WO2006103872A1 - Transistor à effet de champ à nanotube de carbone - Google Patents

Transistor à effet de champ à nanotube de carbone Download PDF

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Publication number
WO2006103872A1
WO2006103872A1 PCT/JP2006/304167 JP2006304167W WO2006103872A1 WO 2006103872 A1 WO2006103872 A1 WO 2006103872A1 JP 2006304167 W JP2006304167 W JP 2006304167W WO 2006103872 A1 WO2006103872 A1 WO 2006103872A1
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WO
WIPO (PCT)
Prior art keywords
substrate
carbon nanotube
electrode
source
substance
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PCT/JP2006/304167
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English (en)
Japanese (ja)
Inventor
Seiji Takeda
Satoshi Hattori
Atsushi Ishii
Koichi Mukasa
Makoto Sawamura
Hirotaka Hosoi
Yoshiki Yamada
Hiroichi Ozaki
Kazuhisa Sueoka
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National University Corporation Hokkaido University
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Priority to JP2007510347A priority Critical patent/JPWO2006103872A1/ja
Publication of WO2006103872A1 publication Critical patent/WO2006103872A1/fr

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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
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4146—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS involving nanosized elements, e.g. nanotubes, nanowires
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4145—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for biomolecules, e.g. gate electrode with immobilised receptors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/221—Carbon nanotubes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene

Definitions

  • the present invention relates to a field effect transistor and a manufacturing method thereof. More specifically, the present invention relates to a method for manufacturing a field effect transistor having a channel having a carbon nanotube force.
  • a field effect transistor is usually a three-electrode transistor having a source electrode and a drain electrode, a channel connecting both electrodes, and a gate electrode. A voltage is applied to the gate electrode, It is a transistor that controls the current between the source and drain electrodes. If the channel is a carbon nanotube, it is called a carbon nanotube FET.
  • the method of manufacturing a carbon nanotube FET can be broadly divided into two depending on how the channel is manufactured.
  • One is a method of forming a channel that bridges the source electrode and the drain electrode on the substrate by vapor growth of carbon nanotubes in the presence of hydrocarbon gas (see Patent Document 1).
  • One is a method in which separately produced carbon nanotubes are provided on a source electrode and a drain electrode on a substrate to form a channel (see Patent Document 2).
  • vapor phase epitaxy is often used.
  • Biosensors using carbon nanotube FETs have been developed.
  • a recognition molecule is bound to the carbon nanotube FET used in the biosensor, and a change in current between the source electrode and the drain electrode is caused by the reaction between the recognition molecule and the substance to be detected.
  • the biosensor detects a substance to be detected based on this change (see Patent Document 3).
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-347532
  • Patent Document 2 US Patent Application Publication No. 2004Z0200734
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-79342
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-34970
  • the method for producing the carbon nanotube FET can be roughly divided into two methods.
  • an object of the present invention is to provide a technique for improving the production yield of a channel composed of carbon nanotubes, and to provide a method for efficiently producing the carbon nanotube FET without lowering the performance of the carbon nanotube FET. It is.
  • the present inventor has found that the production yield of carbon nanotube FETs can be improved by producing a channel composed of carbon nanotubes using a substance having an affinity for carbon nanotubes.
  • the first of the present invention relates to the following carbon nanotube field effect transistor.
  • a field effect transistor having a source electrode and a drain electrode formed on a substrate, and a channel having a carbon nanotube force connecting the source electrode and the drain electrode, and fixing the carbon nanotube to the substrate
  • a field effect transistor comprising a carbon nanotube compatible material.
  • the present invention provides a method for producing a carbon nanotube field effect transistor described below.
  • Preparation site force of the source electrode and drain electrode A step of preparing a substrate modified with a carbon nanotube compatible substance; a step of providing a carbon nanotube to provide a carbon nanotube at an electrode formation scheduled site of the substrate; And an electrode forming step of forming a source electrode and a drain electrode, respectively, in the electrode formation planned portion of the substrate,
  • the carbon nanotube providing step at least a part of the carbon nanotube is fixed to the substrate by the interaction with the carbon nanotube affinity substance.
  • the method for producing a transistor according to [1] [3] preparing a substrate on which the source electrode and the drain electrode are formed; an electrode modifying step of modifying the source electrode and the drain electrode of the substrate with a carbon nanotube affinity substance; and a carbon nanotube on the electrode A step of providing a carbon nanotube, wherein at least a part of the carbon nanotube is fixed to a substrate by interaction with the carbon nanotube affinity substance, The method for producing a transistor according to [1].
  • a step of preparing a carbon nanotube modified with a carbon nanotube affinity substance; a step of providing a carbon nanotube that provides the modified carbon nanotube at a portion of the substrate where the electrode is to be formed; and a portion of the substrate where the electrode is to be formed Each including an electrode forming step of forming a source electrode and a drain electrode,
  • a carbon nanotube FET can be produced simply and efficiently.
  • the carbon nanotube FET can be used as an element, and for example, it can be easily applied to a biosensor.
  • FIG. 1 is a schematic view of a carbon nanotube field effect transistor. 1 for substrate, 3 and
  • 4 is a source electrode and drain electrode, 7 is a channel, 8 is a gate electrode, and G is a gap.
  • FIG. 2 is a diagram showing an example of a substrate of a carbon nanotube field effect transistor.
  • 400 is a support substrate made of a semiconductor
  • 402 and 404 are insulating films
  • 410 is a substrate made of an insulator
  • 420 is a support substrate also having a metal force
  • 422 and 424 are insulating films.
  • FIG. 3 Shows a source / drain electrode entirely covered with a coating.
  • 1 is a substrate
  • 3 and 4 are source and drain electrodes
  • 28 is a coating.
  • FIG. 4 Shows source and drain electrodes. 1 is a substrate, 3 and 4 are source and drain electrodes, 7 is a channel, and G is a gap.
  • FIG. 5 is a diagram showing an outline of a source / drain electrode whose part is covered with a film.
  • 1 is a substrate
  • 3 and 4 are a source electrode and a drain electrode
  • 7 is a channel
  • 28 is a film
  • 29 is a film and 29 is covered with a film.
  • FIG. 6 Carbon nanotube field effect transistor with source and drain electrodes protected by an insulating film.
  • 1 is a substrate
  • 3 and 4 are source and drain electrodes
  • 7 is a channel
  • 8 is a gate electrode
  • 13 is a substance to be detected
  • 15 is a sample solution
  • 30 is an insulating protective film.
  • FIG. 7 A carbon nanotube field-effect transistor in which the source and drain electrodes are protected by an insulating film.
  • 7609 is a substrate (7608 is a supporting substrate, 7607 is an insulating film), 7610 and 7611 are source and drain electrodes, 7612 is a channel, 7613 is a molecule to be detected, 7803b is a gate electrode, and 8501 is an insulating protective film .
  • FIG. 8 is a diagram showing how molecules having two or more polycyclic aromatic functional groups selectively fix carbon nanotubes. 45a and 45b indicate carbon nanotubes with different diameters.
  • FIG. 9 is a diagram for explaining a method for vapor phase growth of carbon nanotubes on a substrate.
  • 1 Is a substrate, 3 and 4 are a source electrode and a drain electrode, 7 is a carbon nanotube fixed to the substrate by a dispersion fixing method, 10 is a reaction vessel, and 11 is a hydrocarbon gas that is a raw material of the carbon nanotube.
  • FIG. 10 shows a carbon nanotube field effect transistor whose 1-Vg characteristic was measured.
  • Reference numeral 102 denotes a support substrate having a silicon force
  • 104 and 106 are insulating films which also have a silicon oxide force
  • 108 and 110 are source and drain electrodes
  • 112 is a channel made of carbon nanotubes
  • 512 is a gate electrode.
  • FIG. 11 is a graph showing the I-Vg characteristics of the field effect transistor shown in FIG.
  • the vertical axis is the source-drain current, and the horizontal axis is the gate voltage.
  • FIG. 12 shows an example of a back gate type carbon nanotube field effect transistor.
  • 1 is a substrate
  • 3 and 4 are source and drain electrodes
  • 7 is a channel
  • 8 is a gate electrode
  • 13 is a molecule to be detected
  • 15 is a sample solution.
  • FIG. 13 is an example of a back gate type carbon nanotube field effect transistor.
  • 1 is a substrate
  • 3 and 4 are source and drain electrodes
  • 7 is a channel
  • 8 is a gate electrode
  • 13 is a molecule to be detected
  • 15 is a sample solution.
  • FIG. 14 is an example of a back gate type carbon nanotube field effect transistor.
  • 1 is a substrate, 3 and 4 are source and drain electrodes, 7 is a channel, 8 is a gate electrode, 13 is a substance to be detected, 15 is a sample solution, and 30 is an insulating protective film.
  • FIG. 15 shows an example of a back gate type carbon nanotube field effect transistor.
  • 1 is a substrate
  • 3 and 4 are source and drain electrodes
  • 7 is a channel made of carbon nanotubes
  • 16 is a recess formed in the substrate (the back gate electrode is not shown).
  • FIG. 16 shows an example of a back gate type carbon nanotube field effect transistor.
  • 3 and 4 are source and drain electrodes, 7 is a channel, 16 is a recess formed in the substrate, 13 is a substance to be detected, 15 is a sample solution (the back gate electrode is not shown).
  • FIG. 17 shows an example of a back gate type carbon nanotube field effect transistor.
  • 3 and 4 are source and drain electrodes, 7 is a channel, 8 is a gate electrode, and 15 is a sample solution.
  • FIG. 18 shows an example of a back gate type carbon nanotube field effect transistor.
  • 3 And 4 are source and drain electrodes, 7 is a channel, 15 is a sample solution, 16 is a recess formed in the substrate, and 41 is a gate electrode.
  • FIG. 19 shows an example of a back gate type carbon nanotube field effect transistor.
  • 1 is a substrate
  • 3 and 4 are source and drain electrodes
  • 7 is a channel made of carbon nanotubes
  • 13 is a substance-recognizing molecule
  • 15 is a sample
  • 17 is a short needle (probe etc.)
  • 41 is a gate electrode.
  • FIG. 20 shows an example of a back gate type carbon nanotube field effect transistor.
  • 102 is a support substrate
  • 104 and 106 are insulating films
  • 108 and 110 are source and drain electrodes
  • 112 is a channel
  • 472 is a substance to be detected substance recognition
  • 490 is a sample solution
  • 512 is a gate electrode.
  • FIG. 21 shows an example of a back gate type carbon nanotube field effect transistor.
  • 102 is a support substrate
  • 104 and 106 are insulating films
  • 108 and 110 are source and drain electrodes
  • 112 is a channel
  • 472 is a substance to be detected substance recognition
  • 490 is a sample solution
  • 522 and 532 are gate electrodes.
  • FIG. 22 shows an example of a back gate type carbon nanotube field effect transistor.
  • 102 is a support substrate
  • 104 and 106 are insulating films
  • 108 and 110 are source and drain electrodes
  • 112 is a channel
  • 472a-b are target substance recognition molecules
  • 490a-b are sample solutions
  • 522a-b and 532a- b represents a gate electrode.
  • FIG. 23 shows an example of a back gate type carbon nanotube field effect transistor.
  • 102 is a supporting substrate
  • 104 and 106 are insulating films
  • 108 and 110 are source and drain electrodes
  • 112 is a channel
  • 114 is a gate electrode
  • 472 is a molecule to be detected
  • 482 is a sample solution
  • 640 is an insulating protection The membrane is shown.
  • FIG. 24 is an example of a side-gated carbon nanotube field effect transistor.
  • 1 is the substrate, 3 and 4 are the source and drain electrodes, 7 is the channel, and 8 is the gate electrode.
  • FIG. 25 shows an example of a side-gated carbon nanotube field effect transistor.
  • Reference numeral 102 denotes a supporting substrate
  • 104 denotes an insulating film
  • 108 and 110 denote source and drain electrodes
  • 472 denotes a substance to be detected
  • 640 denotes an insulating protective film
  • 702 denotes a gate electrode.
  • FIG.26 This is an example of a carbon nanotube field effect transistor of side gate (top gate) type. 1 is a substrate, 3 and 4 are source and drain electrodes, 7 is a channel, 8 is a gate electrode, 13 is a molecule to be detected, 15 is a sample solution, and 40 is an insulating protective film.
  • FIG.27 An example of a side gate (top gate) type carbon nanotube field effect transistor.
  • Reference numeral 102 denotes a support substrate
  • 104 and 106 denote insulating films
  • 108 and 110 denote source and drain electrodes
  • 472 denotes a substance to be detected
  • 482 denotes a sample solution
  • 640 denotes an insulating protective film
  • 702 denotes a gate electrode.
  • FIG. 28 shows an example of a separation gate type carbon nanotube field effect transistor.
  • 102 is a supporting substrate
  • 104 and 106 are insulating films
  • 108 and 110 are source and drain electrodes
  • 112 is a channel
  • 210 is a conductive substrate
  • 202 is a supporting substrate
  • 204 and 206 are insulating films
  • 472 is a substance to be detected
  • 490 is a sample solution
  • 602 is a gate electrode.
  • the element part including the support substrate 102, the insulating films 104 and 106, the source and drain electrodes 108 and 110, and the channel 112 is the carbon nanotube element part 212; the support substrate 202, the insulating films 204 and 206, and the target substance recognition molecule 472
  • the element part including the sample solution 490 and the gate electrode 602 is referred to as a gate element part 214.
  • FIG. 29 shows an example of the gate element portion 214 of FIG.
  • Reference numeral 202 denotes a supporting substrate
  • 204 and 206 denote insulating films
  • 472 denotes a substance-recognizing molecule
  • 490 denotes a sample solution
  • 612 and 622 denote gate electrodes.
  • FIG. 30 shows an example of the gate element portion 214 of FIG. 202 is a supporting substrate, 204 and 206 are insulating films, 472a-b are target substance recognition molecules, 490a-b are sample solutions, 612 & -1) and 622a-b are gate electrodes.
  • FIG. 31 shows an example of a separation gate type carbon nanotube field effect transistor.
  • 102 is a supporting substrate
  • 104 and 106 are insulating films
  • 108 and 110 are source and drain electrodes
  • 112 is a channel
  • 210 is a conductive substrate
  • 202 is a supporting substrate
  • 204 and 206 are insulating films
  • 472a-b are covered
  • Detecting substance recognition molecules 490a-b are sample solutions
  • 622 is a gate electrode.
  • FIG. 32 shows an example of a separation gate type carbon nanotube field effect transistor.
  • 102 Is a support substrate, 104 and 106 are insulating films, 108 and 110 are source and drain electrodes, 112 is a channel, 210 is a conductive substrate, 202 is a support substrate, 204 and 206 are insulating films, and 472a-b are to be detected
  • Substance recognition molecules 490a-b are sample solutions, and 612a-b are gate electrodes.
  • FIG. 33 shows an example of a separation gate type carbon nanotube field effect transistor.
  • 102 is a supporting substrate
  • 104 and 106 are insulating films
  • 108 and 110 are source and drain electrodes
  • 112 is a channel
  • 302 is a conductive substrate
  • 306 is a conductive wire
  • 202 is a supporting substrate
  • 204 and 206 are insulating films
  • Reference numerals 472a to 472 denote target substance recognition molecules
  • 490a to b denote sample solutions
  • 612a to b denote gate electrodes
  • 304 denotes a conductive substrate.
  • FIG. 34 is a view showing a binding mode of an IgG antibody which is a detection substance recognition molecule.
  • 50 is an antibody
  • 51 is a histag
  • 52 is NTA (bitrimethyl triacetate)
  • 53 is an IgG binding protein
  • 54 is a bivalent cross-linking reagent (55 and 56 are functional groups).
  • FIG. 35 shows a biosensor obtained by binding an HA antigen as a substance to be detected to a carbon nanotube field effect transistor.
  • 102 is a support substrate that also has silicon force
  • 104 and 106 are insulating films made of silicon oxide
  • 108 and 110 are source and drain electrodes
  • 112 is a channel made of carbon nanotubes
  • 472 is a substance-recognizing molecule made of HA antigen
  • 490 indicates a sample solution
  • 512 indicates a gate electrode.
  • FIG. 36 is a graph showing the IV characteristics of the biosensor shown in FIG.
  • the vertical axis is the source / drain current, and the horizontal axis is the source / drain voltage (gate voltage: -20V).
  • ni is the IV characteristic curve when the NTA-Ni complex is formed;
  • HA is the IV characteristic curve when the HA antigen is immobilized;
  • Serum is the IV characteristic curve when blocked with human serum albumin ; anti HA-10 ⁇ antiHA-6, respectively, is the I-V characteristic curve when reacted diluted solution diluted with High Priestess dormer supernatant of anti-HA antibody to 5 X 10 _1 ⁇ 5 X 10_ 6 .
  • Carbon nanotube FET of the present invention is Carbon nanotube FET of the present invention
  • the carbon nanotube FET of the present invention has a substrate, a source electrode and a drain electrode on the substrate, a channel made of carbon nanotubes connecting both electrodes, and a gate electrode. Further, the carbon nanochannel for fixing the carbon nanochannel to the substrate. It is preferable to contain a substance having affinity for eu.
  • FIG. 1 is a substrate
  • 3 and 4 are source and drain electrodes
  • 7 is a channel made of carbon nanotubes
  • 8 is a gate electrode.
  • the carbon nanotube affinity material force for fixing the channel 7 is coupled to the source / drain electrode or the substrate.
  • the voltage applied to the gate electrode 8 controls the current between the source electrode and the drain electrode.
  • the substrate included in the carbon nanotube FET of the present invention is preferably an insulating substrate.
  • insulating substrates include 1) a substrate in which one or both sides of a semiconductor or metal support substrate is covered with an insulating film, or 2) a substrate made of an insulator.
  • FIG. 2 shows an example of the substrate.
  • FIG. 2 (C) shows a substrate made of an insulator 410.
  • 2B includes a support substrate 400 made of a semiconductor and a first insulating film 402, and
  • FIG. 2A further includes a second insulating film 404.
  • FIG. 2D includes a support substrate 420 having a metal force and a first insulating film 422, and
  • FIG. 2E further includes a second insulating film 424.
  • the substrate included in the carbon nanotube FET of the present invention is preferably the substrate shown in FIG. 2 (A) or (B), or FIG. 2 (D) or (E), more preferably FIG. 2 (A). Or a substrate shown in (B), more preferably a substrate shown in FIG.
  • the support substrate is made of a semiconductor or a metal over the substrate in which a film such as an insulator is formed on the support substrate.
  • semiconductors include Group 14 elements such as silicon and germanium, III-V compounds such as GaAs and InP, II-VI compounds such as ZnTe, and the like, preferably silicon.
  • the metal include metals that easily form oxides, such as aluminum and magnesium.
  • the thickness of the support substrate is not particularly limited, but is usually about ⁇ , about 0.1 to 1. Omm, preferably about ⁇ to about 0.3 to 0.5 mm.
  • Examples of the material of the insulating film covering the supporting substrate include inorganic compounds such as silicon oxide, silicon nitride, silicon oxide, titanium oxide, and organic materials such as acrylic resin and polyimide. Compounds are included.
  • On at least one side of the support substrate preferably source'drain An insulating film is formed on the surface on which the electrode is disposed. The thickness of the insulating film where the source and drain electrodes are arranged is ⁇ ! About 500 nm, preferably about 20 to 300 nm. This is to prevent leakage current from flowing.
  • Examples of the substrate having the insulating force include a glass substrate in addition to the above-described substrate having the insulating force.
  • Examples of glass materials include quartz, sapphire, and glass containing elements other than sodium.
  • Conventional carbon nanotube transistors are fabricated by vapor deposition, which requires a high temperature (eg about 800 ° C) condition! As a result, glass had a low melting point and glass could not be used as a substrate.
  • the channel that is the carbon nanotube force is not necessarily produced by the vapor phase growth method (that is, the channel composed of the carbon nanotube is dispersed and fixed). It is not necessary to heat the substrate to a high temperature because it can be manufactured by a dredge method.
  • the substrate may be a glass substrate (containing sodium) having a melting point of about 400 ° C.
  • the electrodes can be bridged and connected with carbon nanotubes by a dispersion fixing method described later.
  • a glass substrate As the substrate. 1) When a transparent glass substrate is used, it is possible to use an optical microscope, a fluorescence microscope, a laser microscope, etc. (However, when a total reflection type fluorescence microscope is used, it is more than a quartz substrate due to the refractive index. Ordinary glass substrates are preferably used). In other words, the element can be driven while checking the state of the sample or the substrate with these microscopes. For example, it is possible to detect and detect changes in transistor electrical characteristics (for example, changes in source and drain currents) while observing detection objects such as viruses and antigens labeled with fluorescent molecules with a fluorescence microscope. it can.
  • a transparent glass substrate is used, it is possible to deposit metal on the substrate based on the marker attached on the substrate, so that it is possible to place electrodes etc. in an accurate position.
  • a glass substrate is preferable as a substrate for the FET of the present invention because it is cheaper and easier to process than a silicon substrate and has high insulation.
  • electrodes are formed on a silicon substrate covered with an insulating film, but a no-current is generated (a defect occurs in the insulating film covering the silicon substrate, Current leaked into the silicon substrate). By using a glass substrate Such a phenomenon is suppressed.
  • Glass is difficult to absorb heat, making it easier to cool the device.
  • the substrate may be a plastic substrate that is cheaper than glass and easy to process. Of course, in the case of a plastic substrate, it is necessary to appropriately adjust conditions for depositing metal to form electrodes.
  • a source electrode and a drain electrode are disposed on the substrate of the carbon nanotube FET of the present invention.
  • the material of the source electrode and the drain electrode include metals such as gold, platinum, and titanium.
  • the substrate is a glass substrate, it is preferably a metal such as gold or chromium.
  • the source electrode and the drain electrode are formed by depositing these metals.
  • Each of the source electrode and the drain electrode may have a multilayer structure of two or more kinds of metals. For example, a gold layer may be superimposed on a titanium layer.
  • the film thickness of the source / drain electrode is not particularly limited, but is, for example, several tens of nm.
  • the distance between the source electrode and the drain electrode is not particularly limited, but is usually about 2 to 10 ⁇ m. The distance can be further reduced, which facilitates the connection with the carbon nanotubes by the dispersion-fixed method.
  • the field effect transistor of the present invention can be applied to a biosensor.
  • a substance to be detected may be bound to a carbon nanotube (channel) that connects a source electrode and a drain electrode.
  • a sample solution containing a substance to be detected can be added onto the source electrode and the drain electrode.
  • the added sample solution covers the entire source electrode and drain electrode, a film is formed between the probe and the electrode of the current measuring device (prober etc.) (see Fig. 3), In some cases, the current flowing between the source electrode and the drain electrode (source / drain current) cannot be measured accurately.
  • the source electrode and the drain electrode in the field effect transistor of the present invention are not entirely covered by the added sample solution.
  • the source electrode and drain electrode channels made of carbon nanotubes You can increase the length of the force. That is, as shown in FIG. 4 and FIG. 5, it is preferable to set the length L3 of the source / drain electrode to 500 m or more, for example, 1 mm or more. Good.
  • W2 is preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less. Yes (up to a few micro).
  • the connecting portion of the electrode with the channel may have a protruding structure, and in this case, W1 may be about 10 / zm, for example.
  • the probe of the measuring device may be applied to the electrode in the part not covered with the film.
  • the channel connecting the source electrode and the drain electrode of the carbon nanotube FET of the present invention is composed of carbon nanotubes.
  • the carbon nanotubes constituting the channel may be either single-walled or multi-walled carbon nanotubes, but are preferably single-walled carbon nanotubes.
  • a defect may be introduced into the carbon nanotube constituting the channel.
  • “Defect” means a state in which the carbon five-membered ring or six-membered ring constituting the carbon nanotube is opened.
  • the carbon nanotubes with defects introduced may have a structure that is barely connected in a state of being cut off. The actual structure is not clear.
  • a method for introducing a defect into the carbon nanotube will be described later.
  • the defect can be obtained by annealing the carbon nanotube.
  • SET single-electron transistor
  • the performance as a SET will be described later.
  • the channel may be connected by a single carbon nanotube or a plurality of carbon nanotubes.
  • the source and drain electrodes may be connected by a bundle of carbon nanotubes, or a plurality of carbon nanotubes may be folded and connected between the source and drain electrodes! / ⁇ .
  • the state of the carbon nanotubes connecting the source and drain electrodes is AFM (atomic It can be confirmed by an atomic force microscope.
  • the channel of the carbon nanotube FET of the present invention can be produced by a dispersion-immobilization method, the channel is not necessarily constituted by one carbon nanotube.
  • the channel of the carbon nanotube FET of the present invention may be in contact with the substrate! /, And V may be formed, and a gap may be formed between the substrate and the substrate (FIG. 1). (See Gap G).
  • the channel included in the carbon nanotube FET of the present invention may be protected by an insulating protective film.
  • the carbon nanotubes that make up the channel easily interact with various molecules and change their electronic state. This change in the electronic state appears as a change in the source / drain current, and may be a noise source depending on the sensor mode. Therefore, the whole or part of the carbon nanotubes and, if necessary, the whole or part of the source / drain electrode may be covered with an insulating protective film. As a result, the carbon nanotubes are prevented from interacting with solution vapor and the like, and noise can be reduced.
  • the entire transistor can be cleaned ultrasonically or using a strong acid or a strong base. Further, since the damage is prevented by providing the protective film, the service life of the transistor can be significantly extended. Since the characteristics of carbon nanotube transistors can vary from individual transistor to transistor, it is very important to extend their service life.
  • the insulating protective film that protects the channel also having the carbon nanotube force may be formed using a nosedation film that may be formed of an insulating adhesive. Furthermore, if the insulating protective film is an oxide silicon film, a substance-recognizing molecule such as an antibody can be easily bound to the insulating protective film.
  • FIG. 6 and FIG. 7 show examples of field effect transistors (back gate type) in which a channel having carbon nanotube force is protected by an insulating protective film.
  • the entire carbon nanotube 7 and a part of the source / drain electrode are protected by the insulating protective film 30.
  • the entire carbon nanotube 7612 and the entire source / drain electrodes 7610 and 7611 are protected by an insulating protective film 8501.
  • the connection site between the carbon nanotube 7612 and the source electrode 7610, and the car is protected by an insulating protective film 8501.
  • the substance-recognized molecule 7613 (described later) can be directly bonded to the carbon nanotube, so the sensitivity when used as a sensor is improved, and single molecule detection becomes possible. sell. On the other hand, since the contact part that is easily damaged is protected, the service life can be extended and noise can be prevented.
  • the channel of the carbon nanotube FET of the present invention can be formed by any method, it is preferably formed by connecting the source and the drain with a carbon nanotube by a dispersion fixing method.
  • the dispersion fixed key method will be described in detail later.
  • the carbon nanotube FET of the present invention preferably contains a carbon nanotube affinity substance that fixes the carbon nanotubes constituting the channel to the substrate.
  • the carbon nanotube affinity substance is preferably bonded (preferably covalently bonded) to the substrate and the source / drain electrodes on the substrate, and the carbon nanotube is fixed to the substrate by affinity with the carbon nanotube. To do. That is, the channel made of carbon nanotubes is fixed to the substrate via the carbon nanotube affinity substance.
  • Examples of the substance having affinity for carbon nanotubes include aromatic polycyclic molecules exhibiting ⁇ - ⁇ interaction with carbon nanotubes.
  • Examples of the aromatic polycyclic molecule include aromatic hydrocarbons such as pyrene, naphthalene, acetracene and phenanthrene, and aromatic heterocycles.
  • the aromatic polycyclic molecule is preferably pyrene.
  • the carbon nanotube affinity substance may be a molecule having two or more aromatic functional groups. If there are two or more aromatic functional groups, the van der Noles force with the carbon nanotubes will increase, and the carbon nanotubes can be fixed stably, and carbon nanotubes with the desired diameter will be selected according to the angle of these two functional groups Can be fixed.
  • FIG. 8 shows that a molecule having two aromatic functional groups (the bonding angle ⁇ of the two functional groups) does not fix the carbon nanotube 45b having a diameter larger than the force for fixing the carbon nanotube 45a. Examples of molecules having two or more aromatic functional groups include those obtained by crosslinking two molecules of pyrene via lysine or the like.
  • the carbon nanotube-affinity substance is preferably covalently bonded to the substrate or the electrode.
  • the carbon nanotube affinity substance may be bonded to the hydroxyl group, amino group, or carboxy group introduced into the substrate by an ester bond or an amide bond.
  • the channel of the carbon nanotube FET of the present invention is preferably formed using a carbon nanotube affinity substance. This forming method will be described later in detail.
  • the field effect transistor of the present invention includes a gate electrode.
  • An example of the material of the gate electrode is a force including gold, platinum, titanium, brass, aluminum, or the like, preferably gold, like the source / drain electrodes. This is because gold has high conductivity and small error due to current leakage. It can be formed by depositing these metals.
  • the gate electrode may be disposed on an aluminum substrate, for example.
  • the arrangement of the gate electrode is not particularly limited as long as the gate electrode is arranged so that the current (source-drain current) flowing between the source and drain electrodes arranged on the substrate can be controlled by the voltage. In view of conditions or viewpoints such as transistor use and manufacturing advantages, the transistors may be arranged as appropriate.
  • the gate electrode include (A) a back gate electrode; (B) a side gate electrode; (C) a separation gate electrode.
  • a back gate electrode is formed by forming a source / drain electrode of a substrate on which a source electrode and a drain electrode connected by carbon nanotubes are arranged! Wow! /, Means the gate electrode placed on the surface (back surface).
  • the term “arranged on the surface” means that the substrate may be disposed in contact with the substrate surface or may be disposed apart from the substrate surface.
  • the back gate electrode arranged apart from the substrate surface is sometimes referred to as a sandwich type back gate electrode.
  • an insulating film be formed on the substrate surface on which the knock gate electrode is disposed (the back surface of the source / drain electrode).
  • the side gate electrode is the same surface as the surface on which the source and drain electrodes are formed on the substrate on which the source electrode and the drain electrode connected by carbon nanotubes are arranged. It means the gate electrode arranged on the top.
  • the term “arranged on the surface” means that the substrate may be disposed in contact with the substrate surface or may be disposed apart from the substrate surface.
  • the side gate electrode disposed away from the substrate surface is sometimes referred to as a top gate electrode.
  • the separation gate electrode is an insulating substrate that is separate from the substrate on which the source / drain electrodes are disposed, and is disposed on the electrically connected insulating substrate.
  • the term “insulating substrate” as used herein is the same as the substrate on which the source / drain electrodes are disposed, and is a substrate made of an insulator; or a support substrate made of semiconductor or metal; and at least one of the support substrates
  • the substrate may include an insulating film formed on the substrate. Examples of the “conductive substrate” include a glass or brass substrate on which a gold thin film is deposited.
  • the isolation gate electrode is disposed on the insulating substrate, may be disposed in contact with the substrate surface, or may be disposed away from the substrate surface.
  • the source / drain current is controlled by the voltage applied to the gate electrode.
  • the gate voltage is The source / drain current is in the 10 _9 to 10 _5 A level in the range of 20 V to +20 V, and the source and drain current changes according to the change in the gate voltage.
  • the carbon nanotube FET of the present invention can be produced by any method.
  • a separately manufactured carbon nanotube may be manufactured in the same manner as a normal method, including a force including a step of forming a channel by fixing the carbon nanotube to a substrate with a substance having an affinity for the carbon nanotube.
  • the carbon nanotube FET manufacturing method of the present invention is a method for forming a channel. Therefore, it can be classified into the following modes.
  • Sites where source and drain electrodes are to be formed Force Prepare a substrate modified with a carbon nanotube-affinity substance; provide carbon nanotubes on the substrate where electrodes are to be formed; and form source and drain electrodes .
  • a substrate on which a source electrode and a drain electrode are formed is prepared; the electrode on the substrate is modified with a carbon nanotube-affinity substance; and a carbon nanotube is provided on the electrode.
  • a carbon nanotube modified with a carbon nanotube affinity substance is prepared; a substrate on which a source electrode and a drain electrode are formed is prepared; and the modified carbon nanotube is provided to an electrode of the substrate.
  • the substrate used in the production method of the present invention is the same as the above-described substrate.
  • the carbon nanotubes provided in the production method of the present invention are preferably single-walled single-bonn nanotubes.
  • the average length of the provided carbon nanotubes is usually 0. or more, more preferably 1. O / zm or more.
  • the upper limit of the average length is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less. In any case, the length of the carbon nanotubes is preferably longer than the distance between the source and drain electrodes.
  • the average length of the carbon nanotubes provided can be measured by AFM.
  • the carbon nanotubes measured by AFM are preferably washed with an acid.
  • Examples of the provided carbon nanotubes include single-walled carbon nanotubes manufactured by Carbon Nanotechnologies Inc. (CN I., US).
  • the carbon nanotubes provided in the production method of the present invention may be subjected to an acid treatment.
  • the acid treatment of the carbon nanotube is performed, for example, by washing the carbon nanotube with sulfuric acid, nitric acid or a mixture thereof, and further ultrasonicating.
  • a carboxyl group can be introduced on the surface of the carbon nanotube.
  • Acid-treated carbon nanotubes have improved hydrophilicity, and therefore dispersibility in water is improved. Therefore, it is possible to provide carbon nanotubes dispersed in water. It becomes easy.
  • the substance having affinity for carbon nanotubes used in the production method of the present invention is as described above, and means an aromatic polycyclic molecule exhibiting ⁇ - ⁇ interaction with carbon nanotubes, and two or more. It may be a molecule having an aromatic functional group.
  • the functional group for bonding to the carbon nanotube-affinity substance is bonded to the substrate surface (preferably, the electrode formation planned portion of the substrate) or the surface of the source / drain electrode formed on the substrate. It is preferable.
  • a carboxyl group or an ester group is introduced into the carbon nanotube affinity substance; a carboxyl group is present on the substrate surface or the electrode surface. If there is, it is preferable that an amino group is introduced into the carbon nanotube affinity substance!
  • Examples of carbon nanotube-affinity substances into which carboxyl groups have been introduced include 1-pyren ebutyric add, etc., and carbon nanotube-affinity substances into which ester groups have been introduced. -Hyroxysuccinimide ester power included.
  • Examples of the carbon nanotube affinity substance into which 7-amino group is introduced include 1-pyrenemethylamine.
  • the substrate surface may be treated with a silane coupling agent containing a functional group that can be converted into a carboxyl group, and the functional group is converted into a carboxyl group.
  • a silane coupling agent containing a functional group that can be converted into a carboxyl group
  • the functional group is converted into a carboxyl group.
  • amino groups on the surface of the substrate for example, the surface of the substrate is treated with aminosilane. Examples of aminosilane include 3-aminopropyltriethoxysilane (APS).
  • the surface of the electrode may be treated with thiocarboxylic acid.
  • thiocarboxylic acid include 11-mercapto undecanoic acid.
  • the gold electrode may be treated with aminothiol. Examples of aminothiols include 11-
  • the resist film may be made of PMMA or the like, and the film thickness may be about 1 ⁇ m to 3 ⁇ m.
  • an aminosilane solution such as APS may be dropped onto the electrode formation planned site and dried to form a film.
  • the film is a condensation polymer such as APS. It should be about ⁇ 1 ⁇ m.
  • the carbon nanotube affinity substance may be provided by being dissolved in an organic solvent such as DMF.
  • an organic solvent such as DMF.
  • a solution of a carbon nanotube affinity substance dissolved in an organic solvent is added little by little to a solvent (for example, an aqueous solution) in which the substrate is immersed. It is preferable to remove the solvent remaining on the substrate by drying with an inert gas during the cleaning after the reaction (the same applies hereinafter).
  • the provision of the carbon nanotubes is preferably performed by providing a dispersion of separately prepared carbon nanotubes. What is necessary is just to immerse the board
  • dispersion solvents include organic solvents such as DMF and water.
  • the carbon nanotubes subjected to acid treatment are improved in water dispersibility by introducing carboxylic acid. Therefore, the provision of the acid-treated carbon nanotube is preferably carried out by dispersing it in an aqueous solvent.
  • the pH of the aqueous dispersion is at least pKa (about 4) of the carboxylic acid, preferably 7-8.
  • the concentration of carbon nanotubes in the carbon nanotube dispersion is preferably from 0.001 mgZml to 0.1 mgZml. If the concentration is as high as 0.1 mgZmU, the strong bon nanotubes tend to aggregate and it may be difficult to prepare a dispersion.
  • the carbon nanotube at the modification site By providing the carbon nanotube at the modification site, at least a part of the carbon nanotube is fixed to the substrate to connect the source and drain electrodes.
  • the carbon provided Not all of the nanotubes are fixed to the electrode formation scheduled portion of the substrate. Therefore, after providing the carbon nanotubes, it is preferable to clean the substrate and remove the unfixed carbon nanotubes before forming the electrodes.
  • the substrate is cleaned by, for example, washing the substrate with a solvent (for example, DMF) or sonicating the substrate in the solvent.
  • a solvent for example, DMF
  • the formation of the source electrode and the drain electrode may be performed by depositing metal using lithography.
  • the portion where the source or drain electrode and the channel overlap can be welded by a high electric field electron beam or a locally applied electric field using STMZAFM, so that the electrode and the channel can be integrated (the same applies hereinafter).
  • the carbon nanotubes on the substrate may be vapor-phase grown after providing the carbon nanotubes (more preferably after washing).
  • the vapor growth of carbon nanotubes is performed by using a substrate 1 on which carbon nanotubes 7 are fixed and a reaction vessel to which hydrocarbon gas (methane gas, etc.) 11 that is a raw material for carbon nanotubes is supplied. Put in 10 and heat to about 700-900 ° C. Thereby, the carbon nanotubes 7 grow as shown by the dotted line. Apply voltage between source and drain electrodes (3 and 4)! You may do it.
  • a metal is deposited by lithography.
  • a self-assembled film is formed on the electrode surface using a metal-thiol bond, and Introducing a functional group (for example, a carboxyl group or amino group) on the electrode surface; providing a force-bonn nanotube affinity substance having a functional group (for example, an amino group or ester group) that reacts with the functional group introduced on the electrode surface Is done.
  • a functional group for example, a carboxyl group or amino group
  • the electrode surface is treated with a compound having a functional group (for example, thiol group) that specifically reacts with the electrode material (for example, thiolated carboxylic acid or aminothiol). Good.
  • the carbon nanotube affinity material is provided by being dissolved in an organic solvent such as DMF.
  • a reagent for example, calpositimide
  • a functional group for example, carboxyl group
  • the functional group for example, amino group
  • a dispersion liquid in which the carbon nanotube is dispersed in an organic solvent such as DMF or water may be provided to the modification site.
  • the acid-treated carbon nanotubes are preferably provided dispersed in water.
  • the dispersion liquid may be added to the substrate, or the substrate may be immersed in the dispersion liquid.
  • the carbon nanotubes that are not fixed by washing the substrate after providing the carbon nanotubes are not fixed. Is preferably removed.
  • the substrate is washed, for example, by rinsing the substrate with a solvent or sonicating the substrate in the solvent.
  • an electrode is formed by further depositing a metal on the electrode already provided on the substrate. Is preferred.
  • an appropriate source / drain current for example, about 0.1 to 1.0 A
  • an element through which a current of about 0.1 to 1.0 A flows is not easily damaged even by washing several times with water or the like.
  • the carbon nanotubes on the substrate may be vapor-phase grown (FIG. 9). reference).
  • the carbon nanotube affinity substance for modifying the carbon nanotubes preferably has a functional group for binding to the electrode surface.
  • the carbon nanotube may be modified with a carbon nanotube affinity substance into which an amino group is introduced.
  • the carbon nanotube for modifying the carbon nanotube It is preferable that the affinity substance has a functional group that binds to the substrate surface (preferably, the electrode formation planned site).
  • the carbon nanotubes may be treated with a carbon nanotube-affinity substance into which amino groups have been introduced.
  • the carbon nanotubes may be modified by adding the carbon nanotubes to a solution containing a carbon nanotube compatible substance (the solvent is ethanol or the like).
  • a carbon nanotube compatible substance the solvent is ethanol or the like.
  • carbon nanotubes are treated with pyrene derivatives, which are examples of carbon nanotube affinity substances, and hydrophilicity is added, the dispersibility of carbon nanotubes in aqueous solution improves, so carbon nanotubes are more uniformly used as a substrate. Can be dispersed on top.
  • the carbon nanotube dispersion liquid is dropped on the substrate, or the substrate is immersed in the carbon nanotube dispersion liquid. do it.
  • the carbon nanotube dispersion liquid is dropped on the substrate, or the substrate is immersed in the carbon nanotube dispersion liquid. do it.
  • Nanotubes may be vapor grown (see Figure 9).
  • a metal is further provided on the electrode already provided on the substrate. It is preferable to form an electrode by vapor deposition.
  • the silicon oxide film on the surface of the silicon substrate (the film thickness of the silicon oxide film should be about 300 nm) is washed with 50% sulfuric acid for 30 minutes at room temperature and then with water.
  • a photoresist film (OEPR-800) is spin-coated by spin coating on the cleaned silicon oxide film. Site where source and drain electrodes are to be formed using photolithography The pair of regions of the photoresist film is removed.
  • the obtained substrate is immersed in a mixed solution of ethanol and water (volume ratio 1: 4, 50 ml) and heated to 65 ° C. 1.
  • 101 of the obtained solution is dropped into the mixed solution in which the substrate is immersed, and reacted at 65 ° C for 1 hour. (This causes pyrene to bind to the substrate surface.)
  • the obtained substrate is heated at 115 ° C. for 5 minutes and then immersed in DMF to remove the photoresist film.
  • CM Co., US 0.5 mg of single-walled carbon nanotubes (CM Co., US) is washed with a mixed solution of sulfuric acid and nitric acid, and then dispersed in 1 ml of a buffer solution.
  • the obtained solution is centrifuged, and the resulting residue is suspended in a mixed solvent of sulfuric acid and hydrogen peroxide solution and sonicated for 1 hour.
  • the resulting black solution is diluted with water and dialyzed against distilled water to neutralize the solution.
  • One-bonn nanotube solution (which is sonicated before use) is dropped on the above-mentioned substrate and left for 1 hour to fix the carbon nanotubes to the pyrene-modified region.
  • the obtained substrate is washed with DMF and ethanol.
  • the state of the area where the carbon nanotubes are fixed can be observed with an AC-mode AFM, and it can be confirmed whether the areas where the electrodes are to be formed are connected with carbon nanotubes.
  • a pattern for forming source / drain electrodes is formed on the obtained substrate.
  • a method similar to the method for patterning pyrene described above may be used.
  • the source and drain electrodes are formed by evaporating 30nm thick Pt film and lOOnm thick Au film using EB vapor deposition. The distance between both electrodes shall be about 3 m.
  • a gold electrode is formed by vapor deposition on the silicon oxide film of the silicon substrate (the film thickness of silicon oxide may be about 300 nm).
  • 11-mercaptoundecano substrate with gold electrode Immerse in ic acid solution (0.5 mM) and let stand at room temperature for 10 hours. After washing with ethanol, blow dry with nitrogen gas. (This introduces carboxyl groups on the gold electrode surface.)
  • a dimethylformamide solution of carbon nanotubes (0.5 mg / 5 ml) is dropped on the substrate and left for 10 hours. Then, after ultrasonic cleaning in DMF and ethanol, nitrogen gas is blown over the entire substrate and dried.
  • the gold electrode formed on the substrate in this method is preferably sufficiently deposited so that a current of about 0.1 to 1.0 / z A flows. This is to obtain an element that operates stably.
  • the source / drain current is excessively low, and the device may change its conductivity during use, and may lose its conductivity. Stable conductivity even when washed.
  • the obtained solution is added to a solution in which 0.6 mg of 11-amino-1-undecanethio 1 is dissolved in 100 / zL of DMF and allowed to react at room temperature for 1 hour.
  • the obtained reaction solution is added to 0.05 mg ZmL of an aqueous solution (500 L) of acid-treated carbon nanotubes and stirred at room temperature for 12 hours.
  • a substrate on which a gold electrode is formed is put into the obtained solution and reacted at room temperature for 12 hours to fix the carbon nanotubes to the substrate.
  • a DMF solution of 1-pyrenebutyric acid (5 mg / ml, 50 ⁇ 1) was added to a DMF dispersion of carbon nanotubes (0. Olmg / ml, 500 / zl) and sonicated for 2 hours at room temperature. Tetraethylenediamine 50 ⁇ 1, ethanol 50 ⁇ 1, and water 25 1 are added to the resulting solution (100 ⁇ 1) to obtain a dispersion. The resulting dispersion is filtered through a filter to remove a large excess of 1-pyrenebutyric acid. Add water-ethanol (1: 1) mixed solution to the filtrate to make lml. Thus, a carbon nanotube dispersion solution is obtained. Fix the dispersion solution of carbon nanotubes modified with 1-pyrenebutyric acid to the planned electrode treated with aminosilane using a condensation reagent such as carbodimit.
  • a condensation reagent such as carbodimit.
  • the provided carbon nanotubes are arranged along the steps of atoms on the crystal surface of the substrate; or arranged in a certain direction by electrophoresis.
  • the source and drain electrodes can be connected with the carbon nanotubes more efficiently and reproducibly.
  • the characteristics of the formed channel can be confirmed by a four-probe method.
  • Electrodes A, B, C, D Four acicular electrodes (electrodes A, B, C, D) are installed in a straight line in the channel, a constant current is passed between the two outer electrodes (electrodes A, D), and the two inner electrodes ( The resistance value is obtained by measuring the potential difference generated between the electrodes B and C), and the volume resistance value of the channel can be calculated by multiplying the obtained resistance value by the channel thickness and the correction coefficient RCF.
  • channel transport characteristics may be evaluated. Specifically, it is possible to evaluate the characteristics of noistic electrical conduction, the possibility of spin injection, and the possibility of spin transport.
  • the source and drain electrodes can be connected with carbon nanotubes (channels can be formed) with a high probability (almost 100%). Therefore, the yield of transistor manufacturing can be improved. Further, since it is necessary to vapor-phase carbon nanotubes, it is possible to employ a heat-resistant low-temperature substrate material (for example, glass).
  • Defects may be introduced into the carbon nanotubes forming the formed channel! Force Introduction of defects into a single-bonn nanotube can be done, for example, by chemically modifying; passing an excess current (several mA); irradiating with an ion or electron beam; Done.
  • the state of defects can be observed by scanning probe methods (Kelvin probe method, Maxwell probe method, etc.). And the density, distribution, and size (such as size and energy barrier) of defects can be evaluated.
  • a transistor having desired properties can be manufactured. Examples of desired properties include the property as SET (single electron transistor). Since the SET channel has a quantum dot structure, electrons stay in the dot area and the amount of current becomes very small, so that a slight change in charge on the channel can be detected sensitively.
  • a carbon nanotube FET (shown in Fig. 10) including a knock gate electrode was produced.
  • the channel was formed in accordance with the above-described specific example A of the dispersion fixing method.
  • the silicon thickness of the support substrate is 500 m
  • the thickness of the silicon oxide film on the source / drain electrode side is 3 OOnm
  • the thickness of the silicon oxide film on the gate electrode side is 300 nm
  • the thickness of the APS film is 5 to 10 nm.
  • the area of the source and drain electrodes was 0.20 to 0.25 mm 2
  • the area of the substrate was lcm 2 (lcm X lcm).
  • AFM confirmed that the source and drain electrodes were connected by several carbon nanotubes.
  • the carbon nanotube FET of the present invention can be applied to any application, it is preferably used for a biosensor.
  • a carbon nanotube FET including various types of gate electrodes and an embodiment in which the carbon nanotube FET is used as a biosensor will be described.
  • the aspect of the carbon nanotube FET and the aspect of the biosensor are not limited to these.
  • FIG. 12 shows an example of a carbon nanotube FET including a back gate electrode.
  • reference numeral 1 denotes an insulating substrate.
  • a source electrode 3, a drain electrode 4, and a channel 7 made of carbon nanotubes are provided on one surface of the insulating substrate 1, and on the other surface of the insulating substrate 1.
  • the gate electrode 8 is provided (with the surface force separated) (sandwich type gate electrode). If the substance-recognized molecule 13 is bonded to the surface of the insulating substrate 1 on the gate electrode side, the other surface of the insulating substrate 1 (the surface to which the substance-recognized molecule 13 is bonded) and the gate electrode 8 are placed. By interposing a sample solution, it can be used as a sensor for detecting a substance to be detected.
  • the substance-recognized molecules 13 are arranged on the back surface of the substrate surface on which the carbon nanotubes are arranged. Can be cleaned and reused.
  • the carbon nanotube FET shown in FIG. 12 can bind the target substance recognition molecule to the entire surface of the insulating substrate (surface without the channel), a relatively large number of recognition molecules are bound. be able to.
  • a substance-to-be-detected molecule is bound to a carbon nanotube that is a channel, it can be easily used for detection repeatedly by washing.
  • Washing can be performed, for example, with a solution having a pH equal to or lower than the dissociation constant (when NTA-Ni complex is used to bind the substance to be detected, the solution is reduced to pKa (about 6) or less of the imidazole ring). This can be done using imidazole, which facilitates liberation of Ni from NTA). Further, if a mirror-surface silicon oxide film is formed by polishing the substrate surface, recognition molecules (eg, antibodies) can be easily bound using a histag or the like.
  • recognition molecules eg, antibodies
  • FIG. 13 and FIG. 14 show examples of carbon nanotubes FET including a back gate electrode, respectively.
  • reference numeral 1 denotes an insulating substrate.
  • a source electrode 3, a drain electrode 4, and a channel 7 made of carbon nanotubes are provided on one surface of the insulating substrate 1, and the other surface of the insulating substrate 1 is provided.
  • a gate electrode 8 is provided on the top.
  • an insulating thin film 30 covering the channel 7 is provided.
  • the sample solution 15 can be used as a sensor for detecting the detection substance by allowing the sample solution 15 to cover the channel 7. . Further, if the substance to be detected recognition molecule 13 is bound to the insulating thin film 30 in FIG. 14, the sample solution can be used as a sensor for detecting the substance to be detected by allowing the sample solution to cover the channel. At this time, it is preferable that the entire force of the source electrode 3 or the drain electrode 4 is not covered with the sample solution. Therefore, as described above, it is preferable that the length of the source electrode 3 or the drain electrode 4 from the channel is long. Also melt It is preferable that the electrode part covered with the liquid is small.
  • the substance-recognizing molecule 13 is directly bonded to the channel 7, and therefore this carbon nanotube FET can provide a highly sensitive sensor.
  • the channel 7 is protected by the insulating thin film 30, the stability is high, and the substance to be detected substance recognition molecule 13 is bonded to the insulating thin film 30 covering the channel. Since the sample solution does not come into direct contact with the electrode, a highly sensitive sensor can be provided.
  • FIGS. 15 to 18 show examples of carbon nanotube FETs including a back gate electrode.
  • reference numeral 1 denotes an oxide silicon film and an insulating substrate which also has a silicon force, and source / drain electrodes 3 and 4 and a channel 7 made of carbon nanotubes are arranged on the silicon oxide film of the insulating substrate 1. . Further, a part of the silicon portion of the insulating substrate 1 is removed to provide a recess 16. The recess 16 can be easily formed by physically or chemically etching the silicon portion. Etch the silicon part until the oxide silicon film is exposed as shown in Figure 15.
  • the silicon oxide film is preferably thin in order to improve the sensitivity to the voltage of the gate electrode (not shown). In order to reduce the film thickness, the silicon oxide film is preferably formed by oxidizing silicon.
  • the volume of the recess 16 By adjusting the volume of the recess 16, an appropriate fixed amount of sample solution can be provided. Further, the added sample solution can be stably held at the sample detection site where it is difficult to escape. Further, the sample solution held in the recess 16 can be transported to another detection device. For example, the sample solution may be continuously flowed into the recess 16 using micro-TAS.
  • a substance-to-be-detected molecule 13 can be bound inside the recess 16 and the sample solution can be held there.
  • the recess 16 may be arranged downward as shown in FIG. 15 or may be arranged upward as shown in FIG. Even if the recess 16 faces downward, a small amount of liquid can be held in the recess 16 by surface tension.
  • the detection target substance recognition molecule 13 is bound to the recess 16 and the sample solution After the measurement, the gate electrode is further arranged, and the change in the IV characteristic or the I Vg characteristic is observed, so that the substance to be detected contained in the sample solution can be detected.
  • the gate electrode of the carbon nanotube FET provided with the recess 16 may be disposed so as to close the recess 16 (see FIG. 17), or may be placed on the silicon portion or the silicon oxide film. They can be placed in contact (see Figure 18).
  • FIG. 17A shows a gate electrode arranged so as to close the recess 16 and not to contact the sample solution.
  • FIG. 17B shows the gate electrode arranged so as to close the recess 16 and to be in contact with the sample solution. If the gate electrode is arranged so as to close the recess 16, evaporation of the sample solution 15 can be suppressed, and the mechanical strength of the FET can be improved.
  • FIGS. 18A and 18D are in contact with the silicon portion. Shown are the gate electrodes arranged in such a way.
  • FIGS. 18B and 18C show the gate electrodes of the silicon oxide film on which the source and drain electrodes are formed, arranged in contact with the same surface and the back surface of the source and drain electrodes, respectively.
  • a short needle 17 to which a substance to be detected recognition molecule 13 is bonded is arranged on the back surface of the substrate 1 on which the source and drain electrodes are formed, and the short needle 17 force knock gate electrode 41 is connected. It is inserted into the sample 15 in contact. If the detection substance recognition molecule 13 is bound only to the tip of the short needle 17, the detection position in the sample 15 can be limited. Examples of sample 15 include the brain or body surface of an animal, and it is considered possible to measure the potential.
  • FIGS. 20 to 23 also show examples in which a substance to be detected is bound to a carbon nanotube FET including a back gate.
  • the carbon nanotube FET substrate shown in these figures is composed of a support substrate 102 that also has metal or semiconductor power, and insulating films 104 and 106.
  • a substance-recognizing molecule 472 is bonded to the insulating film 106 and sandwiched between the gate electrode 512 and the substrate (sandwich gate electrode).
  • Sample solution 490, gate electrode 5 The substance to be detected is detected by being present between 12 and the substrate.
  • the target substance recognition molecule 472 is bonded to the insulating film 106.
  • the force gate electrode 522 is bonded to the substrate.
  • the detection substance can be detected.
  • the sample solution 490 may or may not be in contact with the gate electrode 522 (FIG. 21 (A)) or in contact with /! (FIG. 21 (B)).
  • the substance to be detected recognition molecule 472 is bonded to the gate electrode 532. By contacting the sample solution 490 with the substance-recognizing molecule 472, the substance to be detected can be detected.
  • Fig. 22 (A) when a plurality of gate electrodes are provided, carbon nanotube FETs (Fig. 22 (A)) in which the target substance recognition molecules 472a and 472b are bonded to the insulating film 106 and the gate electrodes 532a and 532b are combined.
  • the carbon nanotube FET (Fig. 22 (B)) is shown.
  • the detected substance can be detected by bringing the detected substance recognition molecules 472a to 472b into contact with the sample solutions 490a to 490b, respectively.
  • FIG. 23 shows a carbon nanotube FET in which a substance-recognizing molecule 472 is bound to an insulating protective film 640 that protects the carbon nanotube 112.
  • the gate electrode is 114.
  • FIG. 24 shows an example of a carbon nanotube FET including a side gate electrode.
  • a gate electrode 8 is provided in contact with the same surface as the substrate surface on which the source / drain electrodes 3 and 4 are formed.
  • Channel 7 is made into an island structure by introducing a force defect that can also be a carbon nanotube force.
  • the gate electrode 8 is usually disposed at a distance of less than lOOnm.
  • Molecules to be detected Can be used as a sensor by binding a recognition molecule to, for example, a force for binding to a gate electrode or a channel or an insulating film covering the channel.
  • FIG. 25 also shows an example of a carbon nanotube FET including a side gate electrode.
  • the carbon nanotube FET substrate shown in FIG. 25 includes a support substrate 102 and an insulating film 104. On the insulating film 104, source / drain electrodes 108 and 110, a channel 112 made of carbon nanotubes, and a gate electrode 702 are arranged. The source / drain electrode and the gate electrode are covered with the insulating film 640, and the substance to be detected is covered with the insulating film 640.
  • the recognition molecule 472 binds and strikes. The target substance recognition molecule 472 binds to any position of the insulating film 640 as long as it is bound to the source / drain electrode part, gate electrode part, channel part, or other part.
  • FIG. 26 shows an example in which a substance to be detected is bound to a carbon nanotube FET including a side gate electrode (top gate electrode).
  • the source electrode 3 and the drain electrode 4 disposed on the surface of the insulating substrate 1 and the channel 7 made of carbon nanotubes are covered with an insulating film 40 (for example, a glass insulating film) (FIG. 26A). Further, the gate electrode 8 is disposed on the insulating film 40! (FIG. 26B).
  • the sample solution 15 is interposed between the insulating film 40 and the gate electrode 8 to be used as a sensor for detecting the substance to be detected. Can do.
  • the gate electrode is connected between the source electrode or the gate electrode and the drain electrode. It is possible to suppress the leakage of current between.
  • a glass insulating film may be provided on the gate electrode 8 shown in FIG. In this case, however, the distance between the channel and the gate electrode increases, which may weaken the properties of the FET. Furthermore, in the carbon nanotube FET in FIG. 26, if the insulating substrate 1 is a glass substrate, the state of the sample is observed from the back side (surface on which no electrode is disposed) of the substrate 1 using an optical microscope, a fluorescence microscope, or a laser microscope. The transistor can be driven while checking the above.
  • FIG. 27 also shows an example in which a substance to be detected is bound to a carbon nanotube FET including a side gate electrode (top gate electrode).
  • a substance to be detected recognition molecule 472 is bonded to an insulating protective film 640 that protects a channel made up of carbon nanotubes.
  • the gate electrode 702 is disposed without being in contact with the substrate (consisting of the support substrate 102, the insulating film 104, and the insulating film 106).
  • FIGS. 28 to 33 show examples in which the substance-recognizing molecule to be detected is bound to the carbon nanotube FET including the separation gate electrode.
  • the carbon nanotube FET shown in Fig. 28 is a device part including source and drain electrodes. 212, an element portion 214 including a gate electrode, and a conductive substrate 210 on which the element portion 212 and the element portion 214 are mounted.
  • the element portion 212 and the element portion 214 are electrically connected.
  • the element section 212 includes a substrate (support substrate 102, insulating films 104 and 106), source / drain electrodes 108 and 110 disposed on the substrate, and a channel 112 made of carbon nanotubes.
  • the element unit 214 includes a substrate (support substrate 202, insulating films 204 and 206) and a gate electrode 602 disposed on the substrate.
  • the gate electrode 602 is disposed without contacting the substrate (sandwich gate electrode).
  • the substance-recognizing molecule 472 is bonded to the insulating film 204 of the substrate on which the gate electrode 602 is disposed. By allowing the sample solution 490 to exist between the gate electrode 602 and the insulating film 204, the substance to be detected can be detected.
  • FIG. 29 shows a modified example of the element portion 214 including the gate electrode in FIG.
  • the gate electrode 612 or 622 in FIG. 29 is placed in contact with the substrate (non-Sanch-type gate electrode).
  • the detection substance recognition molecule 472 is bonded to the insulating film 204 of the substrate, and in FIG. 29C, the detection substance recognition molecule 472 is bonded to the gate electrode 622.
  • the substance to be detected can be detected.
  • the sample solution 490 may or may not be in contact with the gate electrode 612 (FIG. 29 (A)) (FIG. 29 (B)).
  • FIG. 30 shows a further modification of the element portion 214 including the gate electrode in FIG.
  • Two or more gate electrodes 612a and 612b (622a and 622b) and two or more kinds of detected substance recognition molecules 472a and 472b are arranged.
  • the carbon nanotube FET shown in FIG. 31 is a force including two or more element parts 212 including source and drain electrodes and two or more element parts (214a and 214b) including gate electrodes.
  • the carbon nanotube FET shown in FIG. Similarly to the above, all the element portions are mounted on one conductive substrate 210.
  • FIG. 32 and FIG. 33 show another example of the carbon nanotube FET including the separation gate.
  • the carbon nanotube FET in FIG. 32 is sandwiched between the element part 212 including the source and drain electrodes, the element part 214 including the gate electrode, and the substrate of the element part 212 and the substrate of the element part 214.
  • a conductive substrate 210 is included.
  • the carbon nanotube FET of FIG. 33 includes an element part 212 including a source / drain electrode, an element part 214 including a gate electrode, a conductive substrate 302 on which the element part 212 is placed, and a conductive material on which the element part 214 is placed.
  • Conductive substrate 304, and conductive wires 306 that electrically connect conductive substrates 302 and 304.
  • the substance-detecting molecule 472 can be coupled to the gate electrode 612 (force) coupled to the insulating film 204 of the element unit 214 (shown). (Detected substance recognition molecules bound to the electrode 612 are not shown).
  • the carbon nanotube FET of the present invention can be used as a biosensor.
  • the target substance recognition molecule is bound to the carbon nanotube FET.
  • substances to be detected include microorganisms such as viruses and bacteria, chemical substances such as residual agricultural chemicals, carbohydrates, nucleic acids, amino acids, and lipids.
  • the substance to be detected include an antibody, an antigen, an enzyme, a receptor, a nucleic acid, an abutama cell, a microorganism, and the like.
  • the substance to be detected is an antigen, it is an antibody or an Abutama, and when the substance to be detected is an antibody, it is an antigen.
  • microorganisms such as pathogenic viruses and bacteria of infectious diseases can be detected with high sensitivity and in a short time. Therefore, it can be effectively used for early treatment by early detection of infectious diseases and for research on microorganisms. In addition, since the size of the sensor can be reduced, it can be used to detect infectious disease viruses in the field.
  • the biosensor of the present invention is operated with an alternating current using a resonance circuit, and detects the substance to be detected from a change in the source-drain current or voltage caused by binding of the substance to be detected to the substance to be detected. Can be detected.
  • the change in the source / drain current or voltage is confirmed by, for example, an I-V characteristic curve or an I-Vg characteristic curve.
  • the I—V characteristic curve is the curve showing the relationship between the source-drain current and the source-drain voltage when the gate voltage is constant; the I—Vg characteristic curve is the constant source 'drain voltage.
  • FIG. 5 is a curve showing the relationship between the gate voltage and the source / drain current.
  • the target substance recognition molecule in the biosensor of the present invention may be bound so as to react with the target substance and change the source drain current.
  • the gate electrode it is only necessary to be bonded to a channel made of carbon nanotubes, a gate electrode or a substrate, or an insulating film for protecting them! / ⁇
  • the means for binding the force detection substance recognition molecule including the carbon nanotube FET to which the detection substance recognition molecule is bound to the carbon nanotube FET there is no particular limitation on the means for binding the force detection substance recognition molecule including the carbon nanotube FET to which the detection substance recognition molecule is bound to the carbon nanotube FET.
  • the first method uses a histag fusion recognition molecule as a substance to be detected.
  • a histag fusion recognition molecule as a substance to be detected.
  • a method of binding a histag fusion antibody to a channel that also has a carbon nanotube force will be described with reference to FIG.
  • the insulating substrate and the gate electrode can be bonded in the same way.
  • an antibody 50 to which a histag 51 is added is prepared by genetic manipulation.
  • the carbon nanotubes of the field effect transistor are directly modified with a pyrene derivative.
  • NTA52 is bound to carbon nanotubes modified directly with pyrene derivatives.
  • a solution containing transition metal ions (nickel ions, cobalt ions, etc.) is dropped onto the carbon nanotubes to form a complex with NTA52 fixed to the carbon nanotubes.
  • the antibody 50 is immobilized on the carbon nanotubes as shown in FIG. 34 (A) by dropping a solution containing the antibody 50 attached with the histag 51.
  • the antibody 50 thus immobilized has a certain orientation with respect to the binding surface.
  • the insulating film is preferably treated with a silane coupling agent.
  • NTA52 is bonded to the gate electrode (metal, for example, gold), it is effective to use NTA with a thiol group (N-maleimide group attached with a thiol group! /, NTA, etc.) It is. NTA into which a thiol group is introduced is commercially available (for example, Dojindo).
  • the second method is a method using protein A, protein G, protein L, or their IgG binding domain as an IgG-type antibody as a substance to be detected.
  • the antibody described here includes a single chain antibody having a specific binding ability to an antigen, Fab, and F (ab ′) 2.
  • Protein AZG a fusion protein that combines protein A, protein G, or its IgG binding properties, has the ability to bind to the Fc region of IgG-type immunoglobulins.
  • Protein L has the ability to bind to the kappa chain of the light chain of IgG type immunoglobulin. In addition, as with other proteins, all have the property of being easily attached to the gold surface.
  • ⁇ IgG binding protein '' a recombinant protein 53 having a protein A, protein G, protein AZG, protein L, or their IgG binding domain on a gate electrode made of gold.
  • the antibody 50 can be oriented to some extent by binding the IgG-type antibody 50 used as the substance to be detected to the target IgG-binding protein 53.
  • IgG-binding protein 53 is randomly bound to the electrode (see FIG. 34 (B)), so that sufficient orientation may not be obtained.
  • an IgG-binding protein with a histag is prepared, and the IgG-binding protein is bound to a gate electrode or the like via NTA-Ni and a histag, and the same method as in the first method.
  • This is a method of orienting a substance-recognizing molecule (antibody).
  • the target substance recognition molecule antibody
  • the target substance recognition molecule can be oriented to the insulating film or the carbon nanotube.
  • IgG binding protein 53 to which a histag 51 is added is prepared by genetic manipulation.
  • the orientation of the antibody can be improved by setting the position of the his-tagged caro in consideration of the position of the antibody binding site.
  • the insulating film is treated with a silanizing coupling agent to bind NTA52 to the modified substrate; a solution containing transition metal ions (such as nickel ions and cobalt ions) is dropped onto the substrate and fixed on the substrate.
  • transition metal ions such as nickel ions and cobalt ions
  • a substance-recognizing molecule (an antibody, an enzyme, etc.) is divided into two functional groups 55, 56 (which may be the same or different).
  • This is a method of bonding to an insulating film, a gate electrode, or a carbon nanotube through a divalent crosslinking reagent 54 having the following.
  • the bivalent crosslinking reagent 54 includes two functional groups 55 and 56 and a hydrophilic polymer chain such as polyethylene glycol or a hydrophobic chain such as an alkyl chain that connects the two functional groups 55 and 56.
  • Examples of the combination of the functional groups 55 and 56 include a combination of a functional group in which one side forms a covalent bond with an amino group and the other side forms a covalent bond with a thiol group.
  • a functional group in which one side forms a covalent bond with an amino group and the other side forms a covalent bond with a thiol group For example, when binding to an insulating film, 1) react the target substance recognition molecule (antibody 50) with the bivalent crosslinking reagent 54, and then remove the unreacted bivalent crosslinking reagent by dialysis or the like.
  • the substrate insulating film treated with the silane coupling agent and the target substance-recognizing molecule-bivalent cross-linking reagent complex are reacted and fixed, or 2) the substrate treated with the silanization coupling agent It can be immobilized by reacting the insulating film surface with the divalent crosslinking reagent 54; and further reacting with a molecular recognition substance (antibody 50).
  • the method using the bivalent cross-linking reagent 54 requires a genetic modification operation to add a histag to the antibody or protein. It can be prepared quickly.
  • antibodies are detected When used as a sensing molecule, polyclonal antibodies are difficult to use with NTA methods, but polyclonal antibodies can be used with the immobilization method using a bivalent cross-linking reagent, improving sensitivity and accuracy as a biosensor. Can be expected.
  • the bivalent cross-linking reagent has a hydrophilic polymer chain or a hydrophobic chain between the two functional groups 55 and 56, the knock ground during detection can be reduced.
  • a substance to be detected can be detected by using the biosensor of the present invention.
  • the substance to be detected may be detected from the change in the source / drain current or voltage generated by binding to the substance to be detected substance recognition.
  • a solution is used as a sample.
  • a sample solution may be added to a substrate to which a substance to be detected recognition molecule is bound.
  • the sample solution contains a substance to be detected, a reaction (for example, an antigen-antibody reaction) between the substance to be detected and the substance to be detected is recognized.
  • a reaction for example, an antigen-antibody reaction
  • the solvent for example, water
  • the solvent contained in the added sample solution affects the source / drain current, it may generate noise in detection. Examples of means for reducing the noise include the following means.
  • the solvent of the added sample solution is removed by evaporation.
  • the removal by transpiration may be performed using, for example, nitrogen gas or the like, or using a heater, a thermoelectric conversion element (Peltier element), or the like.
  • the transpiration by the blower it is preferable that the sample is made into a uniform thin film by slowly evaporating while slightly applying the blower.
  • Cooling can be performed with a thermoelectric conversion element (Peltier element) or liquid nitrogen.
  • the transistor is driven by applying the gate electrode to the portion where the sample solution is added (preferably after the sample solution is evaporated or cooled). Measure I—V characteristics or I—Vg characteristics. I—V characteristics can be measured in a short time (for example, within a few seconds) by a parameter analyzer.
  • the gate electrode may be applied to a portion where the sample solution is added with a glass thin film interposed therebetween.
  • the insulation between the gate electrode and the source / drain electrodes can be improved, and the leakage current can be reduced.
  • the biosensor of the present invention can also detect two or more types of detected substances just by detecting one type of detected substance. Two or more kinds of detected substances contained in one sample can be detected, and two or more kinds of samples can be detected in parallel.
  • the nanosensor of the present invention may be disposable after one detection when the substance to be detected is a dangerous virus. It can also be used repeatedly for multiple detections.
  • a carbon nanotube FET (Fig. 10) containing a channel prepared according to the specific example A of the above-described dispersion fixing method was prepared.
  • the surface of the silicon oxide film (lc m 2 ) on the back surface of the prepared carbon nanotube FET substrate was washed with a piranno-sodium solution and ethanol and dried.
  • (S810) mercaptopropyltrimethoxysilane of 31 was dropped onto the surface of the silicon oxide film and heated to 180 ° C. for 2 hours. After cooling to 30 ° C, it was treated with 50 mM dithiothreol (DTT) at the same temperature for 1 hour or more, and then washed with water.
  • DTT dithiothreol
  • a maleimide-NTA solution (lm gZml) prepared using a 10 mM phosphate buffer (pH 6.5) was layered on the surface of the above-described acid-silicon film and allowed to stand at room temperature for 1 hour. After standing, it was washed with water and dried with nitrogen gas (dried until no water droplets disappeared).
  • a 50 1 NiC12 solution (50 mM) was dropped onto the surface of the silicon oxide film. 1 After standing for 5 minutes, it was washed with water and dried with nitrogen gas (dried until no water droplets were observed).
  • the probe connected to the semiconductor parameter analyzer was connected to the source drain electrode, and the IV characteristics were measured.
  • the I–V characteristic curve (showing the relationship between the source / drain current and the source / drain electrode) was obtained with a gate voltage of 20V.
  • HA antigen Recombinant hemadalchun (HA) protein an antibody recognition molecule used as a target substance recognition molecule, was prepared. Specifically, it is a recombinant HA protein with a histidine tag added to the C-terminus, with various levels (1-220, 1-250, 1-290, 1-320; the numbers are amino acids on the primary sequence An attempt was made to express a protein that was truncated at the residue number.
  • Recombinant HA protein expression plasmids corresponding to each were introduced into 293T cells. Using monoclonal antibody E2Z3 and polyclonal antibody, it was confirmed that recombinant HA protein was expressed in cells. Furthermore, it was confirmed that the recombinant HA protein was secreted into the supernatant by Western plotting.
  • HA1-290 and HA1-220 were expressed in large quantities. In each case, the supernatant secretion was purified on an NTA-Ni 2+ column. The fraction containing the target recombinant HA protein was confirmed by ELISA and Western blot, and fractionated. The aliquot was dialyzed against PBS to obtain recombinant HA protein. Of HA1-290 and HA1-220, HA1-220 no longer reacts with the monoclonal antibody, so HA1-290 was used as the analyte recognition molecule.
  • the recombinant hemadunchun (HA) protein HA1-290 obtained as described above (1.9 / ⁇ 8 ⁇ 1; 50 / ⁇ 1) was added. And fixed.
  • the IV characteristic curve was obtained in the same manner as described above.
  • FIG. 35 A schematic diagram of the fabricated sensor is shown in FIG. In FIG. 35, ⁇ antigen 472 is immobilized on the silicon oxide film 106 on the substrate on the back gate electrode 512 side of the carbon nanotube FET shown in FIG. 10, and the sample is placed between the knock gate electrode 512 and the silicon oxide film 106. The sensor with solution 490 added is shown. [0113] Reaction with anti-HA antibody
  • Fig. 36 shows the obtained IV characteristic curve.
  • the source and drain currents differ significantly depending on the concentration of the anti-HA antibody. That is, according to the dilution rate of the antibody stock solution is 5 X 10 _9, 5 X 10_ 8, 5 X 10 _7, the absolute value of the source 'drain current is increased. Therefore, anti-HA antibody can be detected based on the change in the source / drain current. On the other hand, the dilution ratio in the case of 5 X 10_ 6, the absolute value of the current compared with the case of 5 X 10_ 7 is reduced.
  • the channel of the carbon nanotube FET of the present invention can be formed by the dispersion-fixing method, it can be easily manufactured and the manufacturing cost is remarkable as compared with the conventional carbon nanotube FET. Can be reduced.
  • the carbon nanotube FET of the present invention has a performance equal to or higher than that of the conventional carbon nanotube FET.
  • the carbon nanotube FET of the present invention has a performance equal to or higher than that of the conventional carbon nanotube FET.
  • highly sensitive detection is possible.

Abstract

La présente invention concerne un transistor à effet de champ à nanotube de carbone, c.-à-d. un transistor à effet de champ dans lequel un canal formé par un nanotube de carbone est fixé à un substrat par un matériau d'affinité avec les nanotubes de carbone. Le transistor à effet de champ est fabriqué par un procédé comportant : une étape de préparation d’un substrat sur lequel l'emplacement où doivent être situées une électrode de source et une électrode de drain est modifié par le matériau d’affinité avec les nanotubes de carbones ; une étape de placement du nanotube de carbone pour placer le nanotube de carbone sur l’emplacement de position des électrodes sur le substrat ; et une étape de placement des électrodes pour placer une électrode de source et une électrode de drain sur l’emplacement de position des électrodes sur le substrat.
PCT/JP2006/304167 2005-03-28 2006-03-03 Transistor à effet de champ à nanotube de carbone WO2006103872A1 (fr)

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JP2009064925A (ja) * 2007-09-05 2009-03-26 Brother Ind Ltd 薄膜トランジスタの製造方法及びその製造方法により製造された薄膜トランジスタ。
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