Source: http://www.google.com/patents/US7948041?dq=5,973,252
Timestamp: 2015-05-30 18:42:56
Document Index: 278620067

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'application No. 60', 'application No. 60', 'application No. 60', 'Application No. 2003', 'Application No. 2003', 'Application No. 2004', 'Application No. 60', 'application No. 60', 'Application No. 2004']

U.S. Application No. 60/967,552 filed Sep. 4, 2007, entitled “Sensor Having A Thin-Film Inhibition Layer, Nitric Oxide Converter And Monitor”; and U.S. Application No. 60/922,642 filed Apr. 10, 2007, entitled “Ammonia Nanosensors, and Environmental Control System”; This application claims priority pursuant to 35 USC. �120 of the following U.S. Applications, each of which applications are incorporated by reference:
U.S. Ser. No. 11/636,360 filed Dec. 8, 2006 (published 2008-0093226), entitled “Ammonia Nanosensors, and Environmental Control System”; which claims priority to US provisional application. No. 60/748,834 filed Dec. 9, 2005; U.S. Ser. No. 11/588,845 filed Oct. 26, 2006 (published 2008-0021339), entitled “Anesthesia Monitor, Capacitance Nanosensors and Dynamic Sensor Sampling Method”; which claims priority to US provisional application No. 60/730,905 filed Oct. 27, 2005; U.S. Ser. No. 11/488,456 filed Jul. 18, 2006 (published 2007-0048,181) entitled “Improved Carbon Dioxide Nanosensor, And Respiratory CO2 Monitors”; which claims priority to U.S. provisional application No. 60/700,944 filed Jul. 20, 2005; and U.S. Ser. No. 11/437,275 filed May 18, 2006 (published 2007-0048,180) entitled “Nanoelectronic Breath Analyzer and Asthma Monitor”; which claims priority to U.S. provisional application No. 60/683,460, filed May 19, 2005. Each of the following patent applications is incorporated by this reference in its entirety for all purposes and relates to aspects of the invention in some manner:
U.S. Ser. No. 11/541,794 filed Oct. 2, 2006 (published 2010-0323925), entitled “Sensor Array Based On Metal Decorated Carbon Nanotubes”; U.S. Ser. No. 11/259,414 filed Oct. 25, 2005 (published 2006-0228,723), entitled “Systems and method for electronic detection of biomolecules”; which claims priority to No. 60/622,468 filed Oct. 25, 2004; U.S. Ser. No. 11/019,792 filed Dec. 18, 2004 (published 2005-0245,836), entitled “Nanoelectronic Capnometer Adapter”“; U.S. Ser. No. 10/940,324 filed Sep. 13, 2004 (published 2005-0129,573), entitled “Carbon Dioxide Nanoelectronic Sensor”; U.S. Ser. No. 10/656,898 filed Sep. 5, 2003 (published 2005-0279,987), entitled “Polymer Recognition Layers For Nanostructure Sensor Devices”; U.S. Ser. No. 11/090,550 filed Mar. 25, 2005 (Pat. No. 6,894,359), entitled “Sensitivity Control For Nanotube Sensors”; U.S. Ser. No. 10/177,929 filed Jun. 21, 2002 (equivalent publication U.S. 2007-0140,946), entitled “Dispersed Growth Of Nanotubes On A Substrate” ; and U.S. Ser. No. 10/388,701 filed Mar. 14, 2003 (Pat. No. 6,905,655), entitled “Modification Of Selectivity For Sensing For Nanostructure Device Arrays”. BACKGROUND
NO detection in breath is a proven marker for airway inflammation (as well as for other tissue inflammation, immune responses, and other conditions). Therefore, the ability to measure NO as an exhaled breath parameter, for example as fractional exhaled nitric oxide (FeNO), is a valuable tool for diagnosis, monitoring, and managed treatment of asthma and other disorders. See, for example, U.S. Pat. No. 6,010,459 entitled “Method and apparatus for the measurement of components of exhaled breath in humans”, which is incorporated by reference. However, medical systems for the measurement of NO suffer from generally the same limitations as capnograph devices, e.g., high cost, weight and complexity.
CO2 detection in breath has been used as an indicator of perfusion and heart function as well as ventilator effectiveness. In addition, CO2 is useful, by itself or in combination with other measurements, in diagnosing and monitoring airway status and pulmonary function. For example, see U.S. Pat. No. 6,648,833 entitled “Respiratory analysis with capnography”, which is incorporated by reference.
It has also been proposed to monitor medical conditions, such as asthma, using detection of more than one metabolic species, for example considering both NO and CO2 in exhaled breath. For example, see US Published Application No. 2003-0134,427 entitled “Method and apparatus for determining gas concentration”; and C. Roller et al., “Simultaneous NO and CO2 measurement in human breath with a single IV-VI mid-infrared laser”, Optics Letters (2002) Vol. 27, No. 2, pgs. 107-109; each of which is incorporated by reference.
There are several different conventional technologies for sensing NO gas for medical breath analysis applications. In laser detection, a laser may be tuned to a frequency which is selectively absorbed by NO. A photo detector then detects the transmission of laser light through a sample column, the degree of absorption by the gas being related to NO concentration. NO may also be detected by such methods as chemiluminescence, and other optical detection methods. See, for example, U.S. Pat. No. 6,038,913 entitled “Device for determining the levels of NO in exhaled air”; US Published Application No. 2003-0134,427, entitled “Method and apparatus for determining gas concentration”, and US Published Application No. 2004-0017,570 entitled “Device and system for the quantification of breath gases”, each of which is incorporated by reference. However, each of the conventional NO detection strategies suffer limitations in equipment size, weight, cost and/or operational complexity that limit their use for a low-cost, patent-portable.
Devices fabricated from random networks of SWNTs eliminates the problems of nanotube alignment and assembly, and conductivity variations, while maintaining the sensitivity of individual nanotubes For example, such devices are suitable for large-quantity fabrication on currently on 4-inch silicon wafers, each containing more than 20,000 active devices. These devices can be decorated with specific recognition layers to act as a transducer for the presence of the target analyte. Such networks may be made using chemical vapor deposition (CVD) and traditional lithography, by solvent suspension deposition, vacuum deposition, and the like. See for example, U.S. Ser. No. 10/177,929 filed Jun. 21, 2002 (equivalent publication US 2007-0140,946), entitled “Dispersed Growth Of Nanotubes On A Substrate”; U.S. Pat. No. 6,894,359 entitled “Sensitivity Control for Nanotube Sensors”; U.S. Ser. No. 10/846,072 filed May 14, 2004 (published 2005-0184,641), entitled “Flexible Nanotube Transistors”; and L. Hu et al., Percolation in Transparent and Conducting Carbon Nanotube Networks, Nano Letters (2004), 4, 12, 2513-17, each of which application and publication is incorporated herein by reference.
The nanoscale elements can be fabricated into arrays of devices on a single chip for multiplex and multiparametric applications See for example, the following patent applications: U.S. Ser. No. 10/388,701 filed Mar. 14, 2003 (U.S. Pat. No. 6,905,655), entitled “Modification of Selectivity for Sensing for Nanostructure Device Arrays”; U.S. Ser. No. 10/656,898 filed Sep. 5, 2003 (published U2005-0279,987), entitled “Polymer Recognition Layers for Nanostructure Sensor Devices”, U.S. Ser. No. 10/940,324 filed Sep. 13, 2004 (published 2005-0129,573), entitled “Carbon Dioxide Nanoelectronic Sensor”; and U.S. Ser. No. 11/111,121 filed Apr. 20, 2005 (published 2006-0055,392) entitled “Remotely Communicating, Battery-Powered Nanostructure Sensor Devices”; each of which is incorporated herein by reference.
Sensor 102 may further comprise a layer of inhibiting or passivation material 118 covering regions of the sensor, such as adjacent to the connections between the conductive elements 110, 112 and conducting channel 106, and/or covering all or portions of exposed substrate or electrode surfaces. The inhibiting material may be impermeable to at least one chemical species, such as to the analyte 101 or to environmental materials such as water or other solvents, oxygen, nitrogen, and the like. The inhibiting material 118 may comprise a passivation material as known in the art, such as silicon dioxide, aluminum oxide, silicon nitride, or other suitable material. Further details concerning the use of inhibiting materials in a NTFET are described in prior U.S. Pat. No. 6,894,359 entitled “Sensitivity Control For Nanotube Sensors” which is incorporated by reference herein.
FIG. 2 (views a-d) are photographic views of an exemplary embodiment of a sensor system 100 having aspects of the invention and generally as shown in FIG. 1, wherein views (a-c) include SEM images showing (a) showing the layout of interdigitated source and drain contacts S 110 and D 112, (b) showing an enlarged detail of a nanotube network N 106 and the contacts S 110 and D 112, and (c) showing an enlarged detail of the margin of network N 106. View (d) shows an example of a sensor device 100 mounted in a conventional electronic device package 130. Note that the extent of a carbon nanotube network may be conveniently controlled by selective or masked removal of nanotubes, such as by oxidation of nanotubes from peripheral regions of the substrate 104 (“ashing”), by etching techniques, or the like.
In certain alternative embodiments, the substrate may comprise a flexible insulating polymer, optionally having an underlying gate conductor (such as a flexible conductive polymer composition), as described in U.S. application Ser. No. 10/846,072 (published 2005-0184,641) entitled “Flexible Nanotube Transistors”, which application is incorporated by reference. In further alternative embodiments, the substrate may comprise a microporous material permitting suction to be applied across the substrate, e.g., porous alumina for vacuum deposition of a nanotube network channel 106 from suspension or solution, as described in U.S. Application No. 60/639,954, filed Dec. 28, 2004, entitled “Nanotube Network-On-Top Architecture For Biosensor”, which application is incorporated by reference. Alternatively, the substrate may comprise a polymeric or organic material, which may be formed to a convenient shape or layered structure, such as a plastic sheet material (e.g., PET sheet).
Contacts or electrodes. In an NTFET example, the conductor or contacts 110, 112 used for the source and drain electrodes can be any of the conventional metals used in semiconductor industry, or may be selected from Au, Pd, Pt, Cr, Ni, ITO, W or other metallic material or alloy or mixture thereof. In the alternative, other conductive materials may be employed, such as conductive polymers, graphitic materials and the like. The contacts may comprise a multi-layer or composite of conductive materials, for example, to improve the adhesion of the metal to the substrate. In one example, electrical leads may be patterned on top of a nanotube network channel from titanium films about 10-30 nm thick capped with a gold layer about 100-120 nm thick. In another example, The dimension of the distance between source 110 and drain 112 may be selected to achieve desired characteristics for a particular application. It should be understood that one or more of each of a source and drain electrode may be arranged in an interdigitated or spaced-apart electrode array, permitting a comparative large area of nanostructure channel 106 having a comparatively small source-drain gap to be arranged compactly. Spacing of contacts may be selected to suit particular applications (see description below re nanostructure or nanotube networks and “statistical” conduction across nanotube networks). In one example, contacts may be spaced at about 1 micron to about 100 microns apart. In an array, different devices may be configured with different characteristic spacing.
In addition, a conducting channel 106 comprising a generally random dispersion of individual nanoparticles advantageously permits a “statistical,” rather than a “localized” approach to nanostructure device fabrication, which may be more amenable to demanding mass production techniques. In the “statistical” approach, electrical contacts can be placed anywhere on the dispersion of individual nanostructures to form devices, without a specific correspondence between electrode position and any particular nanoparticle position. The random dispersion of nanoparticles ensures that any two or more electrodes placed thereon can form a complete electrical circuit with functioning nanostructures providing the connection. By distributing a large plurality of randomly oriented nanotubes in a dispersion over (or under) an electrode array, uniform electrical properties in the individual devices can be assured with higher yields and faster processing than is possible using the prior art approach of controlled placement or growth of individual nanotubes or other nanostructures. Note that in this approach, in a source-drain example device, conduction across the film between source and drain may be a function of nanotube-to-nanotube charge transmission, in which substantially none of the nanotubes span between source and drain contacts.
Network Formation (vapor deposition example). Nanostructure networks may be formed by various suitable methods. One suitable approach may comprise forming an interconnecting network of single-wall carbon nanotubes directly upon the substrate, such as by reacting vapors in the presence of a catalyst or growth promoter disposed upon the substrate. For example, single-walled nanotube networks can be grown on silicon or other substrates by chemical vapor deposition from iron-containing catalyst nanoparticles with methane/hydrogen gas mixture at about 900 degree C. Advantageously, the use of highly dispersed catalyst or growth-promoter for nanostructures permits a network of nanotubes of controlled diameter and wall structure to be formed in a substantially random and unclumped orientation with respect to one another, distributed substantially evenly at a selected mean density over a selected portion of the substrate. The particle size distribution may be selected to promote the growth of particular nanotube characteristics, such as tube diameter, number of walls (single or multi-walled), conductivity, or other characteristics. Other catalyst materials and gas mixtures can be used to grow nanotubes on substrates, and other electrode materials and nanostructure configurations and are disclosed in U.S. application Ser. No. 10/099,664, filed Mar. 15, 2002 entitled “Modification Of Selectivity For Sensing For Nanostructure Sensing Device Arrays”, and in U.S. application Ser. No. 10/177,929 (equivalent to published 2007-0140946) entitled “Dispersed Growth Of Nanotubes On A Substrate”, both of which applications are incorporated by reference.
Multi-walled and single-walled carbon nanotubes (collectively “CNTs”) may be used in pristine or purified condition to form interconnecting networks by deposition from a solution or suspension. However, in alternative exemplary embodiments having aspects of the invention, pre-functionalized nanotubes may be included, for example, where functionalization groups promote solubility in solvents (e.g., hydrophilic groups permitting aqueous suspension.
In one example, the nanotube network was formed from SWNTs which were functionalized by covalently bonded poly-(m-aminobenzene sulfonic acid (“PABS”). A suitable nanotube composite material (“SWNT-PABS”) may be obtained from Carbon Solutions, Inc. of Riverside, Calif. in the form of a dry powder. A variety of alternative functionalization carbon nanotube species may be included, such as conductive polymeric materials, polyaniline (PANI), polypyrrole, polyaniline derivatives, and the alternative materials described in TABLE 1 below.
Further description of methods and devices including nanotube networks deposited from solution or suspension may be found in (a) U.S. Ser. No. 11/636,360 filed Dec. 8, 2006 (published 2008-0093226), entitled “Ammonia Nanosensors, and Environmental Control System”; (b) U.S. Ser. No. 11/274,747 filed Nov. 14, 2005 (published 2007-0208243), entitled “Nanoelectronic Glucose Sensors”; (c) U.S. application Ser. No. 10/846,072, (published 2005-0184,641) entitled “Flexible Nanotube Transistors”; and (d) U.S. provisional application No. 60/937,256 filed Jun. 25, 2007 entitled “Nanoelectronic Electrochemical Test Device”; each of which is incorporated by reference.
Functionalization or Recognition Layer. Functionalization or recognition material 120 may be selected for a wide range of alternative chemical or biomolecular analytes. Examples include functionalization specific to gas analytes of industrial or medical importance, such as carbon dioxide as disclosed in application Ser. No. 10/940,324 filed Sep. 13, 2004 entitled “Carbon Dioxide Nanoelectronic Sensor”, which is incorporated herein by reference. See also application Ser. No. 10/656,898 referenced hereinabove. Examples of functionalization materials specific to biomolecules, organisms, cell surface groups, biochemical species, and the like are disclosed in application U.S. application Ser. No. 10/345,783, filed Jan. 16, 2003, entitled “Electronic Sensing Of Biological And Chemical Agents Using Functionalized Nanostructures” (published 2003-0134433), and in application Ser. No. 10/704,066 referenced hereinabove, both of which applications are incorporated herein by reference. Additional examples of useful functionalization layers or materials may be found in 2007-0048,181 (Mar. 1, 2007)
Functionalization or recognition material 120 may comprise as little as a single compound, element, or molecule bonded to or adjacent to the nanostructure channel 106. In addition, or in the alternative, functionalization materials may comprise a mixture or multilayer assembly, or a complex species (e.g., including both synthetic components and naturally occurring biomaterials). Functionalization material 120 may comprise more than one material and/or more than one layer of material, also referred to as “functionalization material”, “functionalization layer” or “functionalization”.
poly(ethylene imine), “PEI”
“PABS”
Al2O3 ZrO2 Fe2O3 CaCl2 Materials in the functionalization layer may be deposited on the NTFET using various different methods, depending on the material to be deposited. It should be understood that mixtures, alloys and composites of the materials may also be included. For many materials, ALD methodology is known which is suitable for depositing thin, uniform layers or coatings, which may be controlled to deposit on selected portions of a device, and which may be employed to produce mixtures or multi-layer coatings also. See, for example, U.S. Ser. No. 11/588,845 filed Oct. 26, 2006 (published 2008-0021339), entitled “Anesthesia Monitor, Capacitance Nanosensors and Dynamic Sensor Sampling Method”, which is incorporated by reference.
See U.S. application Ser. No. 10/655,529 (published 2007-0045,756) entitled “Improved Sensor Device With Heated Nanostructure”, which is incorporated by reference. See also suitable micromachining and/or etching techniques are described in A. Tserepi et al, “Fabrication of suspended thermally insulating membranes using front-side micromachining of the Si substrate: characterization of the etching process”, J. of Micromech, and Microeng, Vol. 13, p. 323-329 (2003); C. Tsamis et al, “Fabrication of suspended porous silicon micro-hotplates for thermal sensor applications”, Physica Status Solidi (a), Vol. 197 (2), p. 539-543 (2003); and A. Tserepi et al, “Dry etching of Porous Silicon in High Density Plasmas”, Physica Status Solidi (a), Vol. 197 (1), p. 163-167 (2003), each of which publication is incorporated by reference herein.
Optionally, the substrate may include protective and surface conditioning layers. For example a diffusion barrier may be included to prevent contamination of a substrate, such as doped silicon, by metallic catalysts or other substances introduced during fabrication steps. See U.S. application Ser. No. 11/354,561 (published 2006-0263,255) entitled “Nanoelectronic Sensor System And Hydrogen-Sensitive Functionalization”; which application is incorporated by reference.
The electronic circuitry described in this example is by way of illustration, and a wide range of alternative measurement circuits may be employed without departing from the spirit of the invention. Embodiments of an electronic sensor device having aspects of the invention may include an electrical circuit configured to measure one or more properties of the nanosensor 120, such as measuring an electrical property via the conducting elements 110, 112. For example, a transistor sensor may be controllably scanned through a selected range of gate voltages, the voltages compared to corresponding measured sensor current flow (generally referred to herein as an I-Vg curve or scan). Such an I-Vg scan may be through any selected gate voltage range and at one or more selected source-drain potentials. The Vg range is typically selected from at least device “on” voltage through at least the device “off” voltage. The scan can be either with increasing Vg, decreasing Vg, or both, and may be cycled positive or negative at any selected frequency. See, for example, dynamic sampling and other measurement methods described in U.S. applications No. 60/922,642 filed Apr. 10, 2007 entitled “Ammonia Nanosensors, and Environmental Control System”; Ser. No. 11/636,630 (published 2007-0079498) entitled “Ammonia Nanosensors, and Environmental Control System”; Ser. No. 11/588,845 entitled “Anesthesia Monitor, Capacitance Nanosensors and Dynamic Sensor Sampling Method”; and Ser. No. 11/437,275 (published 2007-0048,180) entitled “Nanoelectronic Breath Analyzer and Asthma Monitor”; each of which is incorporated by reference.
Optionally, the measurement circuitry may be configured so as to provide compensation for such factors as temperature and pressure and humidity. See U.S. application Ser. No. 11/111,121 (published 2005-0245,836) entitled “Remotely communicating, battery-powered nanostructure sensor devices”; which is incorporated by reference.
a) multiple analytes detected by a plurality of specifically functionalized sensors, b) increased precision and dynamic range by a plurality of sensors each of which is optimized for a different range, c) increased analyte specificity and flexibility by detecting a characteristic “profile” of responses of a target analyte to a plurality of differently-functionalized sensors, d) self calibration systems and isolated reference sensors, e) multiple-use array having a plurality of deployable one-time-use sensor sub-units, or f). ultra-low-cost, direct-digital-output sensor arrays, including a plurality of sensors, each producing a binary signal, and collectively having a range of response thresholds covering a selected analyte concentration range. The nanoelectronic sensors having aspects of the invention are inherently suitable to array configurations, such as may be employed in the multi-analyte integrated breath analysis system described herein. These sensors and sensor arrays can be fabricated by a range of known manufacturing technologies (see U.S. patent application Ser. No. 10/846,072 entitled “Flexible Nanotube Transistors” which is incorporated herein). One preferred approach is to use the wafer processing technology developed for the semiconductor electronics industry. This approach not only permits many sensors to be made on as single chip, but permits sensors of different functional types and different architectures to be produced simultaneously on a common substrate, using appropriate photolithographic techniques, masking, controlled etching, micro-machining, vapor deposition, “ink jet” type chemical application and circuit printing, and the like, to produce the elements of the various sensor devices and associated circuitry.
It should also be noted that alternative sensor embodiments for detection of NO may employ methods of oxidation of NO in a sample, without departing from the spirit of the invention. For example, NO may be oxidized to form NO2, followed by detection of the resultant NO2 using a sensor configured to have a sensitivity to NO2. Various strategies may be employed, such as exposure of a breath sample to a catalyst in the presence of oxygen (e.g., in exhaled air), or by exposure to a suitable oxidizing compound, e.g., permanganate salts, perchlorate salts, various metallic oxides and the like. See for example, U.S. Ser. No. 11/437,275 (published 2007-0048,180) entitled “Nanoelectronic Breath Analyzer and Asthma Monitor”.
Also, US publication 2004-0133,116 entitled “Device and method for the quantitive determination of nitrogen oxides in exhaled air and application thereof” describes oxidation of NO to NO2 using permanganate salts or perchlorate salts applied to a catalyst support including zeolite, alumina or silica gel.
See additional description in of a particular NO to NO2 conversion device having aspects of the invention below with respect to FIG. 9 In one embodiment having aspects of the invention, inhaled air may be passed through a “scrubber” device to remove environmental NO (and/or any other selected substance, such as CO2, NOx and the like) prior to administration to a patient or test subject. During or after a collection of a subsequent exhaled air sample, the sample may be passed through an conversion device to oxidize all or a portion of the NO to NO2. Optionally, the exhaled sample may be passed through one or more filter or absorber devices to remove particulates, water vapor, atomized fluids, and/or gasses such as CO2 and the like.
In an alternative exemplary embodiment having aspects of the invention, a nanotube device such as shown and described with respect to FIG. 1 may be employed, wherein the nanotube network may be coated with a thin polymer layer, such as poly(ethylene imine) (“PEI”) (see layer 120). For example, the polymer layer may be about 10 nm thick. In this configuration, the device may be operated as an n-type FET. FIG. 8 shows the response of a PEI polymer-coated NTFET to four brief exposures to NO2 gas.
For further description, see (a) U.S. Ser. No. 10/656,898 filed Sep. 5, 2003 (published 2005-0279,987), entitled “Polymer Recognition Layers For Nanostructure Sensor Devices”; (b) A. Star, K. Bradley, J.-C. P. Gabriel, G. Gr�ner, “Nano-Electronic Sensors: Chemical Detection Using Carbon Nanotubes”, Pol. Mater.: Sci. Eng. 89, pp 204 (2003); and (c) U.S. Ser. No. 11/259,414 filed Oct. 25, 2005 (published 2006-0228723) entitled “Systems And Method For Electronic Detection Of Biomolecules”; each of which is incorporated by reference.
See, for example, U.S. Ser. No. 11/588,845 filed Oct. 26, 2006 (published 2008-0021339), entitled “Anesthesia Monitor, Capacitance Nanosensors and Dynamic Sensor Sampling Method”; and U.S. Pat. No. 6,894,359 entitled “Sensitivity Control For Nanotube Sensors”; each of which is incorporated by reference.
Further description of methods for applying layer 318 may be found in, for example, U.S. applications No. 60/922,642 filed Apr. 10, 2007; Ser. No. 11/636,630 (published 2007-0079498) entitled “Ammonia Nanosensors, and Environmental Control System”; and Ser. No. 11/588,845 filed Oct. 26, 2006 (published 2008-0021339), entitled “Anesthesia Monitor, Capacitance Nanosensors and Dynamic Sensor Sampling Method”; each of which is incorporated by reference.
See also the ALD methods found in P. Chen, et al, “Atomic Layer Deposition to Fine-Tune the Surface Properties and Diameters of Fabricated Nanopores”, Nano Lett (June 2004) Vol. 4, No. 7, pp 1333-37; D. Farmer et al, “Atomic Layer Deposition on Suspended Single-Walled Carbon Nanotubes via Gas-Phase Noncovalent Functionalization”, Nano Lett (March 2006) Vol. 6, No. 4, pp 699-703; and M. Groner et al, “Gas diffusion barriers on polymers using Al2O3 atomic layer deposition”, Appl. Phys. Lett. (2006) Vol. 88, pp 051907-1; which publications are incorporated by reference. Alternative methods may be used, such as thermal and e-beam evaporation. Additional process elements may be included to improve coating properties, such as rotating and/or tilting a substrate during evaporation.
Although the substrate may comprise materials conventional to semiconductor practice (e.g., silicon wafer, quartz wafer, and the like), the arrangement of device 400 is very suitable to the use of organic sheet materials, such as a flexible polymer sheet (e.g., PET). Contacts 410-412 may comprise metals, such as vapor deposited metal, or advantageously may comprise printed traces of conductive ink composition, such as silver ink, graphite compositions, and the like. In such “printed electronic” embodiments, network 406 may comprise nanotubes such as SWNTs deposited from a solution or suspension applied to the surface device 400, for example by spray deposition. Conventional masking techniques may be used to control deposition region of network 406. Alternatively, ink jet or other printing or automated methods may be used to deposit network 406.
See, for example, (a) S. A. Kharitonov et al, “Increased nitric oxide in exhaled air of asthmatic patients”, The Lancet (1994) vol. 343, pp. 133-135; (b) B. Kimberly et al, “Nasal Contribution to Exhaled Nitric Oxide at Rest and during Breathholding in Humans”, Am. J. Resp. Critical Care Med. (1996) 153 pp. 829-836; (c) A. F. Massaro et al, “Expired nitric oxide levels during treatment of acute asthma”, Am. J. Resp. Critical Care Med. (1995) vol. 152, No. 2, pp. 800-803; and (d) P. E. Silkoff et al, “Airway nitric oxide diffusion in asthma: Role in pulmonary function and bronchial responsiveness”, Am. J. Resp. Critical Care Med. (2000) 161 pp. 1218-1228; each of which publication is incorporated by reference. See also the methodology described in U.S. Pat. Nos. 5,447,165; 5,922,610; and 6,038,913; each of which is incorporated by reference.
Sample collection may include discarding an intitial portion of an exhalation, followed by collecting sample air during a period of exhalation against a flow resistance or back pressure. See for example, (a) P. Silkoff et al., “Marked Flow-dependence of Exhaled Nitric Oxide Using a New Technique to Exclude Nasal Nitric Oxide”, Am. J. Respir. Crit. Care Med., (1997)155 pp. 260-67; (b) U.S. Pat. Nos. 5,795,787 and 6,010,459, each entitled “Method and apparatus for the measurement of exhaled nitric oxide in humans”; (c) U.S. Pat. No. 6,067,983 entitled “Method and apparatus for controlled flow sampling from the airway”; (d) U.S. Pat. No. 6,733,463 entitled “Method and measuring equipment for measuring nitric oxide concentration in exhaled air”; and (e) US Published Application No. 2004-0017,570 entitled “Device and system for the quantification of breath gases”; each of which publication and patent is incorporated by reference.
As may be seen in FIG. 14, the unexposed sensor is initially at an response level (I0). Exposure of the sensor to a first analyte concentration (concentration 1) produces a sensor response that increases over time so as to asymptotically approach (dotted curve) a steady-state response magnitude (Iasym1). If the sensor is isolated from exposure to a sample (or otherwise prevented from responding to an analyte, such as by a controllable inhibitor) at a point when the response reaches a selected cut-off magnitude (Imax), a recovery trend is begun, the response value declining so as to asymptotically approach the initial value I0. If the sensor is again exposed to the analyte sample after a recovery interval (delta t), the sensor response again increases (“rise profile”) in a similar manner until the cut-off value Imax is reached.
A second curve in FIG. 14 represents the response of the sensor to an analyte sample of a differing concentration (heavy dashed line—concentration 2), such that the response that increases over time so as to asymptotically approach (dotted curve) a different steady-state response magnitude (Iasym2). If the exposure is interrupted at a cut-off value (Imax), and the sensor is permitted to recover for a selected interval (delta t), the response curve of concentration 2 is similar to that of concentration 1, but having a differing rise profile (rise profile 1 vs. rise profile 2). Analytical comparison of the rise profiles may be employed to characterized the analyte concentrations, without monitoring the sensor response until a steady-state response magnitude is reached or approached.
FIG. 18 shows the nominal sensor response magnitude with respect to time for two cycles of purge and sample measurement. The sensor response increases during the sample interval, and decreases (recovers) during the purge interval. In this example, the sensor purge interval (sensor recovery), and sample exposure interval are controlled to be pre-selected time periods, dtP and dtS respectively, although alternative cycle control is possible (see also FIGS. 18-21). In the examples shown the sensor response is represented by the conductivity G of channel 306, and the points at which the purge reference and sample characteristics are measured are indicated by “endpoint G/Vg,p” and “endpoint G/Vg,s” respectively.
In an alternative example #3, a “landmark” on each of the purge reference and sample characteristic curves is determined. In this example, the landmark for each curve is based on a maximum-to-minimum modulation range in each characteristic curves over the full range of Vg variation (G,max−G,min)., shown as delta Gp and delta Gs, respectively. For each curve a landmark reference level is determined as a constant percentage k of the modulation variation for the respective curve, i.e., k(delta Gp) being the landmark reference level for the purge characteristic and k(delta Gs) being the landmark reference level for the sample characteristic. The purge-sample comparison represents the landmark movement, shown graphically in FIG. 26 as M,lm in terms of both a differential in Vg and G (dVg, dG). In the example of FIG. 26 a value of k=63% is used.
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No. 11/111,121.142Zhou, C. et al., (Nov. 24, 2000) "Modulated Chemical Doping of Individual Carbon Nanotubes" SCIENCE, 290:1552-1555.* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS8480959 *May 2, 2011Jul 9, 2013Samsung Electronics Co., Ltd.Chemical sensor using thin-film sensing memberUS8754454Apr 11, 2011Jun 17, 2014Nanomix, Inc.Sensor having a thin-film inhibition layerUS8797059Mar 1, 2012Aug 5, 2014International Business Machines CorporationImplementing carbon nanotube based sensors for cryptographic applicationsUS8993346Aug 6, 2010Mar 31, 2015Nanomix, Inc.Magnetic carbon nanotube based biodetectionWO2014191892A1 *May 26, 2014Dec 4, 2014CsirA field effect transistor and a gas detector including a plurality of field effect transistors* Cited by examinerClassifications U.S. Classification257/414, 257/E33.06, 257/E31.119International ClassificationH01L27/14Cooperative ClassificationG01N27/127, B82Y30/00, G01N33/004, G01N27/4146, G01N33/0037, G01N33/497European ClassificationG01N27/414D, G01N27/12E3Legal EventsDateCodeEventDescriptionNov 24, 2014FPAYFee paymentYear of fee payment: 4Oct 30, 2008ASAssignmentOwner name: NANOMIX, INC., CALIFORNIAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BRYANT, CRAIG;CHANG, YING-LAN;GABRIEL, JEAN-CHRISTOPHE P.;AND OTHERS;REEL/FRAME:021772/0540;SIGNING DATES FROM 20080124 TO 20080131Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BRYANT, CRAIG;CHANG, YING-LAN;GABRIEL, JEAN-CHRISTOPHE P.;AND OTHERS;SIGNING DATES FROM 20080124 TO 20080131;REEL/FRAME:021772/0540Owner name: NANOMIX, INC., CALIFORNIAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BRYANT, CRAIG;CHANG, YING-LAN;GABRIEL, JEAN-CHRISTOPHE P.;AND OTHERS;SIGNING DATES FROM 20080124 TO 20080131;REEL/FRAME:021772/0540RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services