Raman scattering optical spectroscopy employs an emission spectrum or spectral components thereof produced by inelastic scattering of photons by an internal structure of the material being illuminated. These spectral components contained in a response signal (for instance, a Raman signal) are to facilitate determination of the material characteristics of an analyte species including identification of the analyte.
The Raman signal level or strength is often significantly enhanced by using a Raman-active material (for instance, Raman-active surface), however. For instance, the Raman scattered light generated by a compound (or ion) adsorbed on or within a few nanometers of a structured metal surface can be 103-1012 times greater than the Raman scattered light generated by the same compound in solution or in the gas phase. This process of analyzing a compound is called surface-enhanced Raman spectroscopy (“SERS”). In recent years, SERS has emerged as a routine and powerful tool for investigating molecular structures and characterizing interfacial and thin-film systems, and even enables single-molecule detection. Engineers, physicists, and chemists continue to seek improvements in systems and methods for performing SERS.
Features of the present disclosure are illustrated by way of example and not limited in the following figure(s), in which like numerals indicate like elements, in which:
For simplicity and illustrative purposes, the present disclosure is described by referring mainly to an example thereof. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. It will be readily apparent however, that the present disclosure may be practiced without limitation to these specific details. In other instances, some methods and structures have not been described in detail so as not to unnecessarily obscure the present disclosure.
Throughout the present disclosure, the terms “a” and “an” are intended to denote at least one of a particular element. As used herein, the term “includes” means includes but not limited to, the term “including” means including but not limited to. The term “based on” means based at least in part on. In addition, the term “light” refers to electromagnetic radiation with wavelengths in the visible and non-visible portions of the electromagnetic spectrum, including infrared and ultra-violet portions of the electromagnetic spectrum.
Disclosed herein is an apparatus for use in a sensing application, such as, SERS, enhanced luminescence, enhanced fluorescence, etc. Also disclosed herein are a method for fabricating the apparatus and a method for performing a sensing application using the apparatus. The apparatus includes a body having a cavity containing an opening, a plurality of nano-fingers positioned in the cavity, and a destructible cover covering the opening in the cavity. The destructible cover is to protect the nano-fingers, for instance, following their fabrication. In one regard, the destructible cover is to be destroyed to enable access to the plurality of nano-fingers. In one example, the destructible cover is to dissolve when introduced into a particular medium, such as, a medium containing a substance to be tested. In this regard, the nano-fingers are protected following their fabrication until such time as the substance to be tested is to be introduced onto the nano-fingers.
According to an example, the destructible cover is attached over the cavity containing the nano-fingers while the apparatus is in a relatively clean environment. In other words, the destructible cover closes the cavity before contaminants are likely to be introduced onto the nano-fingers and more particularly, onto the Raman-active material nano-particles attached to the nano-fingers. The destructible cover also substantially protects the nano-fingers from physical harm that may occur, for instance, during shipping of the apparatus or other handling of the apparatus. Moreover, according to various examples, the gap in the cavity between the nano-fingers and the destructible cover is filled with a filling material that prevents the Raman-active material nano-particles from substantially any undesirable physical or chemical changes. In any regard, the destructible cover is to protect the Raman-active material nano-particles from contamination from air or other possible mechanisms that decrease the performance of the Raman-active material nano-particles for sensing applications. This extends the shelf-life of the apparatus as well as enhances its reliability.
The use of multiple nano-fingers having Raman-active material nano-particles attached to the tips of the multiple nano-fingers as disclosed herein generally enhances the electromagnetic field generation and therefore the Raman scattering of light from a substance to be tested. In other words, the closely positioned nano-particles on the nano-fingers enables hot-spots to have a larger electric field strength as compared with Raman-active material nano-particles that have simply been placed on the component layer because, for instance, the use of the nano-fingers enables the formation of a well controlled arrangement of nano-particles with relatively small (less than about 10 nm wide) gaps between adjacent nano-particles.
According to an example, the sensing application for which the apparatuses 100, 100′ is to be used includes surface enhanced Raman spectroscopy (SERS), enhanced luminescence, enhanced fluorescence, etc. In this example, the apparatuses 100, 100′ are to be used in the performance of the sensing application to detect a molecule in an analyte sample with a relatively high level of sensitivity. More particularly, the apparatuses 100, 100′ each includes the plurality of nano-fingers 110, which include Raman-active material nano-particles (not labeled in
As also shown in
In both apparatuses 100, 100′, the body 102 has any suitable cross-sectional shape, such as, circular, rectangular, triangular, etc., and has thicknesses in the range of about 50 μm to about 10 mm, and widths and lengths in at least the millimeter range. In one example, the body 102 has sufficiently large dimensions, for instance, based upon the type of material from which the body 102 is formed, to be held between a user's fingers. In other words, the apparatuses 100, 100′ are sized to function as test strips. Examples of suitable materials for the body 102 include, paper, silicon, silicon nitride, glass, plastic, polymer, SiO2, Al2O3, aluminum, etc., or a combination of these materials, etc.
In
In
In addition, although the cavity 104 has been depicted as being positioned either within or above the body, it should also be clearly understood that in other examples, the cavity 104 is partially formed within the body 102 and/or positioned below the body 102.
In each of the examples above, openings in the cavities 104 are depicted as being covered by a respective destructible cover 106. The destructible cover 106 is to be stable under normal ambient conditions, for instance, temperature, light, etc. According to an example, the destructible cover 106 is to be destroyed through application of a mechanical force. Thus, for instance, the destructible cover 106 is formed of a relatively fragile material, such as, a thin sheet of glass or other relatively easily destroyed material. In this example, a mechanical force, such as, a bending, twisting, or other force, is to be applied onto the apparatus 100, 100′ to destroy the destructible cover 106, thus exposing the nano-fingers 110.
According to another example, the destructible cover 106 is to dissolve within a predetermined length of time when the destructible cover 106 is subjected to various conditions. The various conditions include being immersed or otherwise coming into contact with certain fluids. In this regard, the destructible cover 106 is formed of a material that is designed and/or known to dissolve in the certain fluids within the predetermined length of time, such as, for instance, sugar, wax, etc. By way of example, a certain fluid comprises water and the destructible cover 106 comprises a water-soluble material, such as, water-soluble polymers, naturally occurring or synthesized polymers, polysaccharides, polyethylene oxide, etc. As another example, a certain fluid comprises gasoline and the destructible cover 106 comprises a material that is soluble in gasoline. Examples of materials for the destructible cover 106 include, for instance, oil soluble materials, such as, homopolymer or heteropolymer of polyacrylate, polystyrene, polyamide, etc. In addition, the predetermined length of time may be, for instance, around one minute, around 10 minutes, around one hour, around one day, etc. The predetermined length of time may be less than around 1 year, one month, one week, etc.
According to a particular example, the destructible cover 106 is formed of a material that is designed and/or known to dissolve in a fluid containing a substance to be tested on the Raman-active material nano-particles. By way of example, the substance to be tested comprises gasoline or gasoline-like fuel products and a sensing application is to be performed on the gasoline molecules around the nano-fingers 110 to test for a specific marker in the fuel product. For instance, the sensing application is to be performed to detect at least one of octane levels, impurities, contaminants, etc. In various respects, therefore, the destructible cover 106 is matched to the particular substance to be tested, such that, the Raman-active material nano-particles are maintained within a protective containment up until the time at which the substance to be tested is ready for application onto the Raman-active material nano-particles.
According to another particular example, the destructible cover 106 is also composed of at least material that does not significantly affect sensing applications performed on the Raman-active material nano-particles. In other words, the destructible cover 106, in this example, is composed of a material(s) that does not substantially affect the substance to be tested, for instance, when the destructible cover 106 is immersed in the substance to be tested. More particularly, for instance, the destructible cover 106 is composed of a material(s) that is inert with respect to the substance to be tested.
As shown in
In alternative examples, the body 102 includes multiple cavities 104 containing nano-fingers 110 and/or multiple openings in the cavity 104. In one example, a plurality of destructible covers 106 are positioned to cover the openings of the multiple cavities 104 and/or cavity 104. In other example, a single destructible cover 106 is positioned to cover the openings of the multiple cavities 104 and/or cavity 104.
Turning now to
Turning now to
According to an example, the nano-fingers 110 are formed of a relatively flexible material to enable the nano-fingers 110 to be laterally bendable, for instance, to enable tips of the nano-fingers 110 to move toward each other, as discussed in greater detail herein below. Examples of suitable materials for the nano-fingers 110 include polymer materials, such as, UV-curable or thermal curable imprinting resist, polyalkylacrylate, polysiloxane, polydimethylsiloxane (PDMS) elastomer, polyimide, polyethylene, polypropelene, fluoropolymer, etc., or any combination thereof, metallic materials, such as, gold, silver, aluminum, etc., semiconductor materials, etc., and combinations thereof.
The nano-fingers 110 are attached to the surface of the substrate 202 through any suitable attachment mechanism. For instance, the nano-fingers 110 are grown directly on the substrate 202 surface through use of various suitable nano-structure growing techniques. As another example, the nano-fingers 110 are integrally formed with the substrate 202. In this example, for instance, a portion of the material from which the substrate 202 is fabricated is etched or otherwise processed to form the nano-fingers 110. In a further example, a separate layer of material is adhered to the substrate 202 surface and the separate layer of material is etched or otherwise processed to form the nano-fingers 110. In various examples, the nano-fingers 110 are fabricated through a nanoimprinting or embossing process in which a template of relatively rigid pillars is employed in a multi-step imprinting process on a polymer matrix to form the nano-fingers 110. Various other processes, such as, etching, and various techniques used in the fabrication of micro-electromechanical systems (MEMS) and nano-electromechanical systems (NEMS) may also be used to fabricate the nano-fingers 110.
A nano-finger 110 is defined, for instance, as an elongated, nanoscale structure having a length (or height) that exceeds by more than several times a nanoscale cross sectional dimension (for instance, width) taken in a plane perpendicular to the length (for instance, length>3×width). In general, the length is much greater than the width or cross sectional dimension to facilitate bending of the nano-finger 110 laterally onto one or more neighboring nano-fingers 110. In some examples, the length exceeds the cross sectional dimension (or width) by more than a factor of about 5 or 10. For example, the width may be about 100 nanometers (nm) and the height may be about 500 nm. In another example, the width at the bases of the nano-fingers 110 may range between about 10 nm and about 1 micrometer (μm) and the length may range between about 50 nm and 2 μm. In other examples, the nano-fingers 110 are sized based upon the types of materials used to form the nano-fingers 110. Thus, for instance, the more rigid the material(s) used to form the nano-fingers 110, the less the width of the nano-fingers 110 may be to enable the nano-fingers 110 to be laterally collapsible. In further examples, the nano-fingers 110 may form ridges in which two of three dimensions (for instance, length and height) exceed by more than several times a nanoscale cross sectional dimension (for instance, width). The nano-fingers 110 may equivalently be referenced as nano-poles or nano-pillars without departing from a scope of the apparatuses 100, 100′.
The nano-fingers 110 have been depicted as having substantially cylindrical cross-sections. It should, however, be understood that the nano-fingers 110 may have other shaped cross-sections, such as, for instance, rectangular, square, triangular, etc. In addition, or alternatively, the nano-fingers 110 may be formed with one or more features, such as, notches, bulges, etc., to substantially cause the nano-fingers 110 to be inclined to collapse in particular directions. Thus, for instance, two or more adjacent nano-fingers 110 may include the one or more features to increase the likelihood that the nano-fingers 110 collapse toward each other. Various manners in which the nano-fingers 110 may be collapsed are described in greater detail herein below.
The array 200 includes a substantially random distribution of nano-fingers 110 or a predetermined configuration of nano-fingers 110. In any regard, according to an example, the nano-fingers 110 are arranged with respect to each other such that the tips of at least two neighboring nano-fingers 110 are able to touch each other when the nano-fingers 110 are in a bent condition. By way of particular example, the neighboring nano-fingers 110 are positioned less than about 100 nanometers apart from each other. In addition, although
As also shown in
Turning now to
In any regard, the Raman-active nano-particles 210 may be deposited onto at least the free ends 208 of the nano-fingers 110 through, for instance, physical vapor deposition (PVD), chemical vapor deposition (CVD), sputtering, etc., of metallic material, or self-assembly of pre-synthesized nano-particles. By way of example, the angle at which the nano-particles 210 are deposited onto the free second ends 208 of the nano-fingers 110 are controlled to thereby substantially control the deposition of the nano-particles 210.
In addition, the Raman-active material nano-particles 210 may one or both of enhance Raman scattering and facilitate analyte adsorption. For instance, the Raman-active material nano-particles 210 comprise a Raman-active material such as, but not limited to, gold (Au), silver (Ag), and copper (Cu) having nanoscale surface roughness. Nanoscale surface roughness is generally characterized by nanoscale surface features on the surface of the layer(s) and may be produced spontaneously during deposition of the Raman-active material layer(s). By definition herein, a Raman-active material is a material that facilitates Raman scattering and the production or emission of the Raman signal from an analyte adsorbed on or in a surface layer or the material during Raman spectroscopy.
Although the nano-fingers 110 have been depicted in
As shown in
Turning now to
In any event, and in one regard, the free ends 208 of the nano-fingers 110 are caused to contact each other as shown in
With reference now to
The sensing apparatus 300 is also depicted as including an illumination source 302 and a detector 304. Molecules of a substance 310 to be tested are also depicted as being positioned in contact with and in close proximity to the Raman-active material nano-particles 210. According to an example, the relative position of the apparatus 100 and the illumination source 302 and the detector 304 is to be modified to thereby enable testing to be performed on various locations of the Raman-active material nano-fingers 110. In this example, the apparatus 100 is movable with respect to the sensing apparatus 300, the sensing apparatus 300 is movable with respect to the apparatus 100, or both.
The illumination source 302 is depicted as emitting electromagnetic radiation, as represented by the arrow 306, which comprises, for instance, light. By way of example, the illumination source 302 comprises a laser that illuminates the substance 310 and the Raman-active material nano-particles 210. Illumination of the Raman-active material nano-particles 210 causes hot spots of relatively large electric field strength to occur. The hot spots are increased at the locations where the Raman-active material nano-particles 210 contact each other (not shown). The electric fields generated at the contact locations between the Raman-active material nano-particles 210 generally enhance the rate at which Raman light is scattered by the substance 310 positioned at or near the contact locations. The Raman scattered light, which is represented by the arrow 308, is shifted in frequency by an amount that is characteristic of particular vibrational modes of the substance 310. The detector 304 is to collect the Raman scattered light 308 and spectral analysis is to be performed on the Raman scattered light 308.
The Raman-active material nano-particles 210 located near or adjacent to the substance 310 is to enhance the production of Raman scattered light 308 from the substance 310 by concentrating or otherwise enhancing an electromagnetic field in or around the substance 310. In this regard, the likelihood that the substance 310 will produce sufficiently strong Raman scattered light 308 to be detected by the detector 304 and processed will thus also be increased.
Although the Raman scattered light 308 has been depicted as being directed toward the detector 304, the Raman scattered light 308 is emitted in multiple directions. In this regard, some of the Raman scattered light 308 may be directed into the body 102, which, in one example, comprises an optical waveguide. More particularly, for instance, Raman scattered light 308 may be generated in the body 102 as a result of the substance 310 coupling to the evanescent field of a waveguide mode. In these instances, the detector 304 may be positioned to detect the waves generated in the body 102 from the Raman scattered light 308. In any regard, the 308 may include a filter to filter out light originating from the illumination source 302, for instance, through use of a grating-based monochrometer or interference filters. The detector 304 may alternatively be positioned at other locations with respect to the nano-fingers 110, for instance, below the body 102 in
In any regard, the detector 304 is generally to convert the Raman scattered light 308 emitted from the substance 310 into electrical signals. In some examples, the detector 304 is to output the electrical signals to other components (not shown) that are to process the electrical signals, such as, a computing device. In other examples, the detector 304 is equipped with the processing capabilities.
Turning now to
At block 402, a body 102 having a cavity 104 is obtained. As discussed above, the body 102 comprises dimensions that enable the body 102 to be used as a test strip. In addition, the body 102 is composed of various types of materials and is either formed with the cavity 104 or the cavity 104 is formed into the body 102. Moreover, the body 102 may be formed as part of an array of bodies 102 as shown in
At block 404, a plurality of nano-fingers 110 is positioned in the cavity 104. According to an example, the nano-fingers 110 are formed directly onto a surface of the body 102 portion of the cavity 104. In another example, the nano-fingers 110 are formed on a substrate 202 and the substrate 202 is positioned within and attached to the surface of body 102 portion of the cavity 104.
According to an example, a nanoimprinting technique or a roll-to-roll process is implemented to form the nano-fingers 110 on the surface of the body 102 or the substrate 202. In this example, a template may be formed through photolithography or other advanced lithography with the desired patterning to arrange the nano-fingers 110 in the predetermined arrangement. More particularly, for instance, the desired patterns may be designed on a mold, by E-beam lithography, photolithography, laser interference lithography, Focused Ion Beam (FIB), self-assembly of spheres, etc. In addition, the pattern may be transferred onto, for instance, silicon, glass, or polymer substrate (PDMS, polyimide, polycarbonate, etc.). In other examples, the nano-fingers 110 may be formed in the predetermined arrangement through implementation of any suitable fabrication process. In addition, the nano-fingers 110 may be provided on the surface of the body 102 or substrate 202 through any suitable attachment mechanism as discussed above.
At block 406, Raman-active material nano-particles 210 are attached to the tips of the nano-fingers 110. More particularly, Raman-active material nano-particles 210 are attached to the tips 208 of the nano-fingers 110 as discussed above with respect to
At block 406, an opening in the cavity 104 is covered with a destructible cover 106 to protect the nano-fingers 110. The destructible cover 106 is attached, for instance, through use of at least one of an adhesive, heat, mechanical fasteners, etc., onto either a surface of the body 102 (
In certain examples, the nano-fingers 110 are collapsed toward each other such that tips 208 of the nano-fingers 110 are substantially in contact with each other prior to covering of the cavity 104 with the destructible cover 106 at block 408. According to an example, the nano-fingers 110 are initially in a first position, in which their tips 208 are in a substantially spaced arrangement with respect to each other. In addition, the gaps between the tips of the nano-fingers 110 are of sufficiently large size to enable a liquid to be supplied in the gaps. Moreover, the gaps are of sufficiently small size to enable the tips 208 of the nano-fingers 110 to move toward each other as the liquid evaporates, through, for instance, capillary forces applied on the tips as the liquid dries. Other non-limiting examples, such as e-beam, ion-beam, magnetic, mechanical force, thermal effect, or electric charge effect, may also or instead be utilized to cause the tips 208 of the nano-fingers 110 to move toward each other. In any regard, the Raman-active material nano-particles 210 may contact each other and remain in contact with each other through, for instance, van der Waals interactions between those contacting nano-particles 210.
In other examples, the tips 208 of the nano-fingers 110 are kept in a substantially separated arrangement prior to covering of the cavity 104 with the destructible cover 106. In these examples, the tips 208 of the nano-fingers 110 may be brought into substantial contact with each other following removal of the destructible cover 106. For instance, the substance to be tested may be introduced between the nano-fingers 110 and dried, which may cause the tips of the nano-fingers 110 to move toward each other and trap molecules of the substance to be tested.
Turning now to
At block 502, at least a portion of the apparatus 100, 100′ is inserted into a substance to be tested. The portion of the apparatus 100, 100′ that is inserted into the substance to be tested comprises the portion of the apparatus 100, 100′ that includes the destructible substrate 106 and the nano-fingers 110, although the entire apparatus 100, 100′ may be inserted. As discussed above, in some examples, the destructible material 106 comprises a material that dissolves in the substance to be tested within a predetermined length of time. The predetermined length of time may comprise, for instance, less than about one minute, less than about one hour, etc. As such, insertion of the section of the apparatus 100, 100′ containing the destructible cover 106 causes the destructible cover 106 to dissolve, thereby exposing the substance to be tested to the Raman-active material nano-particles 210 contained in the cavity 104. Moreover, direct insertion of the destructible cover 106 into the substance to be tested prior to removal of the destructible cover 106 prevents introduction of contaminants onto the Raman-active material nano-particles 210, thus resulting in relatively more accurate sensing application results.
At block 504, the apparatus 100, 100′ is removed from the substance to be tested. During removal of the apparatus 100, 100′, some portion of the substance to be tested remains on the Raman-active material nano-particles 210.
At block 506, a sensing application is performed on the substance that remains on the Raman-active material nano-particles 210. The sensing apparatus 300 may perform the sensing application as discussed above with respect to
According to an example, the tips 208 of the nano-fingers 110 are brought into substantial contact with each other following removal of the apparatus 100, 100′ from the substance to be tested For instance, the substance to be tested may be introduced between the nano-fingers 110 and dried, causing the tips of the nano-fingers 110 to move toward each other and trap molecules of the substance to be tested.
Although described specifically throughout the entirety of the instant disclosure, representative examples of the present disclosure have utility over a wide range of applications, and the above discussion is not intended and should not be construed to be limiting, but is offered as an illustrative discussion of aspects of the disclosure.
What has been described and illustrated herein is an example along with some of its variations. The terms, descriptions and figures used herein are set forth by way of illustration only and are not meant as limitations. Many variations are possible within the spirit and scope of the subject matter, which is intended to be defined by the following claims—and their equivalents—in which all terms are meant in their broadest reasonable sense unless otherwise indicated.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US2011/057884 | 10/26/2011 | WO | 00 | 3/4/2014 |