The present invention relates to a sensor device for detecting small and nanoscale vibrations and accelerations.
The present invention relates to a composition of matter useful structures and configures therefore for forming sensors having an ultra-high sensitivity to acceleration, deformation, vibration and the like physical disturbances.
Prior methods of sensing small mechanical movements, vibration or acceleration generally deploy micro-electrical mechanical systems (MEMS) type devices. Such devices can be fabricated in part on silicon wafers extending technology developed for semiconductor microelectronic processing. The current generation of such sensors needs power, which increases their size and limits the life span. There is a continuing effort to increase the sensitivity of such devices, reduce their size and power consumption to expand their deployment to a wide range of engineering, industrial, aerospace and medical applications. It is particularly desirable to achieve a level of sensor miniaturization to be able to implantable such sensor devices into structures or operating equipment without disturbing operation or taking space.
Ideally, it would be desirable to have sensors that can detect motion on a molecular scale level, without interfering with molecular scale processes. For example, many biological processes occur on a cellular level and are inherently nanoscale. The failure of structures and engineering materials initiates as a nanoscale process.
It is therefore an objective of the present invention to provide sensor devices, capable of sensitivity in the detection of force, acceleration and vibration.
It is a further object of the present invention to provide such sensors that are capable of greater and nanoscale miniaturization than current devices.
It is still another objective of the present invention to provide such miniature, highly sensitive sensor devices that can be manufactured inexpensively a high yields.
In order to detect the smallest movements or vibrations it would be desirable to deploy sensors having nano sized functional element that wherein the changes in the sensor properties would be readily measurable on a macroscopic level for high reliability and facile integration with electronic and instruments. For example, it would be desirable that the state of the sensor device could be read continuously by very low power electrical or optical measurements.
Such a nano sized sensor could conceivably be integrated with other items of manufacture or used in the human body yet without interfering with function. Indeed a nanoscale sensor element would have to be able to respond to affine deformation on a nanoscale to enable nanoscale devices.
Ideally, nanoscale sensor element that can be deposited by thin film deposition methods generally compatible with semiconductor type processing steps used to manufacture MEMS and nanoscale device.
The above an other advantages and objects have been accomplished by the invention of a nano-sensor that comprising a non-rigid substrate, a columnar spacer disposed on said non-rigid substrate, an array of particles bonded to said substrate via said spacer wherein at least one column is connected to each particle, whereby deformation of said non-rigid substrates results in a perturbation to the distribution of the nano-particles in said array to produce a measure change in the aggregate physical property of said array.
In still other and preferred embodiments of the invention, the columnar spacer is a molecular species bond to the substrate and the particles are nanospheres. The use of conductive nanospheres allows a relatively small perturbation to the array to be measured by electrical continuity across the device.
In other embodiments, conductive nanoparticles are disposed as an substantially ordered array by a polymeric spacer on a non-rigid substrate.
In additional embodiments of the invention the aforementioned nanosensor element are portion of a microelectromechanical (MEMS) system that deploys one or more cantilevered beams to detect acceleration and/or vibration. The cantilevered beams are in effect the substrate and hence by deform in response to acceleration and/or vibration thus disturbing the conductive nanoparticles disposed in the ordered array above the substrate. The disturbance of the conductive nanoparticles result in a measurable change in resistance between electrodes placed at on end of the beam.
The above and other objects, effects, features, and advantages of the present invention will become more apparent from the following description of the embodiments thereof taken in conjunction with the accompanying drawings.
Referring to
In accordance with the present invention, a nanoscale device 100 is constructed on a non-rigid substrate 110. As shown in
In accordance with another aspect of the present invention, as illustrated in
The thickness of the polymer spacer is generally at least twice the diameter of the nanoparticles, or about 40 to 200 nm. Attachment of the nanoparticle to outer surface 220a of the polymer layer can be by covalent or ionic bonds. Examples of useful polymers for spacer 220 are both homopolymer and co-polymer, such as PDMS, PMMA, HEMA, cellulose, Azlactone polymers, polystyrene, polystyrene sulfonate, polydimethyl-diallyl-ammonium chloride (PDMDA), polyethylene imine, polyacrylic acid and polylysine. Polymers with azlactone functional groups are particularly desired because an azlactone group at the surface will readily react with available primary amines to produce a highly stable covalent bond. Such polymers include poly(2-vinyl-4,4-dimethylazlactone-co-acrylamide-co-ethylene dimethacrylate). Another preferred polymer spacer of layer 220 is polylysine as negatively charged nanoparticles can be bound to the surface 220a through electrostatic interactions with the pendent amine groups. The polylysine can be linear, branched, hyper branched, cross-linked or dendritic, so long as it can be readily deposited as a thin, smooth layer on an underlying substrate. A convenient form of polylysine is a 0.5% aqueous solution available from Sigma Chemical Company.
It should also be appreciated that with respect to the embodiments of
In order to enable the operative principles discussed with respect to
Preferred embodiments of the examples of
Gold nanoparticles can be made by first dissolving 10 mg HAuCl4 in 98 ml deionized water. While this solution is vigorously refluxing, with stirring or other agitation, 2 ml of a solution of 100 mg of trisodium citrate solution in 10 ml deionized water is rapidly injected to disperse uniformly. Continuing the reflux and stirring for about a 1 hour will produce a clear liquid with a red color. Thereafter, heating is stopped while stirring continues until the red liquid reaches room temperature.
As gold nanoparticles functionalized with a single reactive group are commercially available, they can be readily attached to any of the columnar species or thin polymer layer described herein having a complimentary, that is co-reactive group on the outer surface. For example, Mono-Sulfo-NHS-“NANOGOLD”™ is a 1.4 nm gold nanoparticle with a single reactive group, a sulfo-N-hydroxysuccinimide ester (sulfo-NHS) that reacts with primary amines under mild conditions (circa pH 7.5 to 8.2) (Available from Nanoprobes, Incorporated: 95 Horse Block Road, Yaphank, N.Y. 11980-9710, USA). An array of Mono-Sulfo-NHS-“NANOGOLD”™ particles are readily attached to any amine terminated columnar spacer by incubation of the substrate with the Mono-Sulfo-NHS-“NANOGOLD”™ for 2 hours at room temperature. The substrate is then washed and dried to remove excess “NANOGOLD”™ reagent.
It should be appreciated that alternative ways of depositing the columnar spacers includes bonding a non-conductive columnar spacer produced by self-assembled monolayer (SAM) to the substrate. Such a SAM may consist substantially of —(—CH2-)-, liquid crystal molecules and the like. Further details on these and other methods of binding micro and nano sized metallic particles to substrates are disclosed in U.S. Pat. No. 6,242,264 (to Natan, et al., issued Jun. 5, 2001 for “Self-assembled metal colloid monolayers having size and density gradients”), which is incorporated herein by reference.
In alternative embodiments, the particle or preferred nanoparticles need not be covalently bound to the column or the thin polymer layer. For example, nanoparticles may also be attached to the non-conductive spacer by ionic bonding. For example, an amine group on the top of the column and a citrate functionalized nanoparticle. Alternatively, depending on the threshold of force measurement desired, it is possible use larger particles and form the columnar structure by lithographically etching or molding spacer having micro or possibly nano-dimensions. In such cases, it is possible that the substrate and spacer layer, the collection of columns 120 are formed out of a single monolith, rather than a layered material.
When the initially deposited nanoparticles have a diameter substantially less than the diameter of the columnar molecule that acts as a spacer, it is desirable in an additional step to grow the nanoparticles of gold. It is also desirable to grow or enlarge the as deposited nanoparticles when the columnar molecules have a spacing that is substantially larger than the nanoparticles diameter. It is also desirable to grow the initially deposited conductive nanoparticle when they are not deposited on the thin polymer layer at a insufficient density to form a conductive array. In a preferred embodiment, the initially deposited conductive nanoparticles have a diameter of about 1.4 nm, after which the diameter is preferable grown to about 20 to 100 nm, depending on the initial particle spacing.
Methods of growing conductive metal particle bound to surface are well known in the field of histology, wherein various reagents are commercially available to cover nanospheres of gold with silver, gold or silver followed by a thin gold coating. For example the “GoldEnhance”™ reagent kit is also available from Nanoprobes for this purpose. Alternatively, nanoparticles of gold can be expanded by incubation at room temperature on an aqueous solution of 0.5 mM HAuCl4 and 0.5 mM NH2OH for about 2 minutes. The substrate is then washed with water and blown dry with Nitrogen or another inert gas. The gold particles are grown to the desired size by simply extending the incubation period in the Gold Enhance reagent for as long as is desired.
It should be understood that the desired final size of the conductive nanoparticle is that which sufficiently reduces the interparticle gap to provide the intended device sensitivity and dynamic range. Although it is possible to use repeated electrical continuity measurements to determine when the conductive particles have grown to the point at which they touch, a preferred method utilizes the change in color from blue, for the original NANOGOLD particles, to red as the particles grow to a size where they touch, and no longer interest with incident light as quantum dots. The change in color occurs because the surface plasmon resonance absorption of discrete gold nanoparticles red shifts with a broader spectral shape from the initial spectral placement (centered at roughly 545 nanometers) as the particles move farther apart. Accordingly, in the more preferred embodiments it is preferable that the substrate 110, or the combination of substrate and spacer, are somewhat reflective so this red shift can be observed visually or measured in reflection from the substrate to terminate the growth of the nanoparticles of gold. In the case of this example, it was preferable to grow the gold-nanoparticles to a diameter of about 20 nm. However, in other embodiments depending on the width, length, binding density and flexibility of the molecular species that constitutes of column 120 a different range of final particle size might be preferred. As a generally preferred range of the size of particle 120 is 15 to 40 nm, the height of the columns is generally at least twice this value, or about 30 to 80 nm.
In light of the foregoing, one of ordinary skill in the art will appreciates that alternative nano scale particles include non-conductive particles having a metallic or otherwise stable conductive coating, such as phosphorus or boron-doped nickel that might be deposited by electro less deposition from solution.
It should be appreciated that the particle arrays of the instant invention can be distinguished from prior art sensors or devices that measure changes of resistivity of dispersed conductive particles. Such dispersions are not controlled, that is they are random and hence depend on the density of particles reaching a percolation threshold to function. However, when the percolation threshold is reached their will also be a random separation distance between particles through the material.
However, scale, size and structure of the arrays of the instant invention offers unique advantages over this prior art. First, it should be appreciated that because the spacing between particles can be controlled by the molecular structure of the species forming the column, the device sensitivity can be extremely high (that is detect nanoscale deformation) with a very high dynamic range. This can be understood from the relationship between the resistance, R, between adjacent particles when the conduction mechanism is tunneling which can be calculated as:
R=(8πhs/3a2γe2)exp(γs)
wherein h is Plank's constant, s is the distance between particles, a2 is the effective cross-sectional area and γ is calculated from fundamental constants (wherein m is the electron mass) and the height of the potential barrier is φ as
γ=4π(2mφ)0.5h
Accordingly, a small increase in particle spacing, s, leads to a more than exponential increase in resistance, R. Hence, by selection of the device dimension through the construction with uniform precursors, i.e. the columns 120 and the particle 130, a device can be constructed wherein the slightest perturbation to the dense array of particles will initiate a large change in resistance. Further, since the array is spatially uniform it can be decreased in size to the minimum number of particle necessary to make ohmic contact with external junctions.
However, a dispersed particle array cannot be subdivided to such an extent because as the scale of division approaches the percolation scale their will be massive variations in the particle density and spacing, hence giving wide fluctuations in the base resistance and the dynamic range of each such portion. For the same reasons local deformations of such prior art materials smaller that the percolation scale cannot be reliability measured.
In contrast, the sensor device of the instant invention can be reduced on a lateral scale commensurate with the event or object to be measured, as same local deformation of the substrate will produce the same response regardless of the lateral position in the area. Finally, as the nano-sensor has molecular dimensions it can be expected to be responsive to and detect molecular motion on a comparable scale that is just above phonon vibrations. Further, the homogenous nature of the conductive particle array ensures ohmic contact with external electrodes, which can be problematic when conductive particles are dispersed in an insulating matrix, as the matrix can form an outer layer of the device.
However, a dispersed particle array cannot be subdivided to such an extent because as the scale of division approaches the percolation scale their will be massive variations in the particle density and spacing, hence giving wide fluctuations in the base resistance and the dynamic range of each such portion. For the same reasons local deformations of such prior art materials smaller that the percolation scale cannot be reliability measured.
In contrast, the sensor device of the instant invention can be reduced on a lateral scale commensurate with the event or object to be measured, as same local deformation of the substrate will produce the same response regardless of the lateral position in the array. Finally, as the nano-sensor has molecular dimensions it can be expected to be responsive to and detect molecular motion on a comparable scale, which is just above phonon vibrations. Further, the homogenous nature of the conductive particle array ensures ohmic contact with external electrodes, which can be problematic when conductive particles are dispersed in an insulating matrix, as the matrix can form an outer layer of the device.
As is more apparent in the plan view of
The instant invention differs from prior art MEMS type sensors in several import aspects. Although the general cantilever geometry shown in
Piezoelectric detection requires placing a pair of opposing electrodes on the portion of the beam that undergoes deformation. The beam itself must be a piezoelectric material. Further, the placement of electrodes in the capacitive and piezoelectric detection methods requires more complex manufacturing steps than the instant invention. In the instant invention the electrodes 351 and 352 need not be on the beams itself, but can be disposed solely on the substrate 310 and/or the supporting plate 320 by simply extending the placement of the strain sensitive coating 340 past the portion of the beam that undergoes deformation. As the electrode itself need not deform with the beam, the beam size can be much smaller, and hence more sensitive to lower amplitude vibrations or to detect and discriminate a much lower magnitudes of inertial forces. Further as the strain sensitive coating 340 has a greater effective strain resistance coefficient than piezoelectric materials used to form beam 330, the dynamic range of the device 300 is much larger.
It should be appreciated that the strain sensitive coating 340 can be patterned in a U or other shape by numerous methods known in the art of microfabrication. One such method is to first coat the device with a continuous layer of strain sensitive coating 340 (or just the thin polymer film or columnar spacer) and removing the undesired portion via masking and ablation, as is commonplace in semiconductor device fabrication. In an alternative method, a coupling agent for the columnar spacer (or the thin polymer spacer layer) can be deposited directly in the U-shaped circuit by molecular imprinting. As a non-limiting example, suitable methods of molecular imprinting are taught in U.S. Pat. No. 6,251,280 (issued to Dai, et al. Jun. 26, 2001), which is incorporated herein by reference. It should be further appreciated that as the columnar spacer or thin polymer layer that separates the conductive particles from the substrate is non-conductive, a conductive beam, when suitably masked on selected portions, can serve as one electrode in the circuit itself.
The multiple beams 330, 331, 332 and 332 are different sizes so that selected beams deflect at their particular resonant frequency when the device is excited or energized by a vibration having frequency components that match the self-resonance frequency of the beams in the array. The use of multiple cantilever beams in a vibration wave detection device is disclosed in U.S. Pat. No. 6,079,274 (to Ando et al., issued Jun. 27, 2000).
It is preferable that the device deploys selected beams of the same of resonant frequency for redundancy should some of the beams or circuit fail, as described in U.S. Pat. No. 6,750,775 (to Chan et al, issued Jun. 15, 2005), which is incorporated herein by reference.
While the invention has been described in connection with a preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth, but on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be within the spirit and scope of the invention as defined by the appended claims.
The present application claims priority to the U.S. provisional application having Ser. No. 60/738,927 entitled “Nanoparticle Vibration and Acceleration Sensors”, filed on Nov. 21, 2006 which is incorporated herein by reference. The present application also claims priority to the U.S. provisional application having Ser. No. 60/738,793 entitled “Nanoscale Sensor”, filed on Nov. 21, 2006 which is incorporated herein by reference. The present application further claims priority to the U.S. provisional application having Ser. No. 60/738,778 entitled “Polymer Nanosensor Device”, filed on Nov. 21, 2006 which is incorporated herein by reference.
Number | Date | Country | |
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60738927 | Nov 2005 | US | |
60738793 | Nov 2005 | US | |
60738778 | Nov 2005 | US |