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WO2012082135A1 - Systèmes et procédé de formation de capteurs à nanotubes de carbone - Google Patents

Systèmes et procédé de formation de capteurs à nanotubes de carbone Download PDF

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Publication number
WO2012082135A1
WO2012082135A1 PCT/US2010/060929 US2010060929W WO2012082135A1 WO 2012082135 A1 WO2012082135 A1 WO 2012082135A1 US 2010060929 W US2010060929 W US 2010060929W WO 2012082135 A1 WO2012082135 A1 WO 2012082135A1
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WIPO (PCT)
Prior art keywords
electrode
substrate
carbon nanotube
carbon nanotubes
decorating material
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Ceased
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PCT/US2010/060929
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English (en)
Inventor
Makarand Paranjape
Jianyun Zhou
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Georgetown University
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Georgetown University
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Publication date
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Priority to PCT/US2010/060929 priority Critical patent/WO2012082135A1/fr
Priority to CA2819274A priority patent/CA2819274C/fr
Publication of WO2012082135A1 publication Critical patent/WO2012082135A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the present invention relates generally to the use of carbon nanotube technology in the field of sensor applications. More specifically, this invention relates to processes for forming and functionalizing of carbon nanotube field effect transistors ("CNTFETs”) for use in specific sensor systems, such as chemical and biological sensors.
  • CNTFETs carbon nanotube field effect transistors
  • a first embodiment includes a process for forming a functionalized sensor for sensing a molecule of interest.
  • the process includes: providing at least one single-wall carbon nanotube having a first and a second electrode in contact therewith on a substrate; providing a third electrode including a decorating material on the substrate a predetermined distance from the at least one single-wall carbon nanotube having a first and a second electrode in contact therewith, wherein the decorating material has a bonding affinity for a bioreceptors that react with the molecule of interest; and applying a voltage to the third electrode, causing the decorating material to form nanoparticles of the decorating material on the at least one single- walled carbon nanotube.
  • a second embodiment describes a system for forming a functionalized sensor for sensing a molecule of interest including: at least one carbon nanotube having a first and a second electrode in contact therewith on a substrate; a third electrode including a decorating material on the substrate a predetermined distance from the at least one carbon nanotube having a first and a second electrode in contact therewith, wherein the decorating material has a bonding affinity for a bioreceptors that react with the molecule of interest; wherein a voltage is applied to the third electrode, causing the decorating material to form nanoparticles of the decorating material on the at least one carbon nanotube.
  • Figure 1 illustrates a carbon nanotube field effect transistor (CNTFET) for use with embodiments of the present invention.
  • Figures 2(a) - 2(b) illustrate representative and actual set-up configurations for functionalizing carbon nanotubes.
  • Figures 3(a) - 3(d) illustrate a series of SEM images showing deposition particulars at different voltages.
  • Figure 4 illustrates is a schematic showing anchoring of receptors to
  • nanoparticles deposited on a carbon nanotube are nanoparticles deposited on a carbon nanotube.
  • Figure 5 illustrates a schematic of a CNTFET which has been passivated using a self assembled monolayer (SAM) to avoid non-specific binding of bioreceptors.
  • SAM self assembled monolayer
  • Figure 6 illustrates intermolecular linking of SAM molecules.
  • Figure 7 illustrates an alternative arrangement of the CNT and iSE.
  • CNTFETs may be decorated with nanoparticles as further described to facilitate the binding of chemical/biological molecules of interest thereto.
  • CNTFETs generally includes one or more CNTs, one or more electrodes contacting the two ends of the nanotube(s), an insulating dielectric layer (e.g., Si0 2 ) on top of or underneath the nanotube(s), and a conductive gate (e.g., doped silicon (if underneath of the nanotube), or a metallic top-gate (if on top of the nanotube) within a few hundred nanometers to the nanotube but insulated by the dielectric layer.
  • Various techniques are used to developed CNTs including discharge, laser ablation and chemical vapor deposition (“CVD”) and such techniques are well known to those skilled in the art.
  • the electrodes may be patterned using photolithography or electrode beam lithography. Further, the electrodes may be metallic or non-metallic (e.g., conductive polymers, indium-tin-oxide (ITO) and the like.
  • a single wall CNT (“SWCNT”) is used as the conduction channel in a CNTFET implemented as the sensor in the devices described herein.
  • S source
  • D drain
  • insulating dielectric layer e.g., Si0 2
  • Si conductive gate
  • CNTFETs may be formed using multiple CNTs, including CNT films or networks, including multiple CNTs, as described in the teachings of A. Star, E. Tu, J. Niemann, J-C. P. Gabriel, C. S. Joiner, and C. Valcke, Proc Natl Acad Sci U S A.
  • the specificity of the attachment becomes important since any unintended attachment will potentially introduce noise to the device. While the present embodiments contemplate a conductive substrate and thus a constraint on types of materials that may be used, embodiments are contemplated which utilize a top gate and thus the substrate is not constrained and can include glass, ceramic, plastic, etc. Further, while the specific embodiment described herein refers to at least one single wall CNT, the use of multi wall CNTs are also contemplated.
  • the SWCNT is functionalized using electrically controllable Au nanoparticle decoration.
  • the set up for facilitating Au decoration includes the addition of a third electrode in close proximity to, but not directly in contact with the SWCNT.
  • the third electrode serves as a source of Au and is sacrificed after the Au deposition.
  • the third electrode may be referred to as the "in-situ sacrificial electrode" (iSE).
  • the iSE is composed of a bilayer of metals Cr/Au (Cr used as an adhesion layer for Au - could also use other adhesion layers, e.g.
  • FIG. 2(b) is an actual view of the electrodeposition set-up.
  • a drop of electrolyte PBS is applied to the device, and a positive voltage V d is applied to the sacrificial electrode, with both contact electrodes grounded.
  • Au atoms from the sacrificial electrode are oxidized by the positive potential and dissolve in the PBS as Au ions, and are reduced at the grounded electrode/CNT and redeposit as metal atoms.
  • the applied voltage is reduced to avoid electrolysis of water, and finer adjustments will be made later to control the size and density of Au nanoparticles.
  • FIGS. 3(a)-(d) the high sensitivity of particle density and size in accordance with changes in applied voltage is illustrated.
  • the SEM images show a series of carbon nanotubes decorated with Au nanoparticles. With the deposition time held constant at 2 minutes, by slightly increasing the deposition voltage V d , the number of nanoparticles increases substantially, and the size of the nanoparticles also shows an increasing trend, from 20 nm to as large as 300 nm. Note that at all voltages, the sizes of the nanoparticles are not homogenous, and the variation of particle size increases with deposition voltage.
  • nanoparticles At the highest voltage 1.36V, there are over 30 nanoparticles on the nanotube, and the size ranges from 27 nm to over 300 nm (Fig. 3(d)). In the middle, there are over 10 nanoparticles with diameters less than lOOnm, and on the two sides, nanoparticles are typically much larger, with diameters of hundreds of nanometers.
  • the deposit material such as Ag.
  • Appropriate changes to the deposition set up are implemented to account of use of other deposit materials.
  • select receptors can be anchored to the nanoparticles in order to prepare the CNTFET for use as a sensor. This is shown schematically in Figure 4. Certain metals have strong affinity to specific chemical groups, and the affinity can be utilized to realize effective surface modifications. For example, gold atoms are known to interact strongly with sulfur atoms in thiols and form a strong covalent bond.
  • the Au nanoparticles are deposited on the CNT sidewalls as anchoring sites to immobilize thiol-terminated bio-molecules to the nanotube for sensor applications.
  • the strong covalent bond between the gold and thiol provides for a more robust bond compared to nonspecific adsorption of biomolecules onto the CNT sidewalls.
  • the catalytic nature and suitability for binding to the thiol as well as the excellent conductivity of the metallic Au nanoparticles makes the delivery of the chemical event at the biomolecule to the CNT channel much easier.
  • a self assembled monolayer may be used.
  • An SAM is an organized layer of molecules which consists of a head and a tail, with the head showing a specific affinity for a substrate, and the tail having a desired functional group at the terminal.
  • SAMs have been widely used for surface property modifications in electronic devices, especially microelectrochemical systems (MEMS) and nanoelectromechanical systems (NEMS). Its working mechanism is shown in Figure 5.
  • MEMS microelectrochemical systems
  • NEMS nanoelectromechanical systems
  • the original substrate has an affinity for head group of the SAM, and after modification, the substrate has the property of the terminal functional group R.
  • the use of an SAM provides for an effective method to combine the desirable properties of the substrate such as electrical conductivity, mechanical robustness, to the SAM molecule's chemical properties.
  • the head group should have a strong affinity to Si0 2 surface.
  • the tail should have good protein resistivity.
  • Polyethylene glycol (PEG) SAMs including methoxy-terminated PEG 2000 have been shown to have good protein resistivity.
  • the silane functional group having the following molecular structure is added to one end of the molecule: O OCH 2 CH 3
  • the silane functional groups of the PEG hydrolyze and form trisilanols.
  • the trisilanols interact with the Si0 2 and hydrogen bond with the surface bound water molecules. With mild heating, the water molecule is lost and a covalent siloxane bond is formed.
  • the tri-silanol head groups can interact with each other and intermolecular crosslinking takes place as shown in
  • the electrodeposited Au nanoparticles serve as specific binding sites for thiol-terminated glucose oxidase, and the presence of glucose can be detected using the redox reaction between glucose and glucose oxidase.
  • the particular electrical configurations and processes for sensing reactions within the CNTFETs are well known to those skilled in the art.
  • the glucose oxidase is functionalized with one or multiple thiols to covalently bind to the Au nanoparticles.
  • the thiolated GOx is selectively deposited to the Au nanoparticles of the carbon nanotube FET, using the above mentioned SAM passivation method. Fluorescent labels might also be used on the protein to confirm the successful attachment using confocal fluorescent imaging techniques. After the device is fully functionalized, sensing tests can be taken. For glucose sensing, the device is placed in an aqueous environment. A PBS buffer is applied to the nanotube device, and the device conductance is monitored in real time with a constant gate.
  • the optimized devices may be used as the sensor portion of the transdermal devices described herein.
  • the CNTFET is decorated with metallic (e.g., Au) nanoparticles that are pre-bound with selected bioreceptor molecules (e.g., thiolated GOx).
  • the iSE configuration can have different shapes, as seen in Figure 7, e.g., the rectangular iSE could run parallel to the CNT, and shape of the iSE. Further still,
  • bioreceptors could be pre-bound to the iSE prior to application of the external electric field, such that the metallic nanoparticles already include the bioreceptors at the time of decoration of the CNT.
  • a masking layer is used over the electrodes, e.g. polymethylmethacrylate (PMMA) or the negative-tone photoresist known as SU-8 to protect the contact electrodes from decoration.
  • PMMA polymethylmethacrylate
  • SU-8 negative-tone photoresist
  • the protection layer would form a physical barrier to the decorating species.
  • the decorated CNTFETs are used in place of the photonic-based and other sensors described previously. More particularly, referring, for example, to Figure 2 of U.S. Patent No. 6,887,202, a decorated CNTFET would be in the position of detection layer 203 such that it is exposed to the sample from capillary 202. Using the Au decorated CNTFET with thiol-terminated glucose oxidase bioreceptors bound thereto, glucose present in the sample would react with the bioreceptors and cause a measurable electrical response.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un procédé de formation d'un capteur fonctionnalisé pour la détection d'une molécule d'intérêt, lequel procédé consiste à se procurer au moins un nanotube de carbone mono-paroi ou à parois multiples ayant une première et une deuxième électrode en contact avec lui ou avec eux sur un substrat; se procurer une troisième électrode comprenant une matière décorative sur le substrat à une distance prédéterminée du ou des nanotubes de carbone mono-paroi ou à parois multiples ayant une première et une seconde électrode étant en contact avec lui ou avec eux, la matière décorative ayant une affinité de liaison pour des biorécepteurs qui réagissent avec la molécule d'intérêt; et à appliquer une tension à la troisième électrode, amenant la matière décorative à former des nanoparticules de la matière décorative sur le ou les nanotubes de carbone mono-paroi ou à parois multiples.
PCT/US2010/060929 2010-12-17 2010-12-17 Systèmes et procédé de formation de capteurs à nanotubes de carbone Ceased WO2012082135A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2010/060929 WO2012082135A1 (fr) 2010-12-17 2010-12-17 Systèmes et procédé de formation de capteurs à nanotubes de carbone
CA2819274A CA2819274C (fr) 2010-12-17 2010-12-17 Systemes et procede de formation de capteurs a nanotubes de carbone

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10994990B1 (en) 2018-11-13 2021-05-04 United States Of America As Represented By The Secretary Of The Air Force Inline spectroscopy for monitoring chemical vapor deposition processes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050126913A1 (en) * 2003-02-27 2005-06-16 The Regents Of The University Of California Systems and methods for making and using nanoelectrodes
US20050265914A1 (en) * 2002-03-18 2005-12-01 Honeywell International, Inc. Carbon nanotube-based glucose sensor
US20080093211A1 (en) * 2005-12-27 2008-04-24 Rensselaer Polytechnic Institute Method for site-selective functionalization of carbon nanotubes and uses thereof
US20090212279A1 (en) * 2008-02-27 2009-08-27 Maozi Liu Nanostructure-Based Electronic Device
US20100088040A1 (en) * 2005-03-29 2010-04-08 The Trustees Of The University Of Pennsylvania Single walled carbon nanotubes with functionally adsorbed biopolymers for use as chemical sensors
US20100285514A1 (en) * 2009-01-27 2010-11-11 Jonathan Clay Claussen Electrochemical biosensor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050265914A1 (en) * 2002-03-18 2005-12-01 Honeywell International, Inc. Carbon nanotube-based glucose sensor
US20050126913A1 (en) * 2003-02-27 2005-06-16 The Regents Of The University Of California Systems and methods for making and using nanoelectrodes
US20100088040A1 (en) * 2005-03-29 2010-04-08 The Trustees Of The University Of Pennsylvania Single walled carbon nanotubes with functionally adsorbed biopolymers for use as chemical sensors
US20080093211A1 (en) * 2005-12-27 2008-04-24 Rensselaer Polytechnic Institute Method for site-selective functionalization of carbon nanotubes and uses thereof
US20090212279A1 (en) * 2008-02-27 2009-08-27 Maozi Liu Nanostructure-Based Electronic Device
US20100285514A1 (en) * 2009-01-27 2010-11-11 Jonathan Clay Claussen Electrochemical biosensor

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GRUNER.: "Carbon nanotube transistors for biosensing applications.", 30 August 2005 (2005-08-30), Retrieved from the Internet <URL:http://nano.com/news/archives/publications/biosensing0805.pdf> [retrieved on 20110208] *
ZHOU.: "FABRICATION AND FUNCTIONALIZATION OF CARBON NANOTUBE FIELD EFFECT TRANSISTORS FOR BIO-SENSING APPLICATION", DISERTATION, 17 December 2009 (2009-12-17), Retrieved from the Internet <URL:http:/lcdm15036.contentdm.oclc.org/cgi-bin/showfile.exe? CISOROOT=/p15036co113&CISOPTR=473&filename=474.odf> [retrieved on 20110208] *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10994990B1 (en) 2018-11-13 2021-05-04 United States Of America As Represented By The Secretary Of The Air Force Inline spectroscopy for monitoring chemical vapor deposition processes

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CA2819274A1 (fr) 2012-06-21
CA2819274C (fr) 2018-04-03

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