UV LASERS AND UV RAMAN SYSTEMS FOR EFFECTIVE AND EFFICIENT MOLECULAR SPECIES IDENTIFICATION WITH RAMAN SPECTROSCOPY
20190109431 ยท 2019-04-11
Inventors
- Robert Douglas Waterbury (Palm Harbor, FL, US)
- Darius Vunck (Clearwater, FL, US)
- Robert Dean Babnick (Largo, FL, US)
- Timothy Molner (St. Petersburg, FL, US)
- Hunter Hardy (Pinellas Park, FL, US)
- Ed Dottery (Palm Harbor, FL, US)
- Robert McKinney (Winter Park, FL, US)
- David Welford (Danvers, MA, US)
Cpc classification
H01S3/08054
ELECTRICITY
G01J3/0208
PHYSICS
H01S3/09415
ELECTRICITY
G01J3/021
PHYSICS
G01J3/10
PHYSICS
H01S3/094084
ELECTRICITY
H01S3/0405
ELECTRICITY
International classification
H01S3/08
ELECTRICITY
G01J3/10
PHYSICS
G01J3/44
PHYSICS
Abstract
The present invention relates to a novel stand-off distance chemical detector system such as can be used, for example, for standoff detection of explosives. Instead of a conventional lasing medium, a Pr:YAG or Pr:BYF based UV laser is used which can be advantageously implemented in Raman spectroscopy.
Claims
1. A solid state laser for generating a UV laser for a UV Raman detector comprising: a. a resonator cavity having a main intra-cavity optical path; b. a pumped Pr:YAG or Pr:BYF lasing medium along the main intra-cavity optical path configured to generate a laser with an emission line resonating in the visible light spectrum; c. a frequency doubling crystal along the main intra-cavity optical path configured to convert the visible light oscillation to UV oscillation at <250 nm; d. an optical component along the main intra-cavity optical path configured to direct the UV oscillation out of the cavity for extra-cavity UV laser output for use in a Raman spectrometry detection scheme.
2. The solid state laser of claim 1 wherein: a. the pumped lasing medium comprises: i. a Pr:YAG lasing medium; ii. at least one pump laser diode; iii. adapted to create a visible light oscillation; and b. the doubling crystal comprises a BBO harmonic conversion crystal adapted to covert the visible light oscillation to UV oscillation.
3. The solid state laser of claim 2 wherein the solid state laser is pumped with plural pumping laser diode and: a. the visible light oscillation is at 488 nm; b. the UV oscillation is at 244 nm.
4. The solid state laser of claim 3 wherein the at least one laser pump diode are in one of: a. an end-pumped axial arrangement; or b. a transaxial arrangement.
5. The solid state laser of claim 1 wherein the resonator cavity comprises a concave-convex resonator.
6. The solid state laser of claim 1 wherein the resonator cavity comprises a cross-porro prism resonator.
7. The solid state laser of claim 1 wherein the resonator cavity comprises a double-pass axial concentrator resonator.
8. The solid state laser of claim 7 wherein the double-pass axial concentrator resonator comprises a conductive sapphire heat sink.
9. The solid state laser of claim 1 wherein the optical component for the output laser comprises a dichroic filter.
10. The solid state laser of claim 9 wherein the dichroic filter further comprises a polarizer.
11. The solid state laser of claim 1 further comprising a component which reflects relevant wavelengths of light and attenuates irrelevant wavelengths, wherein the component comprises at least one of: a. an optical coating; b. ASE; and c. AR coating.
12. The solid state laser of claim 1 in combination with a UV Raman system comprising: a. a hand-held housing; b. an on-board power source; c. a processor and circuit; d. collection optics; e. spectrometer; and f range finder.
13. The solid state laser of claim 1 wherein: a. the pumped lasing medium comprises: i. a Pr:BYF lasing medium; ii. at least one pumping laser diode; iii. adapted to create a visible light oscillation; and b. the doubling crystal comprises a BBO harmonic conversion crystal adapted to covert the visible light oscillation to UV oscillation.
14. The solid state laser of claim 13 wherein the solid state laser is with the at least one pumping laser diode and: a. the visible light oscillation is at 495 nm; b. the UV oscillation is at 247.5 nm.
15. The solid state laser of claim 14 wherein the at least one pumping laser diode comprises: a. one pumping laser diode; b. more than one pumping laser diode.
16. The solid state laser of claim 13 wherein the resonator comprises a folded resonator design with two pump lasers diodes.
17. The solid state laser of claim 13 wherein the resonator comprises a linear resonator design.
18. The solid state laser of claim 13 wherein the resonator cavity comprises a cross-porro prism resonator.
19. The solid state laser of claim 13 wherein the resonator cavity comprises a double-pass axial concentrator resonator.
20. The solid state laser of claim 13 in combination with a UV Raman system comprising: a. a hand-held housing; b. an on-board power source; c. a processor and circuit; d. collection optics; e. spectrometer; and f. range finder.
21. A method of creating a UV laser for use in a Raman-based spectroscopy detection comprising: a. generating a UV laser by: i. generating an optimized oscillation in the visible spectrum using pumped Pr:YAG or Pr:BYF as the lasing medium; ii. frequency doubling the optimized oscillation into the UV spectrum at <250 nm; b. using the UV oscillation for Raman-based spectroscopy detection.
22. The method of claim 21 wherein the optimized visible spectrum oscillation is generated by: a. pumping the Pr:YAG with laser diodes at 445 nm; b. producing 488 nm oscillation.
23. The method of claim 22 wherein frequency doubling produces 244 nm oscillation.
24. The method of claim 23 wherein the frequency doubling is through a BBO crystal.
25. The method of claim 21 wherein the UV laser generation is in a resonator cavity comprising: a. a concave-convex arrangement; b. a cross-porro prism arrangement; c. a double pass concentrator with sapphire heat sink arrangement.
26. The method of claim 21 wherein the optimized visible spectrum oscillation is generated by: a. pumping the Pr:BYF with laser diodes at 495 nm; b. producing 147.5 nm oscillation.
27. The method of claim 26 wherein the frequency doubling is through a BBO crystal.
28. The method of claim 26 wherein the UV laser generation is in a resonator cavity comprising: a. a concave-convex arrangement; b. a cross-porro prism arrangement; c. a double pass concentrator with sapphire heat sink arrangement.
29. The method of claim 21 contained with a hand-held sized portable housing including: a. directing the UV laser output to a target; b. collecting reflectance from the target; c. analyzing the reflectance with Raman spectroscopy; d. generating a notification or indicator based on the spectroscopy.
30. The method of claim 21 used for stand-off distance chemical/molecular species detection.
31. The method of claim 30 wherein the notification or indicator relates to detection of chemical/molecular species detection of an explosive.
32. A portable UV Raman system comprising: a. a hand-held portable housing; b. a battery; c. a UV laser source for stand-off distance interrogation of a target; d. a collection optics for collecting reflectance from the interrogated target; e. a spectrometer capable of Raman scattering detection; f a processor and circuit for controlling operation of the system and processing the collected reflectance; g. the UV laser source comprising i. a pumped Pr:YAG or Pr:BYF lasing medium in a resonator cavity configured to generate a laser within the visible light spectrum; ii. a single frequency doubling crystal configured to convert the generated visible light oscillation to UV oscillation; iii. an optical component configured to direct the UV oscillation out of the cavity for extra-cavity UV laser output for interrogation of the target.
33. The system of claim 32 wherein: a. the visible spectrum oscillation is at 488 nm; b. the UV oscillation is at 244 nm.
34. The system of claim 32 wherein: a. the visible spectrum oscillation is at 495 nm; b. the UV oscillation is at 247.5 nm.
35. The system of claim 32 applied to Deep Ultraviolet Raman detection.
Description
III. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
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IV. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS OF THE INVENTION
[0042] A. Overview
[0043] For a better understanding of the invention, some examples of forms it can take all now be described in detail. It is to be understood these are neither exclusive nor inclusive of all such forms or embodiments the invention can take.
[0044] First, several embodiments and options useable with a Raman or LIDOR sensor for chemical detection at standoff distances will be described. Variations obvious to the skill you will be included within these embodiments.
[0045] Second, an expansion of those concepts to optional features or alternatives will be described. It will be understood by those skilled in the art that these are examples only for illustration and variations obvious to those skilled in the art of course possible.
[0046] It will also be understood that the examples focus, just for purposes of simplicity, on detection of explosives such as used with IEDs (improvised explosive devices). The concept of the invention can be applied to a wide variety of chemicals, chemical compounds, and chemical constituents, as is well known in Raman- or LIDOR-based spectroscopy. Form factor and characteristics of the components, as well as the parameters to control them, will, of course, also vary according to need or desire.
[0047] B. UV Generation Using Intra-Cavity Frequency Doubling
[0048] This aspect of the present invention is now described with reference to
[0049] System 10 of
[0050] Strong continuous output UV at a wavelength of 244 nm should be possible by the introduction of a second harmonic non-linear crystal 12 into the resonator 11 previously optimized for the 488 nm oscillation. The non-linear crystal of choice for this wavelength range and for continuous operation is BBO. BBO is widely used for second harmonic generation to the UV both extra-cavity and intra-cavity. BBO is a well-known crystal and is available from many sources. BBO crystal has both high transmission and is impervious to color center formation by the UV energy. BBO crystal also has a high damage threshold, good thermal properties for high average power operation.
[0051] Laser generation with pumping laser diodes and frequency multipliers is well-known. Further details for background can be found at least at US 20130293882 A1 (stand off distance Raman detection and an example of a standoff distance Raman-based spectrometer for chemical detection); U.S. Pat. No. 6,327,281 (BBO-based frequency multiplier resonator and an example of a BBO based laser resonator); U.S. Pat. No. 8,125,627 (a different UV laser and an example of IR visible UV lasers), each of the foregoing incorporated by reference herein in its entirety.
[0052] C. Resonator Concepts and Description Regarding Pr:YAG Laser
[0053] The arrangement within the cavity 11 is as shown in
[0054] The resonator may be terminated with conventional mirrors M1 and M2 with dielectric coatings. The resonator 11 geometry will employ a concave-convex resonator design which will maximize the mode volume and therefore the circulating power of the oscillating fundamental wavelength. This resonator geometry is very stable over environmental changes in temperature and slight structural misalignments.
[0055] As is well-known to those skilled in this technical area, the resonator 11 of
[0056] In this embodiment, the laser 14 comprises a Pr:YAG laser with four pump diodes 15 at 445 nm each. This produces the 488 visible light oscillation from this lasing medium.
[0057] BBO 16 is a specific optical-grade crystal and commercially available. One example is at U.S. Pat. No. 6,327,281 which is incorporated by reference herein.
[0058] Polarizer P1 is commercially available and functions as explained above.
[0059] The above combination can be configured to produce a desired UV output 19 as discussed above. The beneficial aspects are as outlined above.
[0060] 1. Alternate Designs:
[0061] One non-limiting alternative to
[0062] 1. Cross-Porro Design 30: This design 30 employs retro-reflecting porro prisms and the end elements 24 and 26 (
[0063] 2. Double Pass Axial Configuration 40: This design 40 employs 6 pump diodes 22 (instead of four in
[0064] As shown in
[0065] 3. Simple Co-Linear Design: This design 10 (
[0066] To our knowledge nobody has fabricated a Pr:YAG laser in this manner despite the following :
[0067] There is a published article on the material properties of the Pr: YAG crystal: [0068] Wenpeng Liu & Qingli Zhang (2017) Growth and spectral properties of Pr3+-doped Y3Al5O12 crystal for potential use in all-solid state visible laser, Materials Research Innovations, 21:2, 65-68, DOI: 10.1080/14328917.2016. 1 183334; an example of growth and spectral properties of Pr3+-doped Y3Al5O12 crystal for potential use in all-solid state visible laser, and incorporated by reference herein.
[0069] There is published info on PR: YLF lasers: [0070] Vasiliy Ostroumov, Wolf Seelert, Lukas Hunziker, Chris Ihli, 522/261 nm cw generation of Pr:YLF laser pumped by OPS laser'\ Proc. SPIE 6451, Solid State Lasers XVI: Technology and Devices, 645104 (8 Feb. 2007), an example of a 522/261 nm cw generation of Pr:YLF laser pumped by OPS laser, and incorporated by reference herein. [0071] psi.fuw.edu.pl/pub/lPWb/Lasery/ALKAAD_PrYLF_Laser.pdf, another example and incorporated by reference herein.
[0072] There is published patent literature on a Pr-doped optical fiber, and an example of a discussion of a Praseodymium laser, see e.g., U.S. Pat. No. 5,309,452 incorporated by reference herein.
[0073] 2. UV Raman Systems
[0074] Another aspect of the invention is illustrated at
[0075] Most UV Raman systems are rather. Large (>1 cu ft) (see CPEDS and PRIED systems (available commercially from Alakai Defense Systems, Inc., Largo, Fla. (USA) with product descriptions at https://docs.wixstatic.com/ugd/3e1446_cf8257f776944296b3dbe6f6302e260e.pdf and https://docs.wixstatic.com/ugd/3e1446_b9e1071632114fb3b23bdc0ccb9546a1.pdf respectively, and see also US 20130293882 A1 for details; all incorporated by reference herein). Most small portable Raman systems utilize non-UV wavelength lasers (typically 532, 785 nm or 1064 nm).
[0076]
[0077] Alternative embodiments (non-limiting) could include: [0078] 1. the collection optics can use either: [0079] a. a collinear design as shown in
[0093] D. UV LaserPr:BYF@247.5 nm
[0094] Another aspect of the invention utilizes a Pr:BYF-based UV laser (see reference number 20 in
[0095] 1. Praseodymium BYF Solid State Material Characteristics
[0096] The first demonstration of a directly-pumped blue laser using a Pr.sup.3+-doped medium took place in 1977 at the Naval Research Laboratory under the direction of Leon Esterowitz and co-workers Est77 at list of References infra, who demonstrated room temperature lasing of Pr:YLF at 479 nm when pumped with a 444-nm pulsed dye laser. Recent advances in GaN diode lasers operating in the 440-nm to 450-nm range have been used to efficiently pump Pr.sup.3+-doped fluorides (e.g. YLF was the most common) operating in the visible [Cor08, Met13,Rei12b, Str10]. To our knowledge, the only use of Pr with Barium Yttrium Fluoride (BYF) is from [Met13, Met13a] which demonstrated lasing at 495 nm using a 445-nm GaN pump diode.
[0097] While other Pr based lasers have been frequency doubled, none have been frequency doubled and resulted in a wavelength which is <250 nm. The wavelength of <250 nm is important in for Deep Ultra Violet (DUV) Raman because it results in fluorescence free Raman spectroscopy. While the Pr:YAG & Pr:BYF lasers both operate below 250 nm, the Pr:BYF is more efficient (requires less input electrical power to produce the same output power) and has several other advantages.
[0098] 2. UV Generation Using Intra-Cavity Frequency Doubling
[0099] Strong continuous output UV at a wavelength of 247.5 nm should be possible by the introduction of a second harmonic non-linear crystal into the resonator previously optimized for the 495 nm oscillation. The non-linear crystal of choice for this wavelength range and for continuous operation is BBO. BBO is widely used for second harmonic generation to the UV both extra-cavity and intra-cavity. BBO is a well-known crystal and is available from many sources. BBO has both high transmission and is impervious to color center formation by the UV energy. BBO also has a high damage threshold, good thermal properties for high average power operation.
[0100] 3. Resonator Concepts and Description
[0101] Two arrangements of a simple resonator cavity are shown in
[0102] The resonator may be terminated with conventional mirrors with dielectric coatings. The resonator geometry will employ a concave-concave resonator design which will maximize the mode volume and therefore the circulating power of the oscillating fundamental wavelength. This resonator geometry is very stable over environmental changes in temperature and slight structural misalignments.
[0103] Alternate resonator designs: [0104] 1. Two pump sources:
[0105] The following concepts refer to figures which show a Pr:YAG crystal however the concepts will work for Pr:BYF also: [0106] 2. Cross-Porro Design: This design employs retro-reflecting porro prisms and the end elements (see, e.g.,
REFERENCES (EACH INCORPORATED BY REFERENCE HEREIN)
[0108] [Cor08] F. Cornacchia, A Di Lieto, M. Tonelli, A. Richter, E. Heumann, and G. Huber, Efficient visible laser emission of GaN laser diode pumped Pr-doped fluoride scheelite crystals, Opt. Express, 16, (2008), 15932. [0109] [Met13] P. Metz, D. Parisi, K. Hasse, N. Hansen, C. Krnkel, M. Tonelli, and G. Huber, Room temperature cyan Pr.sup.3+:BaY.sub.2F.sub.8 laser at 495 nm, in Advanced Solid-State Lasers Congress, G. Huber and P. Moulton, eds., OSA Technical Digest (online) (Optical Society of America, 2013), paper AF2A. [0110] [Met13a] P. Metz, K. Hasse, D. Parisi, N. O. Hansen, C. Krnkel, M. Tonelli, and G. Huber, Continuous-wave Pr.sup.3+:BaY.sub.2F.sub.8 and Pr.sup.3+:LiYF.sub.4 lasers in the cyan-blue spectral region, Optics lets., 39, 5158, (2013). [0111] [Rie14] R. Riedal et al., Thermal properties of borate crystals for high power optical parametric chirped-pulse amplification, Opt. Express, 22, 17607, (2014). [0112] [Str10] M. Strotkamp, T. Schwarz, B. Jungbluth, H. Faidel, and M. Leers, Efficient, green laser based on a blue-diode pumped rare-earth-doped fluoride crystal in an extremely short resonator, Proc. SPIE., 7578, (2010), 7578-24.
[0113] E. Options and Alternatives
[0114] As will be appreciated by those having skill in this technical art, options and alternatives to the foregoing exemplary embodiments are of course possible. Variations obvious to those skill to be included within the invention which is not limited by the embodiments disclosed herein. Some additional examples of options and alternatives are as follows.
[0115] 1. Form Factor
[0116] As indicated above, the form factor of each of the components can vary according to need or desire. Portability can be approximately less than a fraction of a meter in all dimensions for housing 101 in
[0117] 2. Control System
[0118] Components necessary to allow inter-communication between electrical/electronic functions of the system can be selected and configured in a variety of ways according to the designer's needs and desires. This could include some type of programmable processor or controller.
[0119] 3. Adjustability
[0120] Both factory settings and subsequent adjustments of operation of the system can be easily accomplished by programming and programming of a microprocessor or other intelligent control, including any number of factors, parameters, and the like according to the designer's need or desire. Such programming is well-known.