Patent Application
20090263912
Not Applicable
A portion of the material in this patent document is subject to copyright protection under the copyright laws of the United States and of other countries. The owner of the copyright rights has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the United States Patent and Trademark Office publicly available file or records, but otherwise reserves all copyright rights whatsoever. The copyright owner does not hereby waive any of its rights to have this patent document maintained in secrecy, including without limitation its rights pursuant to 37 C.F.R. § 1.14.
1. Field of the Invention
This invention pertains generally to optical waveguides, and more particularly to subwavelength evanescent field optical sensors.
2. Description of Related Art
Chemically synthesized nanowires represent a unique class of building blocks for the construction of nanoscale electronic and optoelectronic devices. Since nanowire synthesis and device assembly are typically separate processes, nanowires permit more flexibility in the heterogeneous integration of different materials than standard silicon technology allows, although the assembly itself remains a major challenge. The toolbox of nanowire device elements is growing and currently includes various types of transistors, light emitting diodes, lasers, and photodetectors. While the electrical integration of simple nanowire circuits using lithography has been demonstrated, optical integration, which promises higher speeds and greater device versatility, remains unexplored.
Photonics, the optical analogue of electronics, shares the logic of miniaturization that drives research in semiconductor and communications technology. The ability to manipulate pulses of light within sub-micron spaces is vital for highly integrated light-based devices, such as optical computers, to be realized. Recent advances in using photonic bandgap and plasmonic phenomena to control the flow of light show substantial promise in this regard. However, both of these approaches typically rely on difficult and costly lithographic processes for device fabrication and are in their early stages of development.
Compact, reusable chemical sensors are highly desirable for on-site detection in the field, including the identification of water contaminants, hazardous biochemical compounds or blood-serum content. Ideally, a sensing platform should be portable and employ several complementary sensing modalities that allow quantitative chemical identification of extremely small sample volumes. Optical spectroscopy is a powerful analytical tool for characterizing biological and chemical systems, but making a standard optical laboratory portable is a major challenge. Recent advances have been made in the synthesis and assembly of nanomaterials, wherein the integration of these materials into functional device architectures for sensing and monitoring can be considered. Of the well-studied inorganic nanostructures, chemically synthesized one-dimensional (1D) semiconductors have gained significant interest from the photonics community as passive and active components for miniaturized spectroscopic devices. This is due in part to their ability to guide a significant portion of the confined electromagnetic energy outside the cavity (i.e., in the evanescent field) while operating below the diffraction limit of light. Since the evanescent field travels efficiently through fluidic and air dielectrics, it is possible to integrate the waveguides into microfluidic devices and sense molecules located near the surface of the cavity.
One-dimensional semiconductor nanomaterials offer unique advantages over their zero- and two-dimensional counterparts because their geometric shapes allow them to capture and guide light over long distances. Trapping light in volumes smaller than the wavelength of light is essential to the miniaturization of optical characterization techniques. Materials currently being studied for this purpose include photonic crystals, high-index solids, and metal surfaces. However, engineering versatile, reusable optical devices from materials such as photonic crystals and metallic nanostructures remains challenging due to the difficulty in performing spectroscopy with the guided optical energy. In addition, the synthetic steps for producing these materials tend to be labor-intensive and involve costly lithographic techniques.
Fiber-based detection is a unique alternative to free-space sensing because it localizes chemical recognition at the surface of a waveguide. Among the most popular sensing schemes that rely on the evanescent field of a fiber are absorption and fluorescence. Typically these set-ups involve multimode silica fibers with diameters much larger than the free-space wavelength of light. The evanescent field in these experiments has been used to measure refractive indices of liquids, monitor volatile compounds in water and detect shifts in localized surface plasmon resonances of coupled metal colloids. Recently, it has been proposed to use subwavelength silica fibers in a Mach-Zehnder type interferometer to detect index changes caused by molecules interacting with the surface of the fibers. Though these various sensing configuration are promising for high sensitivity, fast cycling times and reversibility, they do not provide versatility in their spectroscopic detection or enable a chemical read-out of the analyte.
Accordingly, the importance of moving beyond fiber sensing on/off detectors is vital toward developing materials that can support multiple analytical modes for chemical identification. The present invention fulfills that need as well as others and overcomes shortcomings of prior solutions.
The present invention is directed at assembling photonic circuits from a collection of nanoribbon/nanowire elements that assume different functions, such as light creation, routing and detection. The subwavelength optical waveguides of the invention are formed from a nanoribbon or nanowire having a diameter that is less than the wavelength of light to be guided and are potentially simpler while being versatile, such as serving as a fundamental element of photonic circuits of various types.
Chemically synthesized nanoribbons and nanowires have several features that make them good building blocks, including inherent one-dimensionality, a variety of optical and electrical properties, good size control, low surface roughness and, in principle, the ability to operate both above and below the diffraction limit. An important step toward integrated nanoribbon/wire photonics is to develop a nanoribbon/wire waveguide that can couple pairs of nanoribbon/wire elements and provide the flexibility in interconnection patterns that is needed to carry out complex tasks, such as logic operations.
The invention is amenable to being embodied in a number of ways, including but not limited to the following implementations.
At least one implementation is a microfluidic optical sensor utilizing a nanowire or nanoribbon waveguide, comprising: (a) at least one fluidic structure configured for conveying one or more molecular species; (b) at least one optical waveguide retained proximal said fluidic structure; (c) said at least one optical waveguide configured with a sub-optical diameter and positioned to optically interrogate nearby molecular species retained within said fluidic structure; (d) means for optically pumping (e.g., laser source) said at least one optical waveguide; and (e) means for detecting chemical species within said fluidic structure in response to optical characterization of sub-picoliter volumes of solution.
A number of variations of the microfluidic optical sensor can be implemented either separately or in combination, such as the following. In one implementation said optical waveguide is retained proximal said fluidic channel such as by bridging one or more sensing channels within said fluidic structure. In at least one implementation metallic nanoparticles are retained adjacent said optical waveguide, the combination thus being configured for exciting the metallic nanoparticles in amplified Raman scattering. In at least one embodiment a charged dye is retained within the analyte to alter fluorescence characteristics of the optical sensor. For example, in one implementation the charged dye is configured for electrostatic adherance to said optical waveguide to attenuate optical waveguide fluorescence with respect to time. The optical waveguide is configured for guiding emissions to a position within said fluidic structure, with optical characterization performed in response to subwavelength evanescent field optical sensing. In one implementation, optical characterization is selected from the group of optical characterization parameters consisting of absorbance, fluorescence and surface enhanced Raman spectroscopy (SERS). In one preferred implementation, the fluidic structure comprises one or more fluidic channels through which an analyte, containing one or more molecular species, is retained and/or communicated. In at least one implementation the means for detecting chemical species includes an optical objective through which optical energy is routed to a spectrometer. In at least one implementation a pumping means is provided for pumping one or more molecular species through said fluidic structure past said at least one optical waveguide.
At least one implementation is an optical sensing method, comprising: (a) providing an optical sensor comprising a flow cell structure having a plurality of microfluidic channels and a nanowire or nanoribbon waveguide positioned across said channels and coupled to said flow cell structure; (b) flowing a material through said microfluidic channels; (c) optically pumping the waveguide to generate evanescent wave emission through said channels; and (d) detecting one or more chemical species in response to optically registering interaction between said chemical species and said evanescent wave emission. A number of variations of the above method can also be implemented without departing from the teachings of the present invention.
The present invention can provide a number of beneficial aspects which can be implemented either separately or in any desired combination without departing from the present teachings.
An aspect of the invention describes the assembly of photonic circuit elements from nanostructures such as SnO2 nanoribbon and ZnO nanowire waveguides.
Another aspect of the invention comprises high aspect ratio (e.g., >1000) nanoribbons/nanowires waveguides having diameters below the wavelength of light (typically 100 nm to 400 nm) for internally generated photoluminescence (PL) and nonresonant UV/visible light emitted from evanescently coupled structures.
Another aspect of the invention describes the length, flexibility and strength of these single-crystalline structures enable them to be manipulated and positioned on surfaces to create various single-ribbon shapes and multi-ribbon optical networks, including ring-shaped directional couplers and nanoribbon/wire emitter-waveguide-detector junctions.
Another aspect of the invention is an ability to manipulate the shape of active and passive nanoribbon/wire cavities to provide a new tool for investigating the cavity dynamics of subwavelength structures.
Another aspect of the invention pushes subwavelength optical fibers beyond the use of silica nanoribbons/nanowires.
Another aspect of the invention teaches fabrication of nanoribbon and nanowires from active, passive, non-linear and semiconducting inorganic crystals, as well as a wide variety of polymers, and combinations thereof.
Another aspect of the invention takes advantage of simultaneous photon, charge carrier and spin manipulation within and between nanowires of different compositions.
Another aspect of the invention takes advantage materials having higher refractive indices than silica-based glasses, therein permitting confinement of light of a given wavelength within thinner structures for denser integration.
Another aspect of the invention is waveguiding in liquids using subwavelength nanoribbon/wire optical waveguides.
Another aspect of the invention provides for the manipulation of freestanding nanoribbons/wires as mechanically flexible elements on surfaces or as mobile probes in fluids providing versatility beyond that of lithographically-defined structures affixed to substrates.
Another aspect of the invention is a nanoribbon/wire optical waveguide having a high aspect ratio and a diameter less than the wavelength of light to be guided, for example an aspect ratio greater than approximately 1000, with a diameter in the range from approximately 100-400 nm.
Another aspect of the invention is a subwavelength optical waveguide formed from a crystalline oxide nanoribbon/wire, for example SnO2, ZnO, or GaN.
Another aspect of the invention is to provide a nanoribbon/wire laser and a nanoribbon/wire photodetector coupled by a nanoribbon/wire optical channel.
Another aspect of the invention is an optical waveguide comprising a nanoribbon/wire dispersed on an SiO2 or mica substrate.
Another aspect of the invention is a method of forming a SnO2 nanoribbon/wire waveguide.
Another aspect of the invention is a method of forming a ZnO nanoribbon/wire waveguide.
Another aspect of the invention is an apparatus for guiding light through liquid media, for example through a nanoribbon or nanowire waveguide comprising SnO2, ZnO, high dielectric waveguides, GaN, and so forth.
Another aspect of the invention is a probe or a sensor comprising a subwavelength nanostructure waveguide.
Another aspect of the invention is an optical router comprising at least two coupled nanoribbon waveguides, such as SnO2, or ZnO nanowire waveguides.
Another aspect of the invention is an optical router comprising a network of nanoribbon waveguides (e.g., SnO2 and so forth) configured to separate white light and route individual colors based on a short-pass filtering effect.
Another aspect of the invention is an optical crossbar grid comprising two pairs of orthogonal nanoribbon waveguides configured to conduct light through abrupt 90° angles, for example SnO2 nanoribbon waveguides.
Another aspect of the invention are on-chip photonic sensors, with structures smaller than the wavelength of the guided light, which control the flow of light through liquids.
Another aspect of the invention are semiconductor nanowire waveguides which provide excellent optical confinement in solutions and can be integrated into microfluidic devices.
Another aspect of the invention is a microfluidic optical sensor that employs a nanowire or nanoribbon waveguide.
Another aspect of the invention is an optical sensor having a plurality of microfluidic channels proximally coupled to a nanowire or nanoribbon waveguide.
Another aspect of the invention is an optical sensor formed from a flow cell structure having a plurality of microfluidic channels, and a single crystalline nanoribbon waveguide coupled to the structure across the microfluidic channels.
Another aspect of the invention is a method of fabricating a microfluidic sensor.
Another aspect of the invention is a sensor having flow cell structure having a plurality of microfluidic channels, providing a nanowire or nanoribbon waveguide, positioning the waveguide across the channels, and coupling the waveguide to the flow cell structure.
Another aspect of the invention is a sensor fabricated having a nanoribbon waveguide, such as SnO2, with a microfluidic flow cell, such as polydimethylsiloxane (PDMS), having a plurality of channels upon which the nanoribbon waveguide is attached.
Another aspect of the invention is an optical sensing method based on evanescent wave emission.
Still another aspect of the invention is an optical sensing method in which evanescent wave emissions are generated from an optically pumped nanowire or nanoribbon waveguide positioned across the channels of a flow cell through which material flows.
Further aspects of the invention will be brought out in the following portions of the specification, wherein the detailed description is for the purpose of fully disclosing preferred embodiments of the invention without placing limitations thereon.
The invention will be more fully understood by reference to the following drawings which are for illustrative purposes only:
Nanoscale ribbon-shaped crystals of binary oxides exhibit a range of interesting properties including extreme mechanical flexibility, surface-mediated electrical conductivity, and lasing. However, as part of a recent study of the photoluminescence (PL) of SnO2 nanoribbons in our laboratory, we discovered that nanoribbons with high aspect ratios (>1000) act as excellent waveguides of their visible PL emission. SnO2 is a wide-bandgap (3.6 eV) semiconductor characterized by PL bands at 2.5 eV (green) and 2.1 eV (orange), and finds application in gas sensors and transparent electrodes. For our studies, we used conventional thermal transport techniques to synthesize single-crystalline nanoribbons of SnO2 with lengths of up to 5000 μm. The structures synthesized possessed fairly uniform (+/−10%) rectangular cross-sections with dimensions as large as 2 μm×1 μm and as small as 15 nm×5 nm. Many of the nanoribbons synthesized were 100 nm to 400 nm wide and thick, which we found to be an optimal size range for efficient steering of visible and ultraviolet light in a subwavelength cavity.
Additionally, we have found that photonic circuit elements can be assembled from, for example, SnO2 nanoribbon and ZnO nanowire waveguides. High aspect ratio nanoribbons/wires with diameters below the wavelength of light (typically 100 nm to 400 nm) were found not only to act as excellent waveguides of both their own internally generated photoluminescence (PL), but also nonresonant UV/visible light emitted from adjacent, evanescently coupled, nanowires or external laser diodes. Furthermore, the length, flexibility and strength of these single-crystalline structures enable them to be manipulated and positioned on surfaces to create various single-ribbon shapes and multi-ribbon optical networks, including ring-shaped directional couplers and nanowire emitter-waveguide-detector junctions. This ability to manipulate the shape of active and passive nanowire cavities provides a new tool for investigating the cavity dynamics of subwavelength structures. Moreover, future advances in assembling the diverse set of existing nanowire building blocks could lead to a novel and versatile photonic circuitry.
It should be appreciated that the use nanoribbons/wires as optical waveguides is based on the nanoribbons/wires having diameters which are smaller than the wavelength of light. It should also be noted that nanoribbons/wires need not have circular cross-sections for use herein. For example, ZnO nanowires typically have a hexagonal cross-section and SnO2 nanoribbons typically have a rectangular cross-section. Therefore, in the case of a non-circular cross-section, the term “diameter” is intended generally to refer to the effective diameter, as defined by the average of the major and minor axis of the cross-section of the structure. However, the term “diameter” is not limited to the foregoing definition and is also intended to encompass dimensions of a nanoribbon/wire which allow for the nanoribbon/wire to function as a subwavelength waveguide.
Initially, waveguiding behavior of individual nanoribbons dispersed on SiO2 and mica substrates were studied using far-field microscopy and spectroscopy.
More particularly,
As can be seen, when in response to a tightly focused continuous wave laser light (3.8 eV) onto one end of a nanoribbon, a large fraction of the resulting PL was guided by the nanoribbon cavity to its opposite end, where the PL emanated with high intensity. Quite surprisingly, it was found that the nanoribbon mimicked had many similarities. It was also found that nanoribbons that were damaged internally during dispersion or which possessed sizeable 3D surface defects scattered guided light in a series of bright spots along their lengths. Referring to
Referring again to
In general, one would expect a subwavelength resonator to show a large optical loss that is highly wavelength dependent, with better confinement of shorter wavelength radiation. To investigate the dependence of optical confinement on wavelength, single nanoribbons were illuminated, such as with monochromatic red, green and blue light at a 30° incidence angle, and their end emission was monitored. It was found that red waveguiding was rare, green waveguiding was common, and blue waveguiding was ubiquitous. We also found that, for a given dielectric material, cavity geometry and wavelength, a critical diameter exists below which all higher order optical modes are cut off and waveguiding becomes increasingly difficult to sustain. More specifically, by treating a nanoribbon waveguide as a cylinder of SnO2 embedded in air, cutoff diameters were found for higher order transverse modes of light at about 270 nm, 220 nm and 180 nm for the 652 nm, 532 nm and 442 nm. While this approximation simplifies the cavity shape and ignores substrate coupling and other effects, these values are in reasonable agreement with scanning electron microscopy measurements of the sizes of the blue and green waveguides. The majority of nanoribbons in our samples were too thin for propagating red light over distances greater than approximately 100 μm. However, it was clearly found that nanoribbons with sufficiently large cross-sectional dimensions as described above would effectively guide wavelengths across the visible spectrum, acting as subwavelength red-green-blue (RGB) optical fibers (e.g., optical transmitters) as shown in
The wavelength-dependent loss of straight nanoribbons was quantified using near-field scanning optical microscopy (NSOM). By way of example and not limitation, nanoribbons were pumped (3.8 eV) at different points along their length relative to a fixed collection probe. We found that losses ranged from 1-8 dB mm−1 for wavelengths between 450 nm and 550 nm, depending on nanoribbon cross-sectional area and the density of surface scattering centers. These values are higher than those reported recently for subwavelength silica waveguides, likely due to the somewhat rougher nanoribbon surfaces and the extra loss due to substrate coupling. It was noted, however, that the losses in this case are better than what is required for integrated planar photonic applications, in which waveguide elements are configured to transmit light over very short distances.
It has also been found that the nanoribbons used in for these tests should be of sufficient length and strength to be pushed, bent and shaped using a commercial micromanipulator under an optical microscope. The large aspect ratio and elastic flexibility of SnO2 nanoribbons allowed manipulating the location and shape of individual nanoribbons under the optical microscope using a commercial micromanipulator tipped with sharp tungsten probes. Waveguiding nanoribbons with one free end (dangling) in air could be elastically bent to large angles (e.g., up to about 180°) without kinking or fracturing, which is remarkable for an oxide that is brittle in its bulk form. In these tests straight nanoribbons could be fashioned into wiggles, circles and other shapes by using nanoribbon-substrate forces to prevent elastic recoil.
The dragging, aligning and cutting of single nanoribbons is routine. Here, the micromanipulator was used to selectively remove the overlying nanoribbon in
It will be appreciated that freestanding nanoribbons can be repeatedly and elastically curved into loops with radii as small as 5 μm, which is remarkable for a crystal that is brittle in its bulk form. On appropriately chosen surfaces, single nanoribbons are easily fashioned into a variety of shapes with the help of nanoribbon-substrate forces to prevent elastic recoil as shown in
Manipulation also makes it possible to investigate the shape-dependent waveguiding of single nanoribbon cavities. For example, a tight S-turn was fashioned in one end of a long, thin nanoribbon (dimensions: 785 μm×275 nm×150 nm) to illustrate the robust nature of optical steering in these structures as shown in
It was also observed that bending a nanoribbon, even slightly, can dramatically change the mode structure of its output light as shown in
The dark field images (
The dark-field images (
Since light diffracts in all directions when it emerges from a subwavelength aperture, nanoribbons must be in close proximity, and preferably in direct physical contact, to enable the efficient transfer of light between them. Various coupling geometries were tested and it was found that a staggered side-by-side arrangement, in which two nanoribbons interact over a distance of several micrometers, outperforms direct end-to-end coupling, which relies on scattering between end facets. Staggered nanoribbons separated by a thin air gap can communicate via tunneling of evanescent waves. It is also possible to bond two nanoribbons together by Van Deer Waals forces, for example by draping one over another, to create a robust optical junction.
Note that
Single-crystalline nanoribbons are intriguing structures with which to manipulate light, both for fundamental studies and photonics applications. As passive elements, they are efficient UV/visible waveguides and filters that can be assembled into optical components, networks and devices. Being semiconductors or, in their doped state, transparent metals, oxide nanoribbons are well suited to combine simultaneous electron and photon transport in active nanoscale components. Key challenges to the wider use of these materials include narrowing their size dispersity and developing better parallel assembly schemes for nanowire integration. Answering the former challenge depends on gaining control over the poorly understood vapor-solid process that is typically used in nanoribbon synthesis.
The 50× dark-field image and 100× dark-field inset of
The dark-field images in
The optical loss of several nanoribbon waveguides was measured by systematically varying the distance between UV excitation (50 μm spot size) and PL collection in the near-field. A loss of about 2 dB mm−1 is estimated at a wavelength of 550 nm for a nanoribbon with a 400×150 nm2 cross-section, which is significantly greater than losses reported recently for subwavelength silica waveguides.
As can be seen from the forgoing, due to their extraordinary length, high flexibility and strength, nanoribbon waveguides are excellent materials with which to study the interplay between mechanics, microstructure and optical confinement in nanoscale cavities. They can be manipulated and assembled to serve as photonic interconnects between single nano-objects, such as nanowire lasers, in optical circuits and devices. Furthermore, nanoribbon waveguides can be used as filter devices.
SnO2 nanoribbon waveguides were synthesized by the chemical vapor transport of SnO powder in a quartz tube reactor operating at 1100° C. and 350 Torr of flowing argon (50 sccm). Milligram quantities of nanoribbons were collected on an alumina boat near the center of the reactor and deposited onto clean substrates by dry transfer. Long ZnO nanowires were grown via oxidation of Zn metal in a quartz furnace at 800° C. and 760 Torr of flowing oxygen/argon, as described in the literature, and also dispersed by dry transfer. InP nanowires produced by a laser-assisted vapor-liquid-solid process (using Au catalyst) were sonicated into ethanol solution and transferred to the surface by drop-casting. Contacts to InP were fabricated by electron beam lithography and thermal evaporation (100 nm Ti), followed by rapid thermal annealing at 475° C. in N2/H2 for one minute.
Optical measurements were carried out using a dark-field microscope outfitted with a cryostat (Janis X-100). The PL excitation source was a HeCd laser operating at 325 nm. Laser pointers (532 nm and 652 nm) and the HeCd laser (442 nm) provided nonresonant illumination. The size of the laser spot was approximately 50 μm for all measurements. Spectra were collected with a fiber-coupled spectrometer (SpectraPro 300i, Roper Scientific) and liquid N2 cooled CCD detector. Images were captured using both a microscope-mounted camera (CoolSNAP, Roper Scientific) and a handheld digital camera (PRD-T20, Toshiba). Loss measurements were made with a commercial NSOM setup operating in collection mode, with 325 nm excitation. For nanoribbon manipulation, we used a three-axis commercial unit tipped with tungsten probes (10 μm ends).
As described above, photonic circuit elements can be assembled from SnO2 nanoribbon and ZnO nanowire waveguides. High aspect ratio nanoribbons/wires with diameters below the wavelength of light (typically 100-400 nm) were shown to act as excellent waveguides of both their own internally generated photoluminescence (PL) and nonresonant UV/visible light emitted from adjacent, evanescently coupled, nanowires or external laser diodes. The length, flexibility and strength of these single-crystalline structures enabled them to be manipulated and positioned on surfaces to create various single-ribbon shapes and multi-ribbon optical networks, including ring-shaped directional couplers and nanowire emitter-waveguide-detector junctions. This ability to manipulate the shape of active and passive nanowire cavities provides a new tool for investigating the cavity dynamics of subwavelength structures. Moreover, future advances in assembling the diverse set of existing nanowire building blocks could lead to a novel and versatile photonic circuitry.
In these tests it has been found, quite surprisingly, that one-dimensional (1D) nanostructures can guide light through liquid media. The fact that light can be delivered through these cavities in solution offers a unique application for high dielectric (n≦2) waveguides in fluidic sensing and probing. Waveguiding in liquids is especially important for integrated on-chip chemical analysis and biological spectroscopy in which small excitation and detection volumes are required. Subwavelength nanostructures can be assembled to probe molecules in a fluorescence or absorption scheme, both of which utilize the decaying light field outside of the cavity to induce photon absorption. The waveguide is strongly coupled to emitted photons near the cavity, allowing the generated fluorescence to be directed back to the point of injection. Also, the nanoscale dimensions of the waveguides afford small liquid volumes (on the order of picoliters) to be sensed and presage the way for miniaturized optical spectrometers.
The following discusses building upon the demonstrations of nanowire/ribbon photonic assembly with several illustrative implementations of optical routing between coupled nanowires. First the ability to deliver individual nanosecond light pulses from lasing GaN and ZnO nanowires through a nanoribbon waveguide is shown. It should be appreciated that pulsed light must be transmissible if nanowire photonic devices are to be useful in communications or computing. Simple networks of SnO2 nanoribbons are then used to separate white light and route individual colors based on a short-pass filtering effect. An optical crossbar grid is also described which comprises two pairs of orthogonal nanoribbons which conduct light through abrupt 90° angles and provides a dramatic example of the nature of optical confinement in these subwavelength cavities. The fact that the waveguiding ability of these freestanding, flexible nanowires and nanoribbons survives in liquid media suggests a role for nanowire light delivery in microfluidics and biological applications.
High dielectric subwavelength waveguides have a considerable advantage for confining light in liquids over low dielectric waveguides such as silica-based structures. The low index contrast between the solution (cladding) and silica core (nsilica≈1.45) hinders efficient propagation of the light wave.
As can be seen from
Intuitively, the replacement of air (n=1) with water (n=1.33) on three sides of a nanoribbon should increase its optical loss and hinder waveguiding, especially for longer wavelengths. One would expect a narrowing of the guided spectrum (a blue shift of the cutoff wavelength). Instead, we found that the spectrum broadens to the red and the end emission changes from blue in air to green in water. This surprising result, which seems to suggest that a smaller index profile between core and cladding results in better, not poorer, confinement, is likely a consequence of the smaller difference in refractive index between water and the SiO2 substrate than between air and the substrate. The less anisotropic water-silica cladding shifts the modal power nearer to the center of the nanoribbon and thereby reduces overall radiative loss. Ribbons that were too large to show a cutoff for PL were unaffected by immersion in water.
Ribbon waveguides can also sense molecules, proteins or larger biological entities in solution by means of either an emission or absorption mechanism as mentioned above. In the former, a nanoribbon provides local excitation for fluorophores passing through the cone of scattered light at its output end, and the emission is collected by a fiber or microscope.
As can be seen, blue light (442 nm) launched into the far end of the nanoribbon resulted in strong fluorescence from within the droplet, where the R6G emission mapped out the spatial intensity distribution of the waveguide output as a cone of light (
Another way that 1D nanostructures may be used for optical detection in solution relies on producing an absorption spectrum of molecules located on and near the nanoribbon surface. Absorbance detection, while inherently less sensitive than fluorescence methods, is applicable to a wider range of molecules and avoids the complications of fluorescent tagging. White PL was launched down a long nanoribbon (260 nm×240 nm×540 μm) onto the midpoint at which a droplet of 1 mM R6G (αmax=535 nm) with a volume of approximately 1 pL was deposited (
A third way that subwavelength nanoribbons/wires can be used for chemical/biological sensing relies on the surface enhanced Raman spectroscopic (SERS) effect. Surface-enhanced Raman scattering occurs when an analyte molecule is probed in proximity to a metal surface (usually Cu, Ag or Au) that serves to massively enhance the local electromagnetic field through resonance with the surface plasmons of the metal. The resulting Raman signal of the analyte can be enhanced by a factor of up to 1014, which allows single-molecule sensing in many cases. The nanoribbons/wires described here were fashioned into subwavelength SERS fibers by decorating their surfaces with a high density of silver nanoparticles. By exposing the nanoparticles-coated nanoribbon/wire to an analyte solution while injecting monochromatic light down the nanoribbon/wire, it is possible to detect the SERS signal of the analyte molecule. This concept allows “fingerprint” identification of analyte molecules based on their SERS vibrational signatures, using a subwavelength waveguide for light introduction and confinement.
The devices shown thus far all operate under single pass geometries. Multi-pass structures would increase sampling lengths and ultimately lead to a more sensitive spectrometer.
The figure illustrates that ring shapes can be easily fashioned using our manipulation capabilities to create a subwavelength cavity shape that would sample an analyte repetitively. The glycol droplet (top inset) serves to identify where the analyte would sit in this particular configuration. The PL/dark-field image shows a two nanoribbon device evanescently coupled (arrow 1 denotes the junction), illustrating the first step to design a multi-pass spectrometer based on free-standing 1D nanostructures. The bottom inset was taken after manipulating the end of NR1 into a ring structure (arrow 2 denotes the junction) showing the second step for creating a multi-cycle instrument. Additional work is necessary to fully realize better sensitivity from these advanced designs, but previous results on coupling efficiencies suggest that up to an order of magnitude increase can be obtained from a multi-pass geometry.
It should be appreciated that the fabrication of a practical subwavelength fiber spectrometer as introduced above would benefit from a more controlled flow-cell type microfluidic design in which the sensing nanoribbon/wire is integrated with microfluidic channels for solution introduction. An integrated device using a poly-dimethylsiloxane (PDMS) stamp patterned with flow channels to control analyte flow past an embedded nanoribbon/wire waveguide have been built according to the present invention. With this microfluidic design multiple analyte solutions can be pulsed past a well-defined section of a sensing nanoribbon/wire, permitting reuse of the sensor for biological and other liquid-based monitoring uses.
It should be noted that the techniques and apparatus set forth herein for chemically synthesized 1D semiconductor nanostructures are entirely compatible with existing lithography techniques. State-of-the-art electron beam and other lithography methods currently offer better size control, reproducibility, and processing speeds to produce subwavelength optical probes and spectrometers than the serial approach discussed here. Future experiments will include lithographically defined structures on various support substrates to discern the limits of detection using nanoscale optics.
In terms of present industrial efforts and interests in small volume detection, NanoDrop© Technologies has developed a UV/Vis is spectrometer (ND-1000) based on patented sample retention technology. The instrument is generally used to detect 1 μL to 2 μL nucleic acid aliquots with a sample detection limit of 2 ng/μL (dsDNA). The path length for the Xe flash lamp (220 nm to 750 nm) is held relatively fixed at 1 mm. The major advantages of a subwavelength spectrometer over the commercially available unit is smaller volume size (˜106 times smaller), shorter path lengths (˜10 times shorter), and possibly higher sensitivity with the advanced multi-pass geometries.
The manipulation of optical energy in structures smaller than the wavelength of light is key to the development of integrated photonic devices for computing, communications and sensing. Small groups of freestanding, chemically synthesized nanoribbons and nanowires were fabricated into model structures that illustrate how light is exchanged between subwavelength cavities made of three different semiconductors. The strength of the optical linkages formed when nanowires are brought into contact depends both on their volume of interaction and angle of intersection. Using simple coupling schemes, lasing nanowires can launch coherent pulses of light through nanoribbon waveguides that are up to several millimeters in length. Also, inter-wire coupling losses are low enough to allow light to propagate across several right-angle bends in a grid of crossed nanoribbons. The fraction of the guided wave power traveling outside the nanowire/nanoribbon cavities is utilized to link nanowires through space and to separate colors within multi-ribbon networks. In addition, it was found that nanoribbons function excellently as waveguides in liquid media and provide a unique way to probe molecules in solution or in proximity to the waveguide surface. Our results lay the groundwork for photonic devices based on assemblies of active and passive nanowire elements and presage the use of nanowire waveguides in microfluidics and biology.
SnO2 nanoribbons were synthesized by the chemical vapor transport of SnO at 1100° C. in flowing argon. ZnO nanowires were grown as epitaxial arrays on sapphire substrates by the oxidation of metallic zinc at 800° C., using gold as a catalyst. GaN nanowires were made by the chemical vapor transport of gallium in a NH3/H2 mixture at 900° C., with nickel as the catalyst. The SnO2 nanoribbons were dry transferred en masse to oxidized silicon substrates (600 nm SiO2, Silicon Sense Inc.). A triple-axis micromanipulator tipped with a tungsten probe (˜400 nm tip diameter) was used to remove individual ZnO and GaN nanowires (chosen by their PL spectra) from their growth substrates and then deposit them with the nanoribbons.
Nanoribbons and nanowires were manipulated with the probe under a dark-field microscope. A HeCd laser provided continuous wave (CW) resonant illumination (325 nm), while the fourth-harmonic of a Nd:YAG laser (266 nm, 8 nm, 10 Hz) was used for pulsed pumping. Laser diodes (652 nm and 532 nm) and the HeCd laser (442 nm) supplied visible light for the filtering and fluorescence demonstrations. The lasers were focused to a beam diameter of approximately 50 μm, giving a CW power density of approximately 175 W/cm2 and a pulsed energy density of approximately 10 μJ/cm2. Spectra were acquired with a fiber-coupled spectrometer (gratings at 150 and 1200 grooves/mm, SpectraPro 300i, Roper Scientific) and liquid N2-cooled CCD setup. Black-and-white and color images were recorded with two microscope-mounted CCD cameras (CoolSnap fx and CoolSnap cf, Photometrics).
Many of the nanoribbons/wires described herein operated as single-mode fibers for some of the experimental wavelengths, while others were multi-mode. For reference, the approximate single-mode cutoff diameters of a cylindrical step-index fiber in air are 140 nm (λ=365 nm) and 265 nm (λ=600 nm) for SnO2, 112 nm (λ=365 nm) for GaN, and 140 nm (λ=380 nm) and 220 nm (λ=510 nm) for ZnO.
In the liquid experiments, large droplets (˜5 μL) of water or various alcohols were transferred to the oxide surface by pipette. The solvent droplets were then diced into smaller volumes (as small as 100 fL) and positioned on the surface using the manipulator.
As can be seen,
To demonstrate the routing of continuous wave light, we excited the GaN nanowire with the focused beam of a HeCd laser operating at 325 nm. Band-edge PL from the GaN cavity was channeled through the SnO2 nanoribbon to emerge primarily at its far end. A fraction of the light was also scattered by imperfections along the length of the nanoribbon (i.e., attached particles or macroscopic step edges). Far-field spectra collected from the output end of the nanoribbon (
It should be appreciated that in contrast to their continuous wave emission, the pulsed emission of ZnO and GaN is nearly devoid of visible PL since the defect bands experience no gain. This is experimental verification that coherent optical pulses can be transferred between nanowires and steered hundreds of micrometers from their source. By utilizing high frequency electrical pumping these nanowire laser/waveguide combinations could be used to transduce and shuttle packets of electro-optical information within future computing and communications devices.
In
As can be seen from
The structure was designed with one long channel for light input and seven short output channels that could be monitored simultaneously. As shown in
Due to their high refractive indices (n≧2), the nanoribbons and nanowires discussed here function well as waveguides in water and other liquids. This is a considerable advantage over subwavelength silica waveguides, which cannot efficiently confine visible light in liquids because of a low dielectric contrast (nsilica≈1.45). Waveguiding in liquids is especially important for integrated on-chip chemical analysis and biological spectroscopy in which small excitation and detection volumes are required.
As can be seen, chemically synthesized nanoribbon and nanowire waveguides have two unique and potentially useful features for subwavelength photonics applications. First, nanowires push subwavelength optical fibers beyond silica. The scores of materials that can now be made in nanowire form include active, passive, nonlinear and semiconducting inorganic crystals, as well as a wide variety of polymers. Simultaneous photon, charge carrier and spin manipulation is possible within and between nanowires of different compositions. Also, many of these materials have higher refractive indices than silica-based glasses, permitting light of a given wavelength to be confined within thinner structures for denser integration. This enables waveguiding in liquids and makes it possible to extend subwavelength guiding to telecommunications wavelengths using, for example, approximately 300 nm diameter Si or GaP nanowires. Second, nanowires are freestanding, mechanically flexible elements that can be manipulated on surfaces or used as mobile probes in fluids. As such, they offer a type of versatility difficult to achieve with lithographically-defined structures that are permanently affixed to their substrates.
The disadvantages of nanowire photonics include (i) the paucity of parallel assembly methods for accurately arranging large groups of nanowires into useful structures; (ii) relatively high inter-wire coupling losses compared to monolithic waveguides formed by lithography (coupling losses could be greatly reduced if branched, multi-component nanowires were developed to replace the staggered or crossed nanowire cavities used here); (iii) the lesser geometric perfection of nanowire assemblies relative to the precise shapes and sizes definable with lithography. Geometric imprecision introduces some uncertainty in the resulting light propagation and adds complexity to nanowire experiment/theory comparisons. However, despite these limitations, nanowires and their assemblies provide an important new platform for photonics studies and applications that is only beginning to be investigated.
It will be appreciated that the subwavelength waveguide described herein can be used as a functional element in photonic circuits such as optical networks, optical filters, optical directional couplers, emitter-waveguide-detector junctions, optical probes, optical sensors, optical routers, optical junctions, optical modulators, optical Y-junctions, optical branch networks, Mach-Zehnder interferometers, optical ring oscillators, nanolasers, optical phase shifters, fluidic sensors, fluidic probes, microfluidic devices, optical spectrometers, and optical crossbar grids. Those skilled in the art will also appreciate that the nanostructures described herein can be fabricated and incorporated into devices, systems and structures using various techniques known in the art. Additionally, reference is made to U.S. Pat. No. 6,882,051, entitled “NANOWIRES, NANOSTRUCTURES AND DEVICES FABRICATED THEREFROM” issued on Apr. 19, 2005, which is incorporated herein by reference in its entirety, and to U.S. Patent Application Publication No. US 2004/0131537 A1, entitled “FUNCTIONAL BIMORPH COMPOSITE NANOTAPES AND METHODS OF FABRICATION” published on Jul. 8, 2004, also incorporated herein by reference in its entirety.
As discussed above, subwavelength waveguides can be utilized as optical probes and sensors. In this section a novel optical sensing platform is described that utilizes the evanescent field of a single-crystalline nanoribbon waveguide to optically characterize sub-picoliter volumes of solution, for example performing absorbance, fluorescence and surface enhanced Raman spectroscopy (SERS). Chemical specificity of SERS was obtained by decorating (configuring) the waveguide with metallic nanoparticles, in this case silver nanocubes, to enhance the field around the nanoribbon. The waveguide sensors exhibited excellent chemical resistance and can withstand cleaning cycles in strong acid, making the devices reusable. These results open the path to our engineering of hand-held, photonic sensors capable of detecting and/or identifying chemical species in solution. The validity of this embodiment has been demonstrated by directly exciting molecules (i.e., absorbance and/or fluorescence) with the evanescent field or by scattering light off metallic nanoparticles immersed in the evanescent field to enhance local Raman modes. The nanowire optical sensing platform described herein complements nanowire field effect sensors with an ability to monitor optical attenuation across the wire element. However, the use of photons instead of electrons allows optical spectroscopy to be carried out on the analyte.
To simplify material manufacturing a plurality of optical waveguides were chemically synthesized having a sub-optical diameter, such as with sub-200 nm diameters, to expose a substantial amount of the guided optical intensity to the surrounding matrix. This field was strong enough to optically interrogate molecular species without disrupting the operation of the waveguide.
Tin dioxide (SnO2) nanoribbons were synthesized through a chemical vapor transport process. An alumina boat filled with tin monoxide powder was heated (1100° C.) in an alumina tube under a continuous flow of argon (300 torr) for approximately 2 hours. After removing the boat from the tube furnace, the nanoribbons were deposited on a clean glass substrate for optical characterization (see below). For surface enhanced Raman spectroscopy (SERS) detection, silver nanocrystals were prepared using a modified polyol process in which silver nitrate is reduced in a solution of 1,5-pentanediol (˜190° C.) in the presence of a capping polymer.
These tests were performed with an upright dark-field microscope operating in reflection mode. Monochromatic laser light was focused onto the sample at a 35° angle normal to the substrate. Broadband light (FWHM>200 nm) was generated in the waveguide by exciting the SnO2 nanoribbon with the 325 nm line of a continuous-wave HeCd laser (Melles Griot, Irvine, Calif.). The broad luminescence of the waveguide was used for the absorbance measurements by detecting the guided light with and without the analyte present. Fluorescence and SERS spectra were captured by focusing either a 442 nm (HeCd) or 532 nm (CW diode) laser spot on one of the end facets of the waveguide. The signal was collected by a 50× objective (Nikon, 0.55 NA) and routed through a fiber to a spectrometer (150 grooves/mm grating, SpectraPro 300i, Roper Scientific, Trenton, N.J.) equipped with a liquid nitrogen cooled CCD. Images were captured either with a digital color camera (CoolSnap cf, Photometrics, Tucson, Ariz.) or an EMCCD camera (iXon, Andor Technology, Belfast, Northern Ireland).
Microfluidic flow cells were cast from polydimethylsiloxane (PDMS) using standard lithography. A silicon master containing five parallel channels (channel lengths of 1.5 mm and inter-channel separation of 100 μm) was prepared with 50 μm wide×50 μm deep channels. After casting and curing PDMS on the silicon master, the stamps were removed from the master, cleaned with ethanol and dried. To increase exposure of the analyte to the surface area of the cavity, the waveguides were deposited in a wet PDMS layer (˜5 μm thick) inked on the structured side of the stamp. This also ensured complete sealing of the channels with the quartz substrate after PDMS curing and eliminated capillary leakage between adjacent channels. With the PDMS layer uncured, nanoribbons were placed across the channels using a micromanipulator (Märzhäuser Wetzlar, Wetzlar-Steindorf, Germany) equipped with an etched tungsten probe. Only ribbons with lengths greater than 350 μm were used in the devices. The stamp was then immediately bonded to a quartz substrate, giving the final device architecture shown in
Unless specified, waveguides were chosen for sensing if their single-mode cut-off wavelengths were 550 nm or shorter. Waveguides were screened optically on a silica surface by pumping one of the ends of the nanoribbon with above band gap light (Eg=3.6 eV) from the HeCd laser (3.81 eV), and collecting the waveguided defect emission in the far-field at the opposite end of the ribbon. The empirical cut-off wavelength (˜550 nm) for the waveguides was determined by identifying the 50% transmission point (inflection point) in the collected emission spectrum. Using the waveguide parameter for a cylindrical fiber, the single-mode cut-off wavelength takes on the form μ=dπ/2.405(nco2−ncl2)112 where d is the single-mode cut-off diameter of the waveguide and nco and ncl are the refractive indices of the waveguide core (n=2.1) and cladding (n=1), respectively. Although the nanoribbons have rectangular cross-sections, it was found that this generalized expression yields cut-off diameters on the order of 200 nm, in good agreement (d=150-200 nm) with the dimensions of the ribbons used.
In the following example SnO2 nanoribbons were utilized as the passive optical components in the devices as their high index of refraction allows efficient waveguiding through the microfluidic devices and analytes. In addition, the superb chemical and mechanical properties of these nanoribbons allows them to withstand harsh cleaning conditions.
The first spectroscopic experiment performed with the optical waveguides was the acquisition of an absorption spectrum. This is achieved by generating the featureless defect emission on one side of the sensing channel and collected on the opposing side after it is guided through the analyte (see
As the SnO2 defect emission travels through the sensing region it is attenuated according to Is=Ioexp∈κLc−Io(NAo2/NA2) where ∈ is the molar absorptivity of the analyte (M−1cm−1), κ is the percent power in the evanescent field, L is the sensor length (cm), c is the analyte concentration, and NA and NAo(NA=(nco2−ncl2)1/2) are the numerical apertures of the waveguide with and without the analyte, respectively. This is a simplified expression that neglects chemical enrichment around the SnO2 ribbon, the shape of the cavity and the dispersion of the field penetration; however, it gives estimates ranging from 15% to 30% for the power available in the evanescent field for the waveguide dimensions used here. These results closely correspond to calculations describing the percent power in the core (η) of a step index fiber which uses the function η=1−[5.784exp(−2/V)/V3] where V=πd/λ(nco2−ncl2)1/2 (d is the diameter of the fiber). For example, a 200 nm fiber (nco=2.1) guiding 500 nm light in water (nco=1.33) contains approximately 80% of the power within the core and approximately 20% in the evanescent field. The penetration depth (defined where the field intensity decays to 10% of the core power) is calculated to be about 125 nm, leading to a probe volume of less than 10 fL for a 50 μm path length. With some simple modifications to path length, index of analyte and cavity size, it should be possible to reach <100 attoliter (10−18 L) probe volumes. The detection limit for absorption with a single pass through the analyte is approximately 0.3 mM, but improvements should be possible by utilizing multi-pass ring geometries (see
Since photons emitted near the ribbon surface can be recaptured by the waveguide, the resulting absorption line shape can be skewed. This causes an artificial decrease in the calculated absorption for longer wavelengths (FIG. 24D—top trace). We observe such an artifact only in thinner waveguides (diameters <150 nm), which carry a larger percentage of the guided field intensity in the cladding. For thicker nanoribbons (diameters >200 nm) the number of photons coupled back into the waveguide is reduced, but the absorption linewidth is slightly larger (FIG. 24D—bottom trace). This can be explained by the variation in penetration depth of the evanescent field as a function of wavelength. Longer wavelengths (in this case >525 nm) show an increase in the absorption because they penetrate deeper into the solution. For all ribbons sizes, however, the peak maximum matches that from a commercial photospectrometer to within approximately 2 nm. More accurate peak shapes can be obtained by using expressions that account for the amount of light accessible to the analyte at different wavelengths as well as the photon flux that is recaptured by the waveguide.
To characterize the fluorescent signals produced by the analyte, monochromatic light is launched down the cavity to excite molecules passing through the evanescent field. This mode of detection is analogous to total internal reflection fluorescence (TIRF); however, a more intense optical field resides near the core-cladding interface of a sub-200 nm nanoribbon. As with TIRF, no quenching or surface effects was observed which alter the fluorescence spectra (
Light can be extracted from the waveguide by immersing particles with large dielectric constants in the evanescent field. This becomes important for ultra sensitive detection with a subwavelength fiber because a single particle can scatter a large percentage (5% to 10%) of the confined optical energy. We found that silver nanocubes 50 nm in diameter readily adsorbed to the waveguide surface and intensely scattered waveguided light (
In addition to simple index measurements the immobilized metal particles can be utilized as substrates for surface enhanced Raman spectroscopy, where monochromatic light (532 nm) from the waveguide or from an external source excites surface plasmons. This excitation is responsible for large increases in the Raman cross-section of molecules near or adsorbed to the metal particle, allowing the collection of vibrational signatures from analytes that are otherwise undetectable with traditional Raman techniques. Resonant SERS occurs when both the analyte (in our case a dye molecule) and the metal plasmons are excited by the same wavelength of the light. To demonstrate resonate SERS we exposed the nanoribbons to a 100 μM solution of Rhodamine 6G (αmax=535 nm) after decorating the waveguide surface with Ag nanocubes 114. The SERS signal was probed either directly with a diffraction-limited confocal spot focused on the waveguide (FIG. 26B—SERS R6G Confocal trace) or via waveguided light (FIG. 26B—SERS R6G WG trace). In the former configuration the waveguide acts simply as a supporting scaffold for the SERS-active particles. Here the power at the sample is approximately 2 μW. In the latter configuration the waveguide channels the excitation to the particles. Due to the coupling geometry the power accessible to the particles is less than 100 nW. Performing SERS with large (˜500 nm) and small (˜150 nm) diameter nanoribbons (
To detect a nonresonant SERS signal from the analyte, we modified the surface of the metal with 1-dodecanethiol ligands, which readily assemble into a monolayer on the metal surface. The SERS spectra in
As can be seen, we have demonstrated a novel photonic sensor based on subwavelength nanowires that is capable of detecting molecules in solution by absorbance, fluorescence and SERS. The future of portable all-optical sensors hinges on the provision of cheap, fast, reliable detectors capable of deconvoluting complex mixtures. An imperative step in this process is the addition of chemical specificity to the sensor while simultaneously providing a multiplexed geometry for high-throughput analysis. Device portability will certainly benefit from the advent of on-chip microcavity lasers and the continual efforts of integrating both active and passive optical elements on a single photonic chip. Use of the evanescent field to guide light and perform spectroscopy will undoubtedly play a major role in the design of compact optical sensors. The initial results shown here are promising for the development of on-site analytical experimentation, field detection of biochemical toxins and portable analysis of water contaminants.
Although the description above contains many details, these should not be construed as limiting the scope of the invention but as merely providing illustrations of some of the presently preferred embodiments of this invention. Therefore, it will be appreciated that the scope of the present invention fully encompasses other embodiments which may become obvious to those skilled in the art, and that the scope of the present invention is accordingly to be limited by nothing other than the appended claims, in which reference to an element in the singular is not intended to mean “one and only one” unless explicitly so stated, but rather “one or more.” All structural, chemical, and functional equivalents to the elements of the above-described preferred embodiment that are known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Moreover, it is not necessary for a device or method to address each and every problem sought to be solved by the present invention, for it to be encompassed by the present claims. Furthermore, no element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. No claim element herein is to be construed under the provisions of 35 U.S.C. 112, sixth paragraph, unless the element is expressly recited using the phrase “means for.”
This application claims priority from, and is a 35 U.S.C. § 111(a) continuation of, co-pending PCT international application serial number PCT/US2007/078021, filed on Sep. 10, 2007, incorporated herein by reference in its entirety, which claims priority from U.S. provisional patent application Ser. No. 60/844,015 filed on Sep. 11, 2006, incorporated herein by reference in its entirety. This application is also a continuation-in-part of U.S. patent application Ser. No. 11/559,244 filed on Nov. 13, 2006, incorporated herein by reference in its entirety, which claims priority to U.S. provisional patent application Ser. No. 60/844,015 filed on Sep. 11, 2006. Priority is claimed to each of the foregoing applications. This application is related to PCT Publication No. WO 2008/033763, published on Mar. 20, 2008, incorporated herein by reference in its entirety.
This invention was made with Government support under Contract No. DE-FG02-02ER-46021 awarded by the Department of Energy, Grant No. DE-AC02-05CH11231 awarded by the Department of Energy. The Government has certain rights in this invention.
| Number | Date | Country | |
|---|---|---|---|
| 60844015 | Sep 2006 | US | |
| 60844015 | Sep 2006 | US | |
| 60571416 | May 2004 | US | |
| 60643612 | Jan 2005 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/US2007/078021 | Sep 2007 | US |
| Child | 12402257 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11559244 | Nov 2006 | US |
| Child | PCT/US2007/078021 | US | |
| Parent | PCT/US2005/017029 | May 2005 | US |
| Child | 11559244 | US |
