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Definitions

• An alternative approach involves using semiconductor nanowires as the building blocks for large area electronic and optoelectronic devices.
• a wide range of Group IV, ⁇ i-V and II- VI semiconductor nanowires can be rationally synthesized with tunable chemical composition, physical dimension and electronic properties, see Duan, X., et al. Nanowire Nanoelectronics Assembled from the Bottom-up, in Molecular Nanoelectronics, Reed, M. ed., American Scientific Publisher, New York (2002); Duan, X. and Lieber, C. M., Adv. Mater. 72:298-302 (2000) and Gudiksen, M. S., et al. J. Phys. Chem.B 105:4062-4062 (2001), each of which are incorporated herein, in their entirety, for all purposes.
• the present invention relates to a process for forming a nanowire array and a nanowire array prepared according to the process.
• the process comprises providing a nanowire-material composite, applying a mask comprising a pattern to the nanowire-material composite to form a masked composite; removing a portion of the material from the composite to expose the nanowires embedded in the portion and form an array of exposed nanowires in said nanowire-material composite.
• FIG. 5 is a flow diagram for a process for producing a freestanding nanowire-material composite, according to an embodiment of the present invention.
• FIGS .6 A-6C illustrate a freestanding nanowire-material composite being fabricated on a substrate, according to the process of FIG. 5.
• FIG. 7 is a flow diagram for a process for aligning nanowires on a substrate, according to an embodiment of the present invention.
• FIGS. 8A-8F illustrate nanowires being aligned on a substrate according to the process of FIG. 7.
• FIG. 9 is a flow diagram for a process of producing an electronic substrate using nanowires, according to an embodiment of the present invention.
• FIG. 9 is a flow diagram for a process of producing an electronic substrate using nanowires, according to an embodiment of the present invention.
• FIG. 19A-19E show a nanowire-material composite being processed to form an electronic substrate, according to an embodiment of the present invention.
• FIG. 20 shows a multilayered light-emitting diode having three layers of different nanowire-material composites, according to an embodiment of the present invention.
• FIG. 21 shows an electronic absorption spectrum of various semiconductor nanowires and their respective absorption spectrum.
• FIG. 22 is a flow diagram of steps in the solution-based process of producing a nanowire-material composite, according to an embodiment of the present invention.
• FIG. 23 A is a flow diagram of steps in a process of producing a nanowire array, according to an embodiment of the present invention. [0047] FIG.
• FIG.26 is a flow diagram of steps in an alternative process of producing a high-capacitance capacitor comprising a nanowire-material composite, according to an embodiment of the present invention.
• FIG. 27A is a flow diagram of steps in a process of producing flexible nanofur, according to an embodiment of the present invention.
• FIG. 27B shows exemplary nanofur being produced according to an embodiment of the present invention.
• FIG. 28 A is a flow diagram of steps in a process of producing a tubular nanowire-material composite, according to an embodiment of the present invention.
• FIG. 28B shows an exemplary tubular nanowire-material composite produced according to an embodiment of the present invention.
• FIG.29 A is a flow diagram of steps in an alternative process of producing a tubular nanowire-material composite, according to an embodiment of the present invention.
• FIG. 29B shows an alternative exemplary tubular nanowire-material composite produced according to an embodiment of the present invention.
• nanowire generally refers to any elongated conductive or semiconductive material that includes at least one cross sectional dimension that is less than 500nm, and preferably, less than 100 nm, and has an aspect ratio (length:width) of greater than 10, preferably, greater than 50, and more preferably, greater than 100.
• Examples of such nanowires include semiconductor nanowires as described in Published International Patent Application Nos. WO 02/17362, WO 02/48701, and WO 01/03208, each of which is incorporated in its entirety for all purposes, carbon nanotubes, and other elongated conductive or semiconductive structures of like dimensions.
• the semiconductor may comprise a dopant from a group consisting of: a p-type dopant from Group HI of the periodic table; an h-type dopant from Group V of the periodic table; a p-type dopant selected from a group consisting of: B, Al and In; an n-type dopant selected from a group consisting of: P, As and Sb; a p-type dopant from Group II of the periodic table; a p-type dopant selected from a group consisting of: Mg, Zn, Cd and Hg; a p-type dopant from Group TV of the periodic table; a p-type dopant selected from a group consisting of: C and Si.; or an n-type is selected from a group consisting of: Si, Ge, Sn, S, Se and Te.
• Nanotubes can be formed in combinations/thin films of nanotubes as is described herein for nanowires, alone or in combination with nanowires, to provide the properties and advantages described herein.
• thin film of nanowires of the present invention can be a heterogeneous film, which incorporates semiconductor nanowires and/or nanotubes, and/or nanowires/nanotubes of different composition and/or structural characteristics.
• a heterogeneous film can include nanowires/nanotubes with varying diameters and lengths, and nanotubes and/or nanotubes that are heterostructures having varying characteristics.
• the substrates to which nanowires are grown, attached or processed may further comprise irregular surfaces.
• nanowires may be grown or attached to substrates such as the interior and exterior surfaces of a tube and interior and exterior surfaces of a porous medium, e.g. reticulated macroporous metals, oxides, ceramics and other porous medium.
• substantially aligned or oriented is meant that the longitudinal axes of a majority of nanowires in a collection or population of nanowires is oriented within 30 degrees of a single direction.
• the majority can be considered to be a number of nanowires greater than 50%, in various embodiments, 60%, 75%, 80%, 90%, or other percentage of nanowires can be considered to be a majority that are so oriented, hi certain prefened aspects, the majority of nanowires are oriented within 10 degrees of the desired direction, hi additional embodiments, the majority of nanowires maybe oriented within other numbers or ranges of degrees of the desired direction.
• the present invention is directed to a method of harvesting nanowires and the use of nanowires in systems and devices to improve system and device performance.
• the present invention is directed to the use of nanowires in semiconductor devices.
• multiple nanowires are formed into a high mobility thin film and/or a nanowire- material composite.
• the thin film and/or composite of nanowires is used to harvest nanowires and or in electronic devices to enhance the performance and manufacturability of the devices.
• FIG. 1 shows a close-up view of a thin film of nanowires 100, according to an example embodiment of the present invention.
• Thin film of semiconductor nanowires 100 can be used instead of amorphous silicon or organic thin films in conventional electronic devices to achieve improved device behavior, while allowing for a straightforward and inexpensive manufacturing process.
• the present invention is particularly adapted to making high performance, low cost devices on large and flexible substrates.
• thin film of nanowires 100 as described herein may be formed in a wide range of possible surface areas.
• thin films of nanowires 100 of the present invention can be formed to have functional areas greater than 1 mm 2 , greater than 1 cm 2 , greater than 10 cm 2 , greater than 1 m 2 , and even greater or smaller areas.
• thin film of nanowires 100 includes a plurality of individual nanowires closely located together.
• Thin film of nanowires 100 can have a variety of thickness amounts that are equal to or greater than the thickness of a single nanowire.
• the nanowires of thin film of nanowires 100 are aligned such that their long axes are substantially parallel to each other.
• the nanowires of thin film of nanowires 100 are not aligned, and instead can be oriented in different directions with respect to each other, either randomly or otherwise, lh an alternative embodiment, the nanowires of thin film of nanowires 100 maybe isotropically oriented, so that high mobility is provided in all directions. Note that the nanowires of thin film of nanowires 100 maybe aligned in any manner relative to the direction of electron flow in order to enhance performance as required by a particular application.
• semiconductor device 200 is shown as a transistor in FIG. 2 for illustrative purposes. It would be understood to persons skilled in the relevant art(s) from the teachings herein that thin film of nanowires 100 can be included in semiconductor device types in addition to transistors, including diodes.
• the nanowires of thin film of nanowires 100 are single crystal semiconductor nanowires that span all the way between source electrode 202 and drain electrode 206. Hence, electric carriers can transport through the single crystal nanowires, resulting in high mobility that is virtually impossible to obtain with current amorphous and polysilicon technologies.
• Source electrodes 202, gate electrodes 204, and drain electrodes 206 are formed of a conductive material, such as a metal, alloy, suicide, polysilicon, or the like, including combinations thereof, as would be apparent to a person having ordinary skill in the art.
• the nanowires of thin film of nanowires 100 can be aligned or oriented.
• the nanowires of thin film of nanowires 100 shown in FIG. 2 can be aligned parallel to the length of the channel between source electrode 202 and drain electrode 206, or can be aligned in alternative ways.
• Thin film of nanowires 100 can be formed with a sufficient number of nanowires to provide desired characteristics for semiconductor device 200.
• thin film of nanowires 100 can be formed of a sufficient number or density of nanowires to achieve a desired operational current density or current level desired for the particular application.
• the current level maybe in the nanoamp range, including 2 nanoamps, and greater and lesser current levels.
• thin film of nanowires 100 can be formed to have a current level in the channel of greater than about 10 nanoamps.
• each formed semiconductor device will have a sufficient number of nanowires to carry current at an operational current level.
• the required number of nanowires per unit area can be 1 nanowire, 2 nanowires, and any other greater number of nanowires, including 5, 10, 100 or more.
• a thin film of nanowires 100 can be formed to have asymmetric mobility. For example, this can be accomplished by asymmetrically aligning the nanowires of thin film of nanowires 100, and/or by doping the nanowires in a particular manner. Such asymmetric mobility can be caused to be much greater in a first direction than in a second direction. For example, asymmetric mobilities can be created in the order of 10, 100, 1000, and 10000 times greater in the first direction than in the second direction, or to have any other asymmetric mobility ratio between, greater, or less than these values.
• the nanowires of thin film of nanowires 100 can be doped in various ways to modify performance and for device fabrication.
• the nanowires can be doped prior to inclusion in semiconductor device 200, or after inclusion.
• the nanowires can be doped during growth and synthesis, prior to being formed into a thin film, after being formed into a thin film or when embedded in a composite.
• a thin film of nanowires can be doped after being formed on the substrate.
• a nanowire can be doped differently along portions of its long axis, and can be doped differently from other nanowires in thin film of nanowires 100.
• FIG. 3 A shows a single crystal nanowire 300.
• Nanowire 300 can be doped or undoped.
• Nanowire 300 can be doped uniformly or non-uniformly.
• Single crystal nanowires can be doped into either p- or n-type semiconductors in a fairly controlled way for device fabrication. The type of dopant and dopant concentration in nanowire 300 can be changed to tune the operating characteristics of a device.
• Carrier mobility in nanowire 300, threshold voltage for device switching and off-state cunent flow are all effected by the type and concentration of doping.
• Carrier mobility levels up to 1500 cm 2 /V_s have been shown for single p-type Si (silicon) nanowires, and carrier mobility levels up to 4000 cm /V_s have been shown for n-type InP nanowires.
• FIG. 3C shows a nanowire 320 that is coated with a dielectric material layer 304, according to another type of core-shell structure.
• Dielectric material layer 304 can be chosen from a variety of dielectric materials, such as SiO 2 or Si 3 N 4 .
• the use of dielectric material layer 304 can act as a protective layer in semiconductor device 200, for example, by reducing leakage and preventing electrical shorts.
• the dielectric layer can act as a gate dielectric in a field effect transistor (FET).
• FET field effect transistor
• the dielectric layer can be formed by oxidizing the nanowire, coating the nanowire, or otherwise forming the dielectric layer.
• FIG. 3D shows a nanowire 330 with core 300 and with a doped shell surface layer 302 according to the core-shell structure shown in FIG. 3B.
• Nanowire 330 is also coated with a dielectric material layer 304, as shown in FIG. 3C.
• Shell material 302 should have a bandgap higher than that of core material 300.
• GaAs nanowires are used for core 300
• GaAlAs can be used for doped shell 302.
• Doped shell 302 has thickness less than the diameter of core 300.
• Dielectric layer 304 is not doped and has thickness in the range of about 5 nanometers to about 100 nanometers.
• dopant layer 402 covers a region of substrate 208 substantially localized around thin film of nanowires 100.
• dopant layer 402 applied to semiconductor device 200 can be patterned to have two or more areas doped according to different n- and p-type characteristics.
• dopant layer 402 has a first portion 404 doped with an n-type characteristic, and a second portion 406 doped with a p-type characteristic.
• a p-n junction can be achieved according to a variety of electronic and optoelectronic devices, including light-emitting diodes (LEDs).
• LEDs light-emitting diodes
• a diode can be fabricated as shown in FIG.4B, although the diode would have electrodes 202 and 206, as gate electrode 204 would not be necessary. Doped areas can vary in dopant type, size and position throughout the device as is necessary in the fabrication particular devices.
• dopant layer 402 can be introduced on substrate 208 prior to or after actual fabrication of semiconductor device 200.
• Collections of nanowires manufactured with these materials are useful building blocks for high performance electronics.
• a collection of nanowires orientated in substantially the same direction will have a high mobility value.
• nanowires can be flexibly processed in solution to allow for inexpensive manufacture. Collections of nanowires can be easily assembled onto any type of substrate from solution to achieve a thin film of nanowires.
• a thin film of nanowires used in a semiconductor device can be formed to include 2, 5, 10, 100, and any other number of nanowires between or greater than these amounts, for use in high performance electronics.
• Nanowires can also be used to make high performance composite materials when combined with polymers/materials such as organic semiconductor materials, which can be flexibly spin-cast on any type of substrate. Nanowire/polymer composites can provide properties superior to a pure polymer materials. Further detail on nanowire/polymer composites is provided below.
• collections or thin films of nanowires can be aligned into being substantially parallel to each other, or can be left non-aligned or random.
• Non-aligned collections or thin films of nanowires provide electronic properties comparable or superior to polysilicon materials, which typically have mobility values in the range of 1-10 cmVVs.
• Aligned collections or thin films of nanowires provide for materials having performance comparable or superior to single crystal materials. Furthermore, collections or thin films of nanowires that include aligned ballistic nanowires (e.g., core-shell nanowires as shown in FIG. 3B) can provide dramatically improved performance over single crystal materials.
• aligned ballistic nanowires e.g., core-shell nanowires as shown in FIG. 3B
• Aligned and non-aligned, and composite and non-composite thin films of nanowires can be produced in a variety of ways, according to the present invention.
• Example embodiments for the assembly and production of these types of thin films of nanowires are provided as follows.
• Randomly oriented thin films of nanowires can be obtained in a variety of ways. For example, nanowires can be dispersed or suspended into a suitable solution. The nanowires can then be deposited onto a desired substrate using spin-casting, drop-and-dry, flood-and-dry, or dip-and-dry approaches. These processes can be undertaken multiple times to ensure a high degree of coverage. Randomly oriented thin films of nanowires/polymer composites can be produced in a similar way, providing that the solution in which the nanowires are dispersed is a polymer solution.
• Aligned thin films of nanowires/polymer composites can be obtained using these techniques, followed by a spin casting of the desired polymer onto the created thin film of nanowires.
• nanowires may be deposited in a liquid polymer solution, alignment can then be performed according to one of these or other alignment processes, and the aligned nanowires can then be cured (e.g., UV cured, crosslinked, etc.).
• An aligned thin film of nanowires/polymer composite can also be obtained by mechanically stretching a randomly oriented thin film of nanowires/polymer composite.
• Thin films of nanowires can be formed on virtually any substrate type, including silicon, glass, quartz, polymeric, and any other substrate type describe herein or otherwise known.
• the substrate can be large area or small area, and can be rigid or flexible, such as a flexible plastic or thin film substrate type.
• the substrate can be opaque or transparent, and can be made from a conductive, semiconductive, or a non-conductive material.
• Nanowire film contacts including sources, drains, and gates, for example, can be patterned on a substrate using standard photolithography, ink-jet printing, or micro-contact printing processes, for example, or by other processes.
• a dielectric layer can be applied to a thin film of nanowires on a substrate to electrically insulate gate contacts, for example.
• These materials can be applied to nanowires by gas-phase deposition processes, including, but not limited to, chemical vapor deposition (CVD), plasma assisted chemical vapor deposition (PACVD) and physical vapor deposition (PVD); solution phase over-coating or simply by spin-coating the appropriate precursor onto the substrate.
• CVD chemical vapor deposition
• PVD plasma assisted chemical vapor deposition
• PVD physical vapor deposition
• solution phase over-coating or simply by spin-coating the appropriate precursor onto the substrate.
• Other known techniques can be employed, for example, sputtering and others.
• Such a deposition of a dielectric layer on a substrate may not be necessary if the nanowires are insulated by their own dielectric layer.
• nanowire films can be patterned on a substrate using various processes, including lithography techniques. Deposition and patterning of thin film of nanowires can be done simultaneously using various processes, such as ink-jet printing or micro-contact printing methods.
• gates 204, sources 202, and drains 206 shown in FIG.2 can be patterned simultaneously with each other, or at different times. They can be all be patterned prior to deposition of the thin film of nanowires 100, or afterwards. Sources 202 and drains 206 can be patterned prior to deposition of the thin film of nanowires 100, while gates 204 are patterned afterwards. Alternatively, gates 204 can be patterned prior to deposition of the thin film of nanowires 100, wlender sources 202 and drains 206 are patterned afterwards. Either of sources 202 and drains 206 can also be patterned prior to deposition of the thin film of nanowires 100, while the other is patterned afterwards.
• more than one layer of a thin film of nanowires can be applied to a substrate in a given area.
• the multiple layers can allow for greater electrical conductivity, and can be used to modify electrical characteristics of a respective semiconductor device.
• the multiple layers can be similar, or different from each other.
• two or more layers of thin films of nanowires having nanowires aligned in different directions, doped differently, and/or differently insulated, can be used in a particular semiconductor device.
• a contact area of a particular semiconductor device can be coupled to any one or more of the layers of a multiple layer thin film of nanowires.
• a thin film of nanowires can be formed as a monolayer of nanowires, a sub- monolayer of nanowires, and greater than a monolayer of nanowires, as desired.
• FIG.5 shows a flowchart 500 showing example steps for producing a nanowire-material composite, according to an embodiment of the present invention.
• FIGS. 6A-6C show example implementations of the steps of FIG. 5.
• Flowchart 500 begins with step 502.
• step 502 a substrate having nanowires attached to a portion of at least one surface is provided.
• step 504 a material is deposited over the portion to form the nanowire-material composite.
• Flowchart 500 optionally further includes step 506.
• the nanowire-material composite is separated from the substrate to form a freestanding nanowire-material composite.
• FIG. 6A shows an example implementation of step 502.
• a substrate 602 is provided having nanowires 606 attached to a portion 604.
• Portion 604 can be all or less than an entire area of a surface of substrate 602. It is understood by one of ordinary skill in the art that nanowires can be prepared by a variety of methods. Nanowires for use in the present invention can be prepared by any method known in the art. Particular methods are exemplified in U.S. Patent No. 5,997,832, U.S. Patent No. 6,036,774 and published U.S. Patent Appl. No. 20030089899, all of which are incorporated herein by reference in their entireties for all purposes. The nanowires are prepared on a substrate and attached to the substrate.
• the gold, or other material, nanoparticles are deposited on the interior and/or exterior surfaces of a three dimensional object, such as an object made from a macroporous metal and/or oxide.
• a three dimensional object such as an object made from a macroporous metal and/or oxide.
• the object is immersed in a solution comprising the nanoparticles and the nanoparticles adhere or bind to the surface of the object.
• the nanoparticles bind to the surface by static charge.
• FIG. 6B shows an example implementation of step 504.
• a material 608 is deposited over portion 604 to form a nanowire-material composite.
• the material for use as material 608 in the present invention can be any material capable of forming a composite with nanowires 606.
• the particular choice of material is dependent on the intended application of the nanowires and the nanowire-material composite.
• Particular examples include but are not limited to polymeric materials, glasses and ceramics.
• Prefened materials for materials 608 include materials that can be separated from the substrate and form freestanding nanowire-material composites.
• Prefened materials include flexible materials, including, but not limited to polymers and resins.
• prefened materials for materials 608 are capable of adhering to and supporting the nanowires 'while the nanowire-material composite is separated from the substrate such that the nanowires are detached from the substrate and become embedded in the composite intact and undamaged from the separation.
• suitable polymers for material 608 include, but are not limited to an elastomer, thennoplastic or thermosetting resin.
• polymers for use include oligomers, which includes, but is not limited to monomers, dimers, trimers, tetramers, pentamers, hexamers, heptamers, octamers, nonamers, decamers, undecamers, and dodecamers; branched, hyperbranched, dendritic and other non-linear structural forms of polymers; prepolymers such as phenoxy and epoxy prepolymers; networked polymers such as inte enetrating and semi-inte ⁇ enetrating network polymers; homopolymers, copolymers, terpolymers and other copolymers including random, statistical, alternating, block and graft copolymers and blends of two or more different polymers.
• the nanowire-material composite shown in FIG.6B optionally comprises additives to modify the properties of the material 608.
• an additive is a plasticizer.
• Plasticizer is used herein to mean any material that can decrease the flexural modulus of a polymer.
• the plasticizer may influence the morphology of the polymer and may affect the melting temperature and glass transition temperature.
• plasticizers include, but are not limited to: small organic and inorganic molecules, oligomers and small molecular weight polymers (those having molecular weight less than about 50,000), highly-branched polymers and dendrimers.
• Specific examples include: monomeric carbonamides and sulfonamides, phenolic compounds, cyclic ketones, mixtures of phenols and esters, sulfonated esters or amides, N-alkylolarylsulfonamides, selected aliphatic diols, phosphite esters of alcohols, phthalate esters such as diethyl phthalate, dihexyl phthalate, dioctyl phthalate, didecyl phthalate, di(2-ethylhexy) phthalate and diisononyl phthalate; alcohols such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, oligomers of ethylene glycol; 2-ethylhexanol, isononyl alcohol and isodecyl alcohol, sorbitol and mannitol; ethers such as oligomers of polyethylene glycol, including PEG-500, PEG 1000
• additives for use in the invention include but are not limited to fillers, antioxidants, colorants, initiators, crosslinking and curing agents, impact strength modifiers, heat and ultraviolet stabilizers, flame retardants, antistatic agents, electrical and thermal conductivity modifiers, drugs and biologically active compounds and molecules.
• material 608 is deposited over portion 604 using any method that allows for the controlled deposition of material 608. It is understood by one of ordinary skill in the art that many different methods of deposition are available and the choice of method depends on the type of material 608 used and the desired final properties of the nanowire-material composite. Methods for depositing material 608 include, but are not limited to drop-casting, spin-coating, dip-coating, langmiur-blodgett techniques and blade coating. It is understood by one of ordinary skill in the art that material 608 can be deposited in a variety of forms. The forms include, for example, but are not limited to a neat liquid or melt and as a solution in a suitable solvent.
• Suitable solvents include aqueous and non- aqueous solvents.
• material 608 is deposited unidirectionally such that nanowires 606 are substantially aligned parallel to their long axis as a result of the deposition.
• material 608 is made to flow over nanowires 606 such that nanowires 606 are substantially aligned parallel to the direction of flow.
• material 608 is deposited by blade coating by moving substrate 602 and/or the blade in such a way that results in the substantial alignment of nanowires 606 parallel to their long axis and parallel to the direction of movement.
• substrate 602 having nanowires 606 attached thereon is dipped into a bath of material 608 or a langmuir-blodgett trough.
• Substrate 602 is removed such that nanowires 606 are substantially aligned parallel to their long axis and parallel to the direction that substrate 602 is removed from the bath.
• alternative means of aligning the nanowires during deposition of material 608 include, for example, electric and/or magnetic field alignment.
• material 608 is optionally further processed.
• a variety of processing steps can be performed, depending on the desired final properties of the nanowire-material composite. Processing steps include, but are not limited to hardening, curing, cross-linking, polymerizing, photo polymerizing, melting, crystallizing, oxidizing and reducing.
• material 608 is deposited over portion 604 as a polymer solution.
• polymer solutions for use in the present invention include, but are not limited to polystyrene, poly(methylmethacrylate), nylon-6 or poly(ethylene terephthalate) dissolved in toluene; polyethylene or polypropylene dissolved in dichloromethane; and poly(lactic acid) dissolved in water.
• Removing the solvent from material 608 hardens material 608 and forms the nanowire-material composite.
• the solvent can be removed by any method known to one of ordinary skill in the art, for example, by evaporating the solvent.
• material 608 is deposited over portion 604, as a mixture of at least one or more prepolymers. Processing the mixture by polymerizing the prepolymers forms the material-nanowire composite.
• low-molecular weight polyurethane oligomers are deposited as a neat film and heat-cured to form a high-molecular weight elastomeric polyurethane composite having nanowires embedded therein.
• a mixture of two or more epoxy prepolymers is deposited over the nanowires as a neat film, or two or more epoxy prepolymers are deposited separately and admixed on the substrate to form an epoxy polymer.
• material 608 is deposited on the interior surface(s) of an inegular object. Any method of deposition can be used.
• a substrate can comprise reticulated macroporous metals such as aluminum, that have nanowires attached on the interior of the pores of the metal.
• the macroporous substrate is then impregnated or injected with material 608.
• material 608 covers the portions of the substrate to which the nanowires are attached. The material covering the nanowires can optionally be further processed, as described herein.
• the nanowire-material composite after forming the nanowire-material composite, it is optionally further processed while attached to substrate 602. Alternatively, the nanowire-material composite is separated from substrate 602 before optional further processing. Optional further processing steps include, but are not limited to, planarization, patterning, separating the patterned nanowire-material composite from substrate 602, doping, metallization and further device fabrication steps.
• FIG. 6C shows an example implementation of step 506. Referring to FIG. 6C, after forming the nanowire-material composite the composite is separated from substrate 602 to form freestanding nanowire-material composite 610. It is understood that a variety of methods are available to separate nanowire-material composite from substrate 602.
• the method of separation results in a freestanding nanowire-material composite 610, wherein the nanowires are detached from substrate 602 and are embedded in material 608 intact, without being damaged during separation.
• Methods of separating nanowire-material composite 610from substrate 602 for use in the present invention include, but are not limited to the three following examples.
• nanowire-material composite 610 is physically lifted from substrate 602.
• the term blade is used herein to refer to any sharp-edged object capable of lifting composite 610 off of substrate 602 and detaching nanowires 606 from substrate 602 without damaging nanowires 606.
• the blade is used to separate the entire composite 610 from the substrate, or alternatively, the blade is used to separate a first portion of composite 610 from substrate 602.
• a second portion of composite 610 is mechanically separated from substrate 602 or lifted from the substrate by hand or hand-held apparatus.
• substrate 602 is etched away from nanowire-material composite 610.
• the method of etching substrate 602 depends on the material of substrate 602. For example, plasma etching is used to etch away a silicon wafer substrate from a nanowire-material composite 610.
• the silicon wafer substrate is chemically etched away from composite 610 using a suitable etching agent, such as hydrofluoric acid and an oxidizing agent such as HNO 3 or H 2 SO .
• suitable etching agent such as hydrofluoric acid and an oxidizing agent such as HNO 3 or H 2 SO .
• Other chemical etching agents include, but are not limited to, KOH and XeF 2 .
• Metal substrates can be electrochemically etched away from nanowire-material composite 610. Polymeric substrates can be separated from nanowire-material composite 610 by dissolving the substrate in a suitable fluid that does not dissolve nanowire-material composite 610.
• a parting layer is used to separate the nanowire-material composite 610 from substrate 602.
• the term parting layer is used herein to refer to any agent capable of facilitating the separation of nanowire-material composite 610 from substrate 602.
• An example of a parting layer for use in the present invention includes, but is not limited to, a chemically removable parting layer between substrate 602 and nanowire-material composite 610.
• substrate 602 is first coated and/or covered on at least one surface with a chemically removable parting layer.
• Nanowires 606 are grown on the chemically removable parting layer.
• Material 608 is deposited over nanowires 606 to form nanowire-material composite 610.
• the nanowire-material composite 610 is separated from substrate 602 by dissolving the chemically removable layer in a suitable solvent.
• the suitable solvent is capable of dissolving the chemically removable layer but does not dissolve nanowire-material composite 610 or the substrate.
• the parting layer can also be a photoremovable layer, in which ultraviolet or other suitable wavelengths of light, or other suitable electromagnetic energy, are used to remove the parting layer and separate nanowire-material composite 610 from substrate 602.
• An example of a photoremovable layer is a substance that breaks down and disintegrates in the presence of ultraviolet light, making it easily removed by washing with a suitable fluid.
• the freestanding nanowire-material composite 610 is collected in sheets and can be stored for later use. Flexible nanowire-material composites 610 are optionally rolled and stored for later use or for further optional processing.
• the freestanding nanowire-material composite 610 is further optionally processed.
• material 608 is separated from nanowires 606 and nanowires 606 are harvested for further processing.
• Any method capable of separating material 608 from nanowires 606 can be used in the present invention. Specific examples include, but are not limited to dissolving material 608 in a suitable solvent, heating the nanowire-material composite 610 to a temperature sufficient to incinerate material 608, and etching away the material. Suitable solvents include those fluids that dissolve material 608 while leaving nanowires 606 intact and undamaged. The solvent contacts nanowire-material composite 610, dissolves material 608 and nanowires 606 are collected by some means, for example filtration.
• FIG. 7 shows a flowchart 700 showing example steps for depositing oriented nanowires according to an embodiment of the present invention.
• FIGS. 8A-8F show example implementations of the steps of FIG. 7.
• Flowchart 700 begins with step 702.
• h step 702 a first substrate having nanowires attached to a portion of at least one surface is provided, wherein each nanowire has a first end attached to said portion.
• the nanowires are oriented substantially perpendicular to the surface of the substrate.
• step 704 a material is deposited over the portion to form a nanowire-material composite, hi step 706, the nanowire-material composite is patterned to form a patterned composite. In step 708, the patterned composite is separated from the first substrate. In step 710, the patterned composite is applied to a second substrate such that the nanowires are aligned substantially parallel to the second substrate.
• FIG. 8 A shows an example implementation of step 702.
• nanowires 804 are grown on a first substrate 802.
• nanowires 804 are grown perpendicular to the surface of substrate 802. Any method known in the art can be used to grow nanowires perpendicular to a surface, including, for example, the methods described in Published U.S. Patent Appl. No. 20020172820, which is incorporated herein, in its entirety, for all purposes.
• nanowires 804 are grown to a length 811, which can be in the range of about 10 to about 20 microns although the invention is not limited to this range.
• nanowires 804 are grown such that a portion 805 of each nanowire at an end that is attached to substrate 802 is doped.
• Methods for doping nanowires are well known in the art. Any method of doping can be used during growth that results in portion 805, which is attached to the substrate, being doped.
• FIG. 8B shows an example implementation of step 704.
• material is deposited over the portion to form a nanowire-material composite 806.
• the material is deposited over the nanowires, to a height 807 such that the nanowires are covered by the material and embedded in nanowire-material composite 806.
• any method known in the art for depositing the material over the nanowires can be used in the present invention.
• the material is optionally processed to form nanowire-material composite 806.
• Optional processing steps are discussed above.
• the material is polymerized or cross-linked in a curing and/or hardening step.
• the material is photopolymerized and/or heat-cured to form nanowire-material composite 806.
• FIG. 8C shows an example implementation of step 706.
• the nanowire-material composite is patterned to form patterned composite 808.
• the nanowire-material composite is patterned into a plurality of patterned composites 808.
• the nanowire-material composite can be patterned into any shape.
• the nanowire-material composite is patterned into a plurality of substantially rectangular blocks 808.
• Blocks 808 can be patterned to have any dimensions, depending on the particular application.
• a height 809 of block 808 is about equal to or greater than the length of the nanowires, which would result in the nanowires being completely embedded in each composite block.
• the nanowires are not completely embedded in block 808, such that the height 809 of the block 808 is less than the length, 811, of the nanowires, leaving a portion 813 not embedded in block 808.
• the height 809 of the blocks 808 can range from about 2 microns to about 50 microns, although the invention is not limited to this range.
• the blocks have a height of less than about 10 microns.
• the plurality of blocks can be uniform in dimensions, or alternatively, the blocks are patterned such that each block, or each group of blocks, has different dimensions. Methods for patterning materials are well known in the art. Any method that results in a well-defined pattern of nanowire- material composite can be used in the present invention.
• a method of patterning for use in the present invention includes, but is not limited to, lithographic patterning, including, but not limited to, photolithography and soft lithography.
• the method of patterning can be reactive ion etching.
• etching in accordance with the invention include, but are not limited to, ions of SF 6 , CF , CHF 3 , CC1 4 , CC1 2 F 2 , Cl 2 , O 2 , H 2 and Ar.
• FIG. 8D shows an example implementation of step 708.
• the patterned blocks 808 are separated from substrate 802. As described above, any method of separation can be used.
• the blocks, once separated, form freestanding nanowire-material blocks 810, and can be stored for later use and further optional processing.
• the blocks are further processed on a second substrate.
• FIG. 8E shows an example implementation of step 710.
• freestanding nanowire-material blocks 810 are laminated to a second substrate 814 such that the nanowires are substantially parallel to the surface of the second substrate.
• a plurality of nanowire-material blocks 810 can be laminated on substrate 814 in a predetermined pattern.
• blocks 810 are areanged on substrate 814 in no pattern or in a random pattern.
• Any method known to one of ordinary skill in the art can be used to laminate blocks 810 to the second substrate 814. The choice of method depends on factors such as the material in block 810 and the type of substrate 814.
• blocks 810 can be designed to adhere to substrate 814 through covalent and/or non-covalent bonds.
• composite blocks 814 can be made from a pressure-sensitive adhesive polymer that adheres to substrate 814 when blocks 810 are arranged on its surface and pressure is applied.
• a separate adhesive canbe used to laminate blocks 810 to substrate 814.
• Adhesives are well known in the art and the choice of adhesive depends on the particular application and the material of block 810 and substrate 814.
• blocks 810 canbe laminated to substrate 814 via covalent chemical bonds. Any method of producing the covalent chemical bond can be used.
• the covalent chemical bond can be a siloxane bond.
• a reaction between hydroxyl groups and halosilanes can be used.
• FIG. 8F shows an example implementation of an optional further processing step.
• the nanowire-material blocks are optionally planarized to form planarized blocks 814 and 816.
• all nanowire-material blocks laminated to the second substrate are planarized to the same height.
• a first plurality of nanowire-material blocks 814 are planarized to a first height and a second plurality of nanowire-material blocks 816 are planarized to a second height.
• the nanowire-material blocks are planarized individually to different heights, further embodiments, one or more nanowire-material blocks laminated to the second substrate are not planarized. Any method known to one of ordinary skill in the art can be used to planarize the nanowire-material blocks.
• oxygen plasma is used to planarize the nanowire-material blocks.
• Planarization removes material from the nanowire-material composite.
• the planarization exposes at least one surface of at least one nanowire.
• the planarization removes all the material from the nanowire- material composite and exposes the nanowires that were embedded in the composite.
• nanowire-material blocks can be optionally detached from the substrate after a first surface of at least one nanowire is exposed. The detached block can then be turned over and re-attached to the substrate and further planarized to expose all other surfaces of the nanowires.
• planarization can remove material and yet not expose any surface of the nanowires.
• the planarization results in a plurality of blocks of exposed nanowires that are patterned on a surface of a substrate.
• the exposed nanowires are optionally further processed to produce electronic devices.
• Optional further processing steps include, but are not limited to coating with a dielectric layer, doping, patterning, planarization, metallization and further device fabrication steps.
• the nanowire-material blocks can be planarized on the second substrate to remove the material from the block.
• a thin film of nanowires is thereby formed on the second substrate having nanowires aligned substantially parallel to the second substrate, with a sufficient density to achieve an operational cunent level.
• a plurality of semiconductor device regions can be defined in the thin film of nanowires. Contacts are formed at the semiconductor device regions to thereby provide electrical connectivity to the plurality of semiconductor devices.
• FIGS. 14A and FIG. 14B show an example implementation of step 1002.
• FIG. 14A shows apian view of dielectric layer 1402 deposited on substrate 1108 and patterned nanowire-material composite 1302.
• FIG. 14B shows a side view of dielectric layer 1402 covering patterned nanowire-material composite 1302, embedded and exposed nanowires 1104, material 1106 and substrate 1108.
• Dielectric layer 1402 can be deposited using any process known in the art, including for example, drop casting, spin-coating or blade coating of polymeric, oxide or any other dielectrics.
• Polymer dielectrics for use in the present invention include any polymers, including for example, polyimides, fluorinated polyimides, polybenzimidazoles, and others.
• FIGS. 18A and 18B show an example implementation of step 908.
• the semiconductor device regions are metallized to form electrical connectivity to the device regions.
• FIG. 18 A shows a plan view of metallized semiconductor device regions 1802, 1804 and 1806, which form source, gate and drain transistor electrodes respectively.
• FIG. 18B shows a side view of regions 1802, 1804 and 1806.
• Metallization can be carried out using any method known in the art.
• the semiconductor device regions are metallized by e-beam evaporation.
• the source and drain electrodes are formed whereby the nanowires form channels having a length between respective ones of the source and drain electrodes, and the nanowires are aligned approximately parallel to an axis between the source and drain contacts.
• the gate electrode is formed on the surface of the nanowire-material composite such that the distance between the gate and the nanowires is 5 nanometers or less, 10 nanometers or less, 50 nanometers or less, or 100 nanometers or less.
• FIG. 29B shows examples of the implementation of flowchart 2900.
• Nanowire-material composite 2950 comprises material 2952 and nanowires 2954 embedded in material 2952 and oriented perpendicular to the surface of the composite.
• Composite strips 2960 show example implementation of step 2904.
• Rolled and bonded composite strips form tubular composites 2970, showing example implementation of step 2906.
• Bonded area 2972 attaches the ends of the composite strip 2960 to form the tubular shape.
• An example implementation of 2908 is shown by tubular composite 2980.
• Tubular composite 2980 comprises nanowires 2954 having a portion 2982 exposed in the inner portion of tubular composite 2980.
• FIG. 32 is a SEM image of an example resulting nanowire-material composite, wherein the nanowires are randomly oriented and the material comprises poly(ethyleneoxide).

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