or source  12 ) that is travelling through the hollow gas sampling structure and then back through the same structure for a second pass to increase the interaction path length and to direct the Raman signals and the non absorbed IR light toward the solid core fiber bundle for Raman and IR signal collection. The signal collection fibers deliver the signals to the detectors  12  and  22 . These detectors can either or both consist of a wavelength selector (e.g., (but not limited to) a spectrometer) and a sensitive CCD camera, or any other detection device for continuously recording Raman and IR signal. 
     In the exemplary embodiment shown in  FIG. 1A , components for the IR gas sensor include an IR light source  12 . This source can be e.g., a broadband light source (e.g., SiC globar) for performing Fourier transform IR spectroscopy, a quantum cascade laser, which emits light at a specific, narrow wavelength and may provide tenability, or a series of quantum cascade lasers, each emitting at different wavelengths. Other IR sources will be apparent to those skilled in the art based on the present disclosure, and are within the scope of the invention. The wavelengths of the light may be, e.g., (but not limited to) in the mid-IR to IR range such as from about 2.5-20 microns. This invention also includes using radiation extending into the far-IR (THz) spectral regime from 20-1000 microns. This light/radiation is coupled into solid core fiber probe proximal end  2  for delivery to the hollow gas sampling structure  16 . The solid core fiber of end  2  comprises a material different than the Raman fiber of end  1  because it needs to transmit in the IR wavelength range. The light is coupled into the HFW  16  and is reflected back by the retro reflector  18 . The hack-reflected light, which is attenuated in intensity because of its absorption by the gas molecules, is collected by the same solid core fiber and sent to the IR detector. In one example, this solid core fiber may be bifurcated in order to split the light away from the direction of the light source and into the IR detector. Alternatively, the solid core IR fiber probe can consist of two or more fibers bundled together, with one fiber delivering the light to the hollow gas sampling structure and the remaining fibers used to collect the attenuated light. 
       FIG. 2  is a schematic of a design and dimensions of a hollow cylindrical structure (such as the hollow gas sampling structure  16 ) for gas analysis. In  FIG. 2  the hollow structure  30  has typical diameter dimensions  32  ranging from tens or hundreds of microns up to several millimeters in diameter. This diameter depends on the coupling conditions of the light  34  into the core of hollow structure  30 . They can be fabricated from capillaries or tubing and can be made of a variety of materials such as silica and quartz. The inner surface  36  of this hollow structure can be coated with different layers  38  (e.g., metallic, dielectric, etc.) depending on the wavelength of the light source that is being used. The length  40  of the structure can vary from, e.g., several tens of centimeters to a few meters. This length is usually defined by the practical size restriction of the field sensor. In other situations, the length can be defined e.g., by the optical limitations of the coating. For example, situations may arise in which there is no benefit to having longer and longer structures, because the reflectivity of the coating sets a maximum throughput threshold for the entire structure. 
     Light from a source can be coupled into the core of the hollow device using, e.g., a focusing lens or micro-optics (e.g., a GRIN lens, etc.), or direct coupling of light delivered from a solid core fiber. Spectroscopic techniques that can be used with this hollow geometry include Raman and IR, absorption, emission, scattering, photo-acoustics and fluorescence spectroscopy. The light sources can be broadband for applications where an entire spectrum of the analyte is desired, or narrow such as from a diode laser or quantum cascade laser, for applications where absorption or Raman scattering of a specific wavelength of light is required or Raman scattering. The detection of the light can be performed either at the proximal or distal end of the hollow structure, depending on the desired optical configuration of the device.  FIG. 3A  shows an example means for end coupling light  50  into a hollow gas sampling structure  52  using a focusing lens  54 .  FIG. 3B  shows an exemplary way to side couple light  60  into a hollow gas sampling structure  62  using a lens  64 .  FIG. 3C  shows an exemplary way to side couple light  70  into a hollow gas sampling structure  72  using an optical fiber  74 . 
       FIG. 4  illustrates an embodiment with a roughened metal coating  80 , represented by circles, on the interior of a glass hollow structure portion  82  and the adsorption of molecules  84  to the surface of the coating  80  for performing surface enhanced Raman spectroscopy (SERS) or surface-enhanced Infrared absorption spectroscopy (SEIRA). In this design, the roughened surface may include nanostructures (e.g., metallic) that can efficiently generate surface enhanced Raman or surface enhanced infrared spectra of analytes that adhere or are in molecularly close proximity to the nanostructures. Molecules may also adhere by functionalization of the internal hollow gas sampling structure surface with appropriate recognition or enrichment elements or by natural adhesion to the bare surface. In addition, nanostructures may also be fabricated at the surface of the coating to perform surface plasmon resonance (SPR) spectroscopy. Other means for surface enhancement will be apparent to those skilled in the art based on this disclosure, and are within the scope of the present invention. 
       FIG. 5  shows a schematic of an optical configuration of an exemplary embodiment of a double pass IR gas sensor portion of the present invention. The fiber-based sensor has one port to which the fiber is connected and the sensor is placed in an enclosed chamber in which the gas molecules are present. Detection of signals from the molecules must be achieved only through this one port and signals are to be collected using the same single fiber probe. In the figure, infrared source  90  is input into fiber  92 , which is coupled through a boundary  94  to an enclosed environment  95  of interest via a single access port  96 . The fiber may be coupled to a second fiber on the environment side of boundary  94 , or fiber  92  can be passed through an opening in the boundary. The distal end of fiber  92  is connected to a hollow gas sampling structure  98  that includes a retro reflector  100 . The hollow gas sampling structure can include any means for surface enhancement as described herein or that will be apparent to those skilled in the art based on this disclosure. Light reflected by the retro reflector will make a second pass through the hollow gas sampling structure, and propagate back in fiber  92  to an IR detector  102 . Gas from environment  95  can enter the hollow structure  98  though openings in the structure as discussed herein. 
     An example of one implementation of the retro reflector double pass design is shown in  FIG. 6 . The solid core fiber probe  110  is connected to the hollow gas sampling structure  112  which includes a retro reflector  114  at the hollow structure end. Light is coupled into the hollow structure using either a focusing element (e.g., lens  116 ) or direct coupling between the hollow structure and a standard solid core optical fiber probe. The hollow gas sampling structure may include a highly reflective inner coating (e.g., Al, Ag, Au, etc.). The light propagates down the hollow gas sampling structure and interacts with the gas molecules that are present within the core. The retro reflector at the end of the fiber reflects light signals back towards the entrance end of the fiber. The retro reflector can be a highly reflective flat mirror or a curved mirror that maximizes the reflected light back to the hollow structure. The coating can be designed to reflect only one specific wavelength or a broad spectral range, depending on the light source that is used. Gas molecules can enter the hollow gas sampling structure, e.g., (but not limited to) through the gaps between the retro reflector and the hollow structure or through gaps between the hollow structure and the solid core optical fiber probe. Light that reaches the entrance of the hollow gas sampling structure will have made a double pass through the hollow structure, which doubles the interaction length between the photons and the molecules without needing to double the length of the HFW. The light is then collected by the same optical fiber probe, which can be split off by using e.g., a bifurcated optical fiber or a beamsplitter, and propagated to a detector. 
     The foregoing description of the invention has been presented for purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. The embodiments disclosed were meant only to explain the principles of the invention and its practical application to thereby enable others skilled in the art to best use the invention in various embodiments and with various modifications suited to the particular use contemplated. The scope of the invention is to be defined by the following claims.