Thin-film spectroscopic sensor

• US 5,082,629 A
• Filed: 12/29/1989
• Issued: 01/21/1992
• Est. Priority Date: 12/29/1989
• Status: Expired due to Term

• Current Assignee: Battelle Development Corporation, Board of Regents of The University of Washington (University of Washington)
• Original Assignee: Battelle Development Corporation, University of Washington
• Inventors: Goldman, Don S., Burgess, Lloyd W. Jr.
• Primary Examiner(s): Warden, Robert J.
• Assistant Examiner(s): EDWARDS, LAURA ESTELLE
• Application Number:
  US07/459,078
• Time in Patent Office: 753 Days
• Field of Search: 422/82.11, 422/82.05, 250/227.14, 350/96.1, 350/96.30, 356/128
• US Class Current: 422/82.11
• CPC Class Codes: G01J 2003/1847 Variable spacing
• CPC Class Codes: G01J 3/18 using diffraction elements, e.g. grating gratings per se G02B
• CPC Class Codes: G01J 3/42 Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry beam switching arrangements G01J3/08
• CPC Class Codes: G01N 21/552 Attenuated total reflection
• CPC Class Codes: G01N 21/80 Indicating pH value

Abstract

There is disclosed an integrated spectrometer for chemical analysis by evanescent electromagnetic radiation absorption in a reaction volume. The spectrometer comprises a noninteractive waveguide, a substrate, an entrance grating and an exit grating, an electromagnetic radiation source, and an electromagnetic radiation sensing device. There is further disclosed a chemical sensor to determine the pressure and concentration of a chemical species in a mixture comprising an interactive waveguide, a substrate, an entrance grating and an exit grating, an electromagnetic radiation source, and an electromagnetic radiation sensing device.

Claims

1. An integrated spectrometer for chemical analysis by evanescent electromagnetic radiation absorption in a reaction volume, comprising:

a noninteractive sample waveguide having a uniform thickness and having a first surface and a second surface, and having an electromagnetic radiation entrance end and exit end, wherein the first surface communicates with the reaction volume along the region between the entrance end and exit end of the sample waveguide;

a substrate having a top surface and a bottom surface and comprising a material characterized by allowing for the transmission of electromagnetic radiation, an entrance grating and an exit grating etched or deposited on the top surface of the substrate, such that the entrance grating communicates with the entrance end and the second surface of the waveguide and couples electromagnetic radiation into the waveguide, and the exit grating communicates with the exit end and the second surface of the waveguide and couples electromagnetic radiation out of the waveguide, wherein the gratings comprise parallel spacings and wherein the refractive index of the substrate is different from the refractive index of the waveguide;

an electromagnetic radiation source directed toward the entrance grating; and

an electromagnetic radiation sensing device directed toward the exit grating.

2. The integratred spectrometer of claim 1, further comprising a thin polymeric overcoat layer communicating with the first surface of the waveguide, wherein the overcoat layer is thinner than the waveguide and wherein the polymeric overcoat permits evanescent interaction of the electromagnetic radiation with the reaction volume.

3. The integrated spectrometer of claim 2 wherein the polymeric overcoat layer is no thicker than 0.01 μ

m.

4. The integrated spectrometer of claim 1, further comprising a thick overcoat layer communication with the first surface of the waveguide and placed over the entrance grating and exit grating, the overcoat layer serving to prevent interaction between the waveguide and the reaction volume in the region of the entrance and exit gratings.

5. The integrated spectrometer of claim 1, further comprising a second waveguide acting as a reference waveguide having a thick overcoat layer over the first surface of the reference waveguide at least in the region between the gratings and being characterized by preventing evanescent interaction of the electromagnetic radiation with the reaction volume, wherein the sample waveguide and the reference waveguide may be communicating with the same substrate or separate substrates.

6. The integrated spectrometer of claim 5 wherein the reference waveguide and the sample waveguide each have separate electromagnetic radiation sources, sensing devices, incoupling gratings, and outcoupling gratings.

7. The integrated spectrometer of claim 5 wherein the reference waveguide and the sample waveguide use the same electromagnetic radiation source bifurcated to direct equivalent electromagnetic radiation to each waveguide.

8. The integrated spectrometer of claim 1, further comprising a polymeric overcoat layer communicating with the first surface of the waveguide, wherein the overcoat layer contains an indicator system that changes its absorption characteristics as a function of an interaction with the reaction volume.

9. The integrated spectrometer of claim 1 wherein the entrance and exit gratings are selected from the group consisting of etched gratings in the top surface of the substrate, ruled gratings in the top surface of the substrate, holographically manufactured gratings, metal gratings, chirped gratings, curved gratings, and combinations thereof.

10. The integrated spectrometer of claim 9 wherein the metal gratings comprise metal lines separated by bare substrate.

11. The integrated spectrometer of claim 1 wherein the noninteractive waveguide material is selected from the group consisting of glass, metal oxides, Ta₂ O₅, ZrO₂, Al₂ O₃, nitrides, fused silica, Si, Ge, zinc selenide, noninteractive polymers, and combinations thereof.

12. The integrated spectrometer of claim 1 wherein the electromagnetic radiation source comprises a plurality of wavelengths and are within the range of ultraviolet light to infrared light.

13. The integrated spectrometer of claim 12 wherein the electromagnetic radiation source is within the range of near-infrared light to infrared light.

14. The integrated spectrometer of claim 1 wherein the electromagnetic radiation source is a collimated visible light source.

15. The integrated spectrometer of claim 1 wherein the spectrometer further comprises fiber optics to transport the electromagnetic radiation between the source and the entrance grating and/or between the exit grating and the sensing device.

16. A method for continuously measuring the concentration of an analyte or analytes in a reaction volume, comprising:

contacting a first surface of a noninteractive waveguide having a uniform thickness with the reaction volume, wherein the waveguide further comprises a second surface communicating with an analysis device, wherein the analysis device comprises a) a substrate having a top surface communicating with the second surface of the waveguide and a bottom surface and further comprising a material that allows for the transmission of electromagnetic radiation, b) entrance and exit gratings etched or deposited on the top surface of the substrate such that the entrance grating couples electromagnetic radiation into the waveguide and the exit grating couples electromagnetic radiation out of the waveguide, c) an electromagnetic radiation source directed toward the entrance grating, and d) an electromagnetic radiation sensing device directed toward the exit grating;

directing electromagnetic radiation to propagate through the waveguide such that the interaction of the analyte or analytes along the first surface of the waveguide in the region between the entrance and exit gratings modulates an evanescent wave; and

detecting the characteristics of electromagnetic radiation by the electromagnetic radiation sensing device.

17. A chemical sensor to determine the presence and concentration of a particular chemical species in a chemical composition, comprising:

an interactive waveguide having a uniform thickness, a first surface, a second surface, and an electromagnetic radiation entrance end and exit end, wherein the first surface communicates with the chemical composition and wherein the waveguide is capable of a physical change in the refractive index or thickness, or both, of the waveguide when the first surface communicates with the chemical composition containing the particular chemical species along the region between the entrance end and exit end of the waveguide;

a substrate having a top surface and a bottom surface and comprising a material of a different refractive index of the waveguide and allowing for the transmission of the appropriate wavelength of electromagnetic radiation, wherein the top surface of the substrate supports the second surface of the waveguide and communicates with the waveguide;

an entrance grating and an exit grating, wherein the entrance grating couples electromagnetic radiation into the entrance end of the waveguide and the exit grating couples electromagnetic radiation out of the exit end of the waveguide;

an electromagnetic radiation source directed toward the entrance grating; and

an electromagnetic radiation sensing device directed toward the exit grating.

18. The chemical sensor of claim 17 wherein the particular chemical species is a solvent or a vapor characterized by the ability to alter the physical characteristics of the interactive waveguide.

19. The chemical sensor of claim 17 wherein the entrance and exit gratings are selected from the group consisting of etched gratings in the top surface of the substrate, ruled gratings in the top surface of the substrate, metal gratings, chirped gratings, curved gratings, and combinations thereof.

20. The chemical sensor of claim 19 wherein the metal gratings comprise metal lines separated by bare top surface of substrate.

21. The chemical sensor of claim 17 wherein the interactive waveguide material is a polymer selected from the group consisting of polystyrene, cellulose acetate, polyvinyl chloride, polyvinyl alcohol, polyphosphazines, silicones, polybenzenes, polyimides, vinyltrimethyl siloxanes, and combinations thereof.

22. The chemical sensor of claim 17 wherein the electromagnetic radiation source is a monochromatic source and is within the range of ultraviolet to near infrared.

23. The chemical sensor of claim 21 wherein the electromagnetic radiation source is a monochromatic laser.

24. The chemical sensor of claim 17 wherein the chemical sensor further comprises fiber optics to transport electromagnetic radiation between the source and the entrance grating and/or between the exit grating and the sensing device.

25. The chemical sensor of claim 17, further comprising a thick overcoat layer communication with the first surface of the waveguide and placed over the entrance grating and exit grating, such overcoat layer serving to prevent interaction between the waveguide and the reaction volume in the region of the entrance and exit gratings.

26. A method for monitoring for the presence and concentration of a particular chemical species in a chemical mixture contained in a reaction volume, comprising:

contacting a first surface of an interactive waveguide having a uniform thickness with the reaction volume, wherein the waveguide further comprises a second surface communicating with an analysis device, wherein the analysis device comprises a) a substrate having a top surface communicating with the second surface of the waveguide and a bottom surface and further comprising a material that allows for the transmission of electromagnetic radiation, b) entrance and exit gratings etched or deposited on the top surface of the substrate such that the entrance grating couples electromagnetic radiation into the waveguide and the exit grating couples electromagnetic radiation out of the waveguide, c) an electromagnetic radiation source directed toward the entrance grating, and d) an electromagnetic radiation sensing device directed toward the exit grating;

directing electromagnetic radiation to propagate through the waveguide such that the interaction of the chemical species with the interactive waveguide in the region between the entrance and exit gratings will change the physical character of the waveguide to affect the electromagnetic radiation propagation through the waveguide; and

detecting electromagnetic radiation leaving the exit grating by the electromagnetic radiation sensing device.

27. The method of claim 26, wherein the electromagnetic radiation is monochromatic at a wavelength in the ultraviolet to infrared range.