OPTICAL SENSOR EMPLOYING A REFRACTIVE INDEX ENGINEERED METAL OXIDE MATERIAL
20210171393 · 2021-06-10
Assignee
- UNIVERSITY OF PITTSBURGH-OF THE COMMONWEALTH SYSTEM OF HIGHER EDUCATION (PITTBURGH, PA, US)
- DEPT. OF ENERGY (PITTSBURGH, PA, US)
Inventors
- Peng Chen (Pittsburgh, PA, US)
- Jacob Lorenzi Poole (Pittsburgh, PA, US)
- Paul R. Ohodnicki (Allison Park, PA)
- MICHAEL PAUL BURIC (PITTSBURGH, PA, US)
Cpc classification
International classification
Abstract
An optical sensor device includes a multilayer hollow waveguide device having a hollow waveguide tube layer, an intermediate layer provided inside the hollow waveguide tube layer, and a metal oxide coating layer inside the intermediate layer.
Claims
1. An optical sensor device, comprising: a multilayer hollow waveguide device having: a hollow waveguide tube layer; an intermediate layer provided inside the hollow waveguide tube layer; and a metal oxide coating layer inside the intermediate layer.
2. The optical sensor device according to claim 1, wherein the intermediate layer is a reflective coating layer.
3. The optical sensor device according to claim 2, wherein the reflective coating layer is provided directly on an inner surface of the hollow waveguide tube layer.
4. The optical sensor device according to claim 2, wherein the metal oxide coating layer is provided directly on an inner surface of the reflective coating layer.
5. The optical sensor device according to claim 2, wherein the reflective coating layer is a metal coating layer.
6. The optical sensor device according to claim 5, wherein the reflective coating layer includes silver.
7. The optical sensor device according to claim 5, wherein the reflective coating layer includes gold.
8. The optical sensor device according to claim 1, wherein the hollow waveguide tube layer is made of silica.
9. The optical sensor device according to claim 1, wherein the hollow waveguide tube layer is made of plastic.
10. The optical sensor device according to claim 1, wherein the hollow waveguide tube layer is made of metal.
11. The optical sensor device according to claim 10, wherein the hollow waveguide tube layer is made of Nickel.
12. The optical sensor device according to claim 1, wherein the hollow waveguide tube layer has a first refractive index, wherein the intermediate layer is a guiding layer having a second refractive index that is greater than the first refractive index, and the metal oxide coating layer is structured to have a third refractive index, the third refractive index being less than the second refractive index.
13. The optical sensor device according to claim 12, wherein the guiding layer comprises glass.
14. The optical sensor device according to claim 12, wherein the guiding layer comprises a dielectric material.
15. The optical sensor device according to claim 14, wherein the dielectric material comprises Al.sub.2O.sub.3.
16. The optical sensor device according to claim 12, wherein the dielectric material comprises ZrO.sub.2.
17. The optical sensor device according to claim 1, wherein the metal oxide coating layer has an engineered refractive index and a porosity of 10 nm-50 nm.
18. The optical sensor device according to claim 17, the engineered refractive index is less than a refractive index of silica.
19. The optical sensor device according to claim 18, wherein the hollow waveguide tube layer comprises silica.
20. The optical sensor device according to claim 2, further comprising a protective dielectric coating provided on either or both sides of reflective coating layer.
21. The optical sensor device according to claim 12, wherein the metal oxide coating layer a nanostructure material.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0020] As used herein, the singular form of “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. As used herein, the statement that two or more parts or components are “coupled” shall mean that the parts are joined or operate together either directly or indirectly, i.e., through one or more intermediate parts or components, so long as a link occurs. As used herein, “directly coupled” means that two elements are directly in contact with each other. As used herein, “fixedly coupled” or “fixed” means that two components are coupled so as to move as one while maintaining a constant orientation relative to each other.
[0021] As used herein, the word “unitary” means a component is created as a single piece or unit. That is, a component that includes pieces that are created separately and then coupled together as a unit is not a “unitary” component or body. As employed herein, the statement that two or more parts or components “engage” one another shall mean that the parts exert a force against one another either directly or through one or more intermediate parts or components. As employed herein, the term “number” shall mean one or an integer greater than one (i.e., a plurality).
[0022] As used herein, the term “metal oxide” shall mean a chemical compound that contains at least one oxygen atom and at least one other element in the form of a metal in its chemical formula, and shall include doped variants thereof and mixed metal oxides. Examples of metal oxides are, without limitation, zeolites, SnO.sub.2, TiO2, ZnO, WO.sub.3, and perovskites such as barium strontium cobalt iron oxide (BSCF).
[0023] As used herein, the term “nanostructure” shall mean an object of intermediate size between microscopic and molecular structures having at least one dimension (e.g., the diameter of a hole, a sphere or a tubular structure) that is much less than the wavelength of the light used (e.g., typically less than one order of magnitude defined as 1/10, not excluding functional designs which may be less strict such as ⅕th). For example, in one particular embodiment, the at least one dimension is ≤100 nm.
[0024] As used herein, the term “sol-gel process or method” shall mean a method for producing solid materials from small molecules (e.g., used for the fabrication of metal oxides, especially the oxides of silicon and titanium), that includes conversion of monomers into a colloidal solution (sol) that acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers.
[0025] Directional phrases used herein, such as, for example and without limitation, top, bottom, left, right, upper, lower, front, back, and derivatives thereof, relate to the orientation of the elements shown in the drawings and are not limiting upon the claims unless expressly recited therein.
[0026]
[0027] D-shaped optical fiber 4 in the exemplary embodiment also includes an in-fiber optic component 10 formed in core 6. In the exemplary embodiment, in-fiber optic component 10 is a Fiber Bragg Grating (FBG). As is known in the art, an FBG consists of a series of perturbations, forming a grating, in the index of refraction along the length of an optical fiber. An FBG reflects a spectral peak of a light that is transmitted through the fiber, and the particular spectral peak (called the resonance wavelength) that is reflected depends upon the grating spacing. In the exemplary embodiment, in-fiber optic component 10 is an FBG with a constant period (meaning the grating elements are evenly spaced), referred to as a uniform FBG. In-fiber optic component 10 may also take on other forms, such as an FBG having gratings that have a varying period (referred to as a chirped FBG), a fiber interferometer, or a Fabry-Perot cavitiy (FP). It will be understood, however, that in-fiber optic component 10 formed in core 6 is optional, and that fiber optic sensor device 2 may also be formed with a D-shaped optical fiber 4 that does not include an in-fiber optic component 10.
[0028] As seen in
[0029] In one particular, non-limiting embodiment, coating layer 12 is formed such that it has a lattice structure wherein the voids 12 have a generally regular and consistent shape (such as a spherical shape). In one such lattice structure, the voids 14 have a characteristic dimension (e.g., width or diameter) of the void network that is less than or equal to a predetermined value. For example, and without limitation, the voids 14 may be spherical and each have a diameter of about 20 nm, of between about 10 nm and about 20 nm, of about ≤20 nm, of between about 10 nm and about 50 nm, or of between about 10 nm and about 100 nm. It will be understood that these dimension are meant to be exemplary only and that it is possible for the void sizes to be much larger, perhaps up to even 200 nm, and still be viable for engineering the refractive index for light at 1550 nm. In still another example, the voids 12 may actually be a continuous network and the characteristic dimension (e.g., 20 nm size) may be the characteristic width of the void network in one dimension.
[0030] In one particular embodiment, characteristic dimension of the void network is chosen so that local light scattering is avoided/minimized by making the characteristic dimension of the voids 14 at least about ten times smaller than the wavelength of the light being used/measured in any particular application.
[0031] The controlled tailoring (via controlled nano-structuring) of the metal oxide porosity as just described is what allows the refractive index of coating layer 12 to be reduced below that of core 6, which in turn enables the development of highly sensitive evanescent wave fiber optic sensors with long interaction lengths. At the same time, it removes the thickness, interaction length, and proximity restrictions that have previously been imposed in the prior art by the high refractive indices of metal oxide materials.
[0032] In addition, in further embodiments, metal oxide coating layer 12 may be modified through doping or by forming a mixed metal oxide to target fiber optic sensor device 2 for a particular gas species of interest. For example, and without limitation, coating layer 12 may be made of SnO.sub.2 as described herein and may be doped with palladium (Pd) or platinum (Pt) in order to target fiber optic sensor device 2 for hydrogen (H) sensing. In another embodiment, the coating layer may be a hybrid metal oxide that contains a mixture of two or more materials. For example, and without limitation, tin oxide with zinc oxide.
[0033] In one particular exemplary embodiment, a polymer-based synthesis technique is employed to form fiber optic sensor device 2 having coating layer 12 such that, as just described, it has a tailored refractive index that is less than the refractive index of core 6. More specifically, a sol-gel approach is used to produce coating layer 12 over D-shaped optical fiber 4. In this sol-gel approach, a polymer additive is used as a structure directing agent such that the porosity of the metal oxide (SnO.sub.2 in the illustrated exemplary embodiment) is controlled at the scale of tens of nanometers for refractive index tailoring. The porosity/refractive index is controlled by varying the included amount of the polymer. In the exemplary embodiment, poloxamer 407, also known by the trade name Pluronic® F127, a triblock copolymer, is used as the structure directing agent. During the process, the structure directing agent is mixed with SnCl.sub.4 in Ethanol to form a precursor. The precursor is then modified by the addition of HCl to adjust the pH to about 0.5 (in the exemplary embodiment, precursor is modified by the addition of 37% HCl dissolved in water). Other chemicals could be used for such purposes as well. For example, refractive index tailored SnO.sub.2 films can also be synthesized by addition of a structure directing agent to a mixture of Sn-isopropoxide and a solvent such as a mixture of isopropanol and toluene among many others. Other acids could include glacial acetic acid, nitric acid, and many others. Also, metal oxides can be coated by non-wet processing, such as sputtering, where the nm-scale voids could be fabricated through nano-lithography and patterning approaches, reactive ion-etching, or other suitable techniques. Other exemplary embodiments include: (i) TiO2 solutions containing TiCl4, ethanol, Pluronic F-127, and 37% HCl in water, and (ii) ZnO solutions containing zinc acetate dihydrate, ethanol, Pluronic F-127, and 30% ammonium hydroxide dissolved in water.
[0034] Coating layer 12 is formed over D-shaped optical fiber 4 by dragging (e.g., manually) D-shaped optical fiber 4 through the precursor, immersed in an open dish, at a rate of approximately 1 cm/s. The coated sample is then exposed to a temperature treatment which includes initially drying the coated sample at 70° C., followed by a slow ramp of temperature to 130° C. and then to 600° C. to form the porous coating layer 12 (porous SnO.sub.2 in the exemplary embodiment). Afterwards, the coated sample is allowed to cool down at a slow rate. Amongst the available choices of copolymers for porosity engineering at the nanoscale, poloxamer 407 (a triblock copolymer as noted above) is the most favored. Poloxamer 407 has been shown to provide highly porous SnO.sub.2 coatings with average feature size of around 20 nm.
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[0037] Moreover, in order to examine the underlying structure of the reduced index nanostructured metal oxide of the present invention, cross-sectional TEM samples were prepared using one particular exemplary embodiment of fiber optic sensor device 2 through standard FIB lift-out procedures. A protective layer of Pt was deposited on the surface prior to sectioning and a tungsten-probe tip was used for sample lift-out and electron transparency was obtained over an approximately 10 μm wide region for the entire film thickness. As expected, and a shown in
[0038]
[0039] Referring to
[0040] CRDS system 20 further includes a quartz tube 30 having an analyte input end 32 and an analyte output end 34. A heating element 36 is provided around a portion of quartz tube 30.
[0041] Furthermore, as seen in
[0042] In operation, an analyte (e.g., a gas species) is introduced into quartz tube 30, and an exciting pulse is transmitted into optical fiber 22. The exciting pulse is circulated within the loop of optical fiber 22 many times (e.g., 1000 times). As will be appreciated, with each circulation, the exciting pulse will experience some loss. While the amount of loss in each circulation is small, that loss will accumulate over time with each circulation. Thus, during the circulation process, decaying pulses are transmitted out of optical fiber 22 and are used to analyze the analyte. For example, the time it takes the exciting pulse to decay to 1/e of its initial intensity (the “ringdown time”) can be used to calculate the concentration of the analyte in quartz tube 30.
[0043] In addition, fiber optic sensor device 2 may also be used in a distributive fiber sensing application wherein the scattered light within a fiber is used for sensing purposes. As is known in the art, distributive fiber sensing can be broken down into two categories. The first is known as Brillouin scattering, which is realized by sending a high energy optical pulse into an optical waveguide. The lattice vibrations generated give rise to a pressure wave traveling at the speed of sound. This pressure wave can be considered as a moving grating along the fiber and its properties will depend on the surrounding environment. The returning probing light will carry information about this environment and can be used for detection. The second type of distributive sensing is known as Rayleigh scattering. Here, one measures the backscattered light which contains information as well about the fiber surroundings, such as refractive index variations, absorption losses, and etc.
[0044] Thus, in another exemplary application of fiber optic sensor device 2, such a device may be provided in an environment, such as a chemical plant, where it would be desirable to be able to detect the presence of a chemical species. In such an application, fiber optic sensor device 2 may have a relatively long length, e.g., 100 m, in order to cover the area of interest, and distributive fiber sensing as described above (Brillouin scattering or Rayleigh scattering) may be used to determine the location along fiber optic sensor device 2 where the chemical species is being absorbed, which may indicate a leak at that location.
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[0047] In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word “comprising” or “including” does not exclude the presence of elements or steps other than those listed in a claim. In a device claim enumerating several means, several of these means may be embodied by one and the same item of hardware. The word “a” or “an” preceding an element does not exclude the presence of a plurality of such elements. In any device claim enumerating several means, several of these means may be embodied by one and the same item of hardware. The mere fact that certain elements are recited in mutually different dependent claims does not indicate that these elements cannot be used in combination.
[0048] Although the invention has been described in detail for the purpose of illustration based on what is currently considered to be the most practical and preferred embodiments, it is to be understood that such detail is solely for that purpose and that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover modifications and equivalent arrangements that are within the spirit and scope of the appended claims. For example, it is to be understood that the present invention contemplates that, to the extent possible, one or more features of any embodiment can be combined with one or more features of any other embodiment.