Raman spectroscopy has been utilized for a number of years to analyze the structure of inorganic materials and complex organic molecules. It has been found that by decorating a surface, upon which a molecule is later adsorbed, with a thin layer of a metal in which surface plasmons have frequencies in a range of electromagnetic radiation used to excite such a molecule and in which surface plasmons have frequencies in a range of electromagnetic radiation emitted by such a molecule, the intensity of a Raman spectrum of such a molecule may be enhanced. This technique has been termed surface enhanced Raman spectroscopy (SERS). The SERS effect is related to the phenomenon of plasmon resonance, in which metal nanoparticles exhibit an increased optical resonance in response to incident electromagnetic radiation, due to the collective coupling of conduction electrons in the metal.
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 are an apparatus and a method for performing spectroscopy. The apparatus includes an optical waveguide having a fluidic channel, a wavelength selective device coupled to the optical waveguide, and a detector coupled to the wavelength selective device. As discussed in greater detail below, a fluid sample is to be supplied into the fluidic channel and an excitation light is to illuminate the fluid sample. The molecules in the fluid sample are to emit a Raman scattered light in response to becoming illuminated by the excitation light. In certain examples, the emission of the Raman scattered light is enhanced by nano-fingers and Raman-active nano-particles provide in the fluidic channel.
The wavelengths and frequencies of the Raman scattered light generally depend upon the type(s) of molecules contained in the fluid sample. In this regard, the wavelengths and frequencies of the Raman scattered light emitted from the molecules in the fluid sample are detected to determine, for instance, the type(s) of molecules contained in the fluid sample. More particularly, a wavelength selective device is coupled to the optical waveguide, in which the wavelength selective device comprises a predetermined bandwidth and is to capture wavelengths and frequencies of light within the predetermined bandwidth. In other words, the wavelength selective device is to be resonant to specific light wavelengths and frequencies. The wavelength selective device, therefore, enables lightwaves having a predetermined frequency and wavelength to propagate from the optical waveguide through the wavelength selective device and onto a detector coupled to the wavelength selective device.
According to an example, each of a plurality of the wavelength selective devices is tuned to be resonant with a particular frequency and wavelength. In this example, the apparatus may be provided with wavelength selective devices that are each tuned to detect a predetermined frequency, such that, if each of the detectors coupled to the wavelength selective devices detects light, then a particular type of molecule may be determined to be present in the fluid sample. Alternatively, the apparatus may be provided with a plurality of wavelength selective devices that are tuned to detect a wide range of frequencies, such that, a determination of which of the detectors coupled to the wavelength selective devices detect light, maybe need to determine the type of molecules contained in the fluid sample.
According to another example, the wavelength selective device(s) comprises a tunable device, in which, the wavelength selective device(s) is tunable to be resonant with different frequencies of light. In this example, the wavelength selective device(s) may be tuned to be resonant with different frequencies of light to determine the frequencies at which light is emitted from the fluid sample. The frequencies of the emitted light that the detectors detect may be analyzed to determine the type of molecules contained in the fluid sample.
Through implementation of the apparatus and method disclosed herein, the type(s) of molecules contained in a fluid sample is to be determined through a determination of the frequencies and wavelengths of light detected to be emitted from the molecules of the fluid sample. In addition, the components of the apparatus may be integrated onto a single chip, such that, the apparatus comprises a relatively small and compact form factor.
The apparatus 100 is implemented to perform SERS to detect a molecule in an analyte sample with a relatively high level of sensitivity. The apparatus 100 includes an optical waveguide 102, which includes a fluidic channel 104. As shown in
The illumination source 140 comprises any suitable type of light source to direct excitation light 142 onto a sample contained in the fluid channel 104 and to cause Raman scattered light to be emitted from the sample. The illumination source 140 may thus comprises a solid state laser, such as, a plasmonic laser, a cavity laser, etc. In addition, or alternatively, the optical range of the excitation light 142 may vary from ultraviolet to infrared. The illumination source 140 is to supply the excitation light 142 to the optical waveguide 102 over free space or directly, for instance, through an optical fiber (not shown).
In any regard, and as discussed in greater detail herein below, the excitation light 142 is to illuminate the molecules of a fluid sample (not shown) contained in the fluidic channel 104. The illuminated molecules of the fluid sample is to emit light, such as, Raman, fluorescence, etc., at a set of frequencies depending upon the molecules contained in the fluid sample. The light emitted from the molecules of the fluid sample may undergo an elastic or inelastic scattering process, which may be directly analyzed as discussed below. Moreover, the optical waveguide 102 is to propagate light at the set of frequencies emitted from the molecules of the fluid sample through the optical waveguide 102.
The optical waveguide 102 is also depicted as being coupled with a plurality of wavelength selective devices 120a-120n, in which the term “n” comprises an integer equal to or greater than one. The wavelength selective devices 120a-120n may be coupled to the optical waveguide 102 in any suitable manner. For instance, the optical waveguide 102 may be provided with integration sites (not shown) at which the wavelength selective devices 120a-120n are coupled to the optical waveguide 102. In addition, or alternatively, the wavelength selective devices 120a-120n are coupled to the optical waveguide 102 through waveguide connectors (not shown) that are to propagate luminescence therethrough. The waveguide connectors may be fabricated out of the same material as the optical waveguide 102.
Generally speaking, the wavelength selective devices 120a-120n operate as filters that selectively capture specific wavelengths of light. In other words, the wavelength specific devices 120a-120n are resonant with particular frequencies and wavelengths of light. As such, light having the particular frequencies and wavelengths of light are able to propagate through the wavelength specific devices 120a-120n, while light having other frequencies and wavelengths do not resonate in the wavelength specific devices 120a-120n. In this regard, as light travels through the optical waveguide 102, the wavelength selective devices 120a-120n may each respectively tune out those frequencies and wavelengths of light that are not resonant with the wavelength selective devices 120a-120n. As such, none of the detectors 130 will detect the lightwaves that are not resonant with any of the wavelength selective devices 120a-120n.
In a first example, each of the wavelength selective devices 120a-120n is tuned to selectively capture a different wavelength or range of wavelengths of light. In this example, the wavelength selective devices 120a-120n comprise different predetermined bandwidths and are to capture the set of frequencies from the luminescence corresponding to frequencies within the predetermined bandwidths. For example, a first wavelength selective device 120a may be tuned to comprise a bandwidth including a frequency of 785 nanometers. In this example, the first wavelength selective device 120a would capture the photons of the luminescence that are propagated through the optical waveguide 102 that include a frequency of 785 nanometers.
Examples of other bands of frequency that may be provided by the molecules of the fluid sample during spectroscopy include but are not limited to the following: 415 nanometers, 572 nanometers, 673 nanometers, 785 nanometers and 1064 nanometers. The wavelength selective devices 120a-120n may be tuned to a relatively narrow bandwidth, and thus, a relatively narrow range of frequencies. Furthermore, in one example, several wavelength selective devices 120a-120n may be finely tuned to cover a small range of wavelengths. The bandwidths of these same wavelength selective devices 120a-120n may be overlapped, thus covering a continuous wavelength band.
In a second example, the wavelength selective devices 120a-120n comprise tunable wavelength selective devices, in which, the wavelength selective devices 120a-120n are tunable to selectively capture different wavelengths or ranges of wavelengths of light. In a third example, the wavelength selective devices 120a-120n comprise a combination of tuned and tunable wavelength selective devices.
As also shown in
The detectors 130 may be sensitive to a relatively large band of frequencies. Alternatively, the detectors 130 may be tuned to a certain band of frequencies, for instance, the frequencies of light that are to be emitted through the respective wavelength selective devices 120a-120n. In any regard, the detectors 130 are to generate electrical signals 132, which may be processed to determine each of the set of frequencies of the luminescence captured by the wavelength selective devices 120a-120n.
According to an example, the wavelength selective devices 120a-120n comprise ring resonators, as shown in
As discussed above, each of the wavelength selective devices 120a-120n may be tuned to a particular frequency or wavelength or may be tunable. In instances where the wavelength selective devices 120a-120n are tunable, the ring resonators may be tuned through any suitable tuning operation. For instance, the ring resonators may be tuned through application of different levels of heat to the ring resonators, application of different charge injections, application of different electro-optical effects, etc. In addition, although the ring resonators 120a-120n have been depicted as comprising circular shapes, the ring resonators may be fabricated in different shapes, such as, an oval shape.
In other examples, the wavelength selective devices 120a-120n comprise other types of wavelength selective devices, such as, distributed Bragg reflectors (DBRs), Fabry-Perot interferometers, etc. An example of an apparatus 150 comprising DBRs as the wavelength selective devices 120a-120n is depicted in
In one example, each of the wavelength selective devices 120a-120n comprises a DBR that is tuned to enable selected frequencies or wavelengths of light to reach the respective detectors 130. In another example, each of the wavelength selective devices 120a-120n comprises a tunable DBR that is tunable to selectively vary the frequency and the wavelength of light that is able to propagate through the wavelength selective devices 120a-120n and onto respective detectors 130. In this example, the DBRs (wavelength selective devices) 120a-120n may be tuned through any suitable tuning operation. For instance, the DBRs (wavelength selective devices) 120a-120n may be tuned through application of electricity onto the DBRs, etc.
Turning now to
In any regard, the nano-fingers 152 may be attached to a surface of the optical waveguide 102 or separate substrate through any suitable attachment mechanism. For instance, the nano-fingers 152 may be grown directly on the optical waveguide 102 or separate substrate surface through use of various suitable nano-structure growing techniques. As another example, the nano-fingers 152 may be integrally formed with the optical waveguide 102 or separate substrate. In this example, for instance, a portion of the material from which the optical waveguide 102 or substrate is fabricated and may be etched or otherwise processed to form the nano-fingers 152. In a further example, a separate layer of material may be adhered to the optical waveguide 102 or separate substrate surface and the separate layer of material may be etched or otherwise processed to form the nano-fingers 152.
Turning now to
In any of the examples above, the nano-fingers 152 are formed of a relatively flexible material to enable the nano-fingers 152 to be laterally bendable, for instance, to enable free ends 206 of the nano-fingers 152 to move toward each other, as discussed in greater detail herein below. Examples of suitable materials for the nano-fingers 152 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. In various examples, the nano-fingers 152 may be fabricated through a nanoimprinting 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 152. 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 152.
A nano-finger 152 may be defined 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 152 laterally onto one or more neighboring nano-fingers 152. 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 base of the nano-finger 152 may range between about 20 nm and about 300 nm and the length may be more than about 1 micrometer (μm). In other examples, the nano-finger 152 is sized based upon the types of materials used to form the nano-finger 152. Thus, for instance, the more rigid the material(s) used to form the nano-finger 152, the less the width of the nano-finger 152 may be to enable the nano-finger 152 to be laterally collapsible. In further examples, the nano-fingers 152 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).
As shown in
The nano-fingers 152 have been depicted in
In addition, in
In any regard, the Raman-active material nano-particles 210 may be deposited onto at least the free ends of the nano-fingers 152 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 Raman-active material nano-particles 210 are deposited onto the free second ends of the nano-fingers 152 may be 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. The Raman-active material nano-particles 210 generally enhance sensing operations, such as, surface enhanced Raman spectroscopy (SERS), enhanced fluorescence, enhanced luminescence, etc., to be performed on particles positioned on or near the nano-fingers 152. The sensing operations are performed on the particles to detect molecules in fluid samples. The Raman-active material nano-particles 210 may 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.
In some examples, surfaces of the nano-fingers 152 may be functionalized to facilitate adsorption of an analyte. For example, the tips or free ends of the nano-fingers 152 in a vicinity thereof (not illustrated) may be functionalized with a binding group to facilitate binding with a specific target analyte species. A surface of the Raman-active material nano-particles 210 may be functionalized, for example. The functionalized surface (that is, either a surface of the nano-finger 152 itself and/or the Raman-active material nano-particles 210) may provide a surface to which a particular class of analytes is attracted and may bond or be preferentially adsorbed. The functionalized surface may selectively bond with protein, DNA or RNA, for example.
Although the nano-fingers 152 have been depicted as each extending vertically and at the same heights with respect to each other, it should be understood that some or all of the nano-fingers 152 may extend at various angles and heights with respect to each other. The differences in angles and/or heights between the nano-fingers 152 may be based upon, for instance, differences arising from manufacturing and/or growth variances existent in the fabrication of the nano-fingers 152 and the deposition of the Raman-active material nano-particles 210 on the nano-fingers 152, etc.
As shown in
Turning now to
In any event, and in one regard, the free ends 206 of the nano-fingers 152 may be caused to contact each other as shown in
According to an example, the apparatus 100, 150 is integrated onto a single chip, for instance, as an integrated electrical circuit (IC). That is, the optical waveguide 102, the wavelength selective devices 120a-120n, the detectors 130, and the illumination source 140 are all integrated onto a single chip. The integrated chip may be in communication with a processor (not shown) that is to at least one of output, for instance, display, and identify the frequencies and wavelengths of light detected by the detectors 130. The processor may be integrated onto the chip or may be external to the chip. The processor may be integrated onto the chip or may be provided on an external device.
In addition, or alternatively, the optical waveguide 102 may be removable, such that, the apparatus 100, 150 may be used to test different samples simply by replacing the optical waveguide 102 and introducing a different fluid sample into the new optical waveguide 102. The optical waveguide 102 may also be fixed and thus may be cleaned out prior to introduction of a different fluid sample into the optical waveguide 102.
Turning now to
At block 302, a fluid sample is introduced into the fluidic channel 104 of the optical waveguide 102. The fluid sample may be introduced through an opening in the fluidic channel 104 either prior to or after the optical waveguide 102 is positioned to receive excitation light 142 from the illumination source 140.
At block 304, the fluid sample contained in the fluid channel 104 is illuminated to cause molecules of the fluid sample to emit Raman scattered light. The Raman scattered light is shifted in frequency by an amount that is characteristic of particular vibrational modes of the molecules. According to an example, the emission of the Raman scattered light from the molecules is enhanced by the nano-fingers 152 and, more particularly, the Raman-active nano-particles 210 discussed above with respect to
The Raman active nano-particles 210 located near or adjacent to the analyte molecule(s) generally enhance the production of Raman scattered light from the analyte molecule(s) by concentrating or otherwise enhancing an electromagnetic field in a vicinity of the analyte molecule(s). In examples where the nano-fingers 152 are formed of a metallic material, the nano-fingers 152 themselves may also enhance the production of the Raman scattered light. As also discussed above, the contacting of two or more of the free ends 206 with each other to trap the analyte molecule(s) may substantially increase the likelihood that the analyte molecule(s) will be positioned near or in contact with some Raman active nano-particles 210 and thus be positioned within a hot spot. In this regard, the likelihood that an analyte molecule(s) will produce sufficiently strong Raman scattered light to be detected by at least one of the detectors 130 will thus also be increased.
Thus, according to an example, following introduction of the fluid sample into the fluidic channel 104 and prior to illumination of the fluid sample at block 304, the nano-fingers 152 are caused to collapse upon each other. Thus, for instance, the fluid sample may be introduced into the fluidic channel 104 while the nano-fingers 152 are arranged, for instance, as shown in
In any regard, the optical waveguide 102 channels the Raman scattered light emitted from the molecules of the fluid sample to the wavelength selective devices 120a-120n.
At block 306, the wavelength selective devices 120a-120n filter the Raman scattered light. As discussed above, each of the wavelength selective devices 120a-120n comprises a predetermined bandwidth and is to capture frequencies of light within the predetermined bandwidth. Thus, each of wavelength selective devices 120a-120n generally operates to allow light having the frequencies and wavelengths that are within the respective predetermined bandwidths to pass therethrough, effectively filtering the light propagating through the optical waveguide 102 from reaching the detectors 130.
At block 308, at least one of the detectors 130 detects the filtered Raman scattered light. More particularly, the detectors 130 coupled to the wavelength selective devices 120a-120n through which the light has propagated through the wavelength selective devices 120a-120n detect the filtered Raman scattered light propagating through the optical waveguide 102 having predetermined frequencies and wavelengths.
At block 310, the detector(s) 130 that detect the filtered Raman scattered light output electrical signal(s). The detector(s) 130 may output the electrical signal(s) to a processor (not shown) that is to determine the set of frequencies that have been detected by the detector(s) 130. In other words, the processor may be provided with information regarding the predetermined bandwidths of the wavelength selective devices 120a-120n to which the detectors 130 are respectively coupled. In addition, the processor may determine which of the detectors 130 outputted the electrical signals and may use that information to determine at least some of the frequencies of the light emitted from the molecules of the fluid sample.
According to an example, wavelength selective devices 120a-120n having predetermined bandwidths are selected for implementation of the method 300. In this example, for instance, the predetermined bandwidths of the wavelength selective devices 120a-120n may be selected to identify a particular type of molecule. Thus, for instance, the particular type of molecule may be determined to be present in a fluid sample if each of the detectors 130 coupled to the wavelength selective devices 120a-120n outputs electrical signals at block 310.
According to another example, a relatively large number of wavelength selective devices 120a-120n covering a relatively wide range of bandwidths are selected for implementation of the method 300. In this example, the types of molecule(s) in a fluid sample may be determined from a determination of which of the detectors 130 coupled to the wavelength selective devices 120a-120n outputted electrical signals at block 310.
According to a further example, a number of tunable wavelength selective devices 120a-120n, which may include a single tunable wavelength selective device 120a, is selected for implementation of the method 300. In this example, the wavelength selective devices 120a-120n are tuned to different bandwidths during different iterations of the method 300. In addition, a determination is made as to which bandwidths resulted in the detector(s) 130 coupled to the tunable wavelength selective device(s) 120a-120n outputting electrical signal(s) at block 310.
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.
This application shares some common subject matter with U.S. Patent Application Publication No. 2011/0267610, titled “Compact Sensor System”, published on Nov. 3, 2011.