CN101070154B

CN101070154B - Carbon nanotube chain and production process for the same, target detector, and target detection method

Info

Publication number: CN101070154B
Application number: CN2007100919336A
Authority: CN
Inventors: 伊藤健一; 益田秀树; 京谷隆
Original assignee: Tohoku University NUC; Fujitsu Ltd; Kanagawa Academy of Science and Technology
Current assignee: Tohoku University NUC; Fujitsu Ltd; Kanagawa Academy of Science and Technology
Priority date: 2006-03-31
Filing date: 2007-03-30
Publication date: 2010-08-18
Anticipated expiration: 2027-03-30
Also published as: CN101070154A; US20070237705A1; DE102007014880B4; JP2007268692A; DE102007014880A1

Abstract

To provide a carbon nanotube chain consisting of a row of carbon nanotubes, the carbon nanotube chain being suitably used for instance as a target detector or sensor, and an efficient production process for the same. The carbon nanotube chain includes a support, and a plurality of carbon nanotubes bonded at one end to a surface of the support, wherein the plurality of carbon nanotubes is oriented in a direction substantially orthogonal to the surface of the support.

Description

Carbon nanotube chain and production technique thereof and object detector and object detection method

The cross reference of related application

The application based on and require the right of priority of the No.2006-100656 of Japanese patent application formerly of on March 31st, 2006 application, its full content is by incorporating this paper into reference to quoting.

Technical field

The present invention relates to by the capable carbon nanotube chain that constitutes of carbon nanotube, also relate to the object detection method of the production technique of carbon nanotube chain, the object detector that uses carbon nanotube chain and use object detector.

Background technology

Carbon nanotube (can be called " CNT " hereinafter) is used as the material of innovation in the various fields that comprise electronics and electrician's industry, and produces via for example arc-over, laser vaporization, thermal chemical vapor deposition (thermal CVD) or plasma activated chemical vapour deposition (plasma CVD).The known carbon nanotube of method production is categorized into the single-layer carbon nano-tube (single-walled nanotube that comprises single graphite flake thus; SWNT) and comprise multilayer carbon nanotube (many walls nanotube of a plurality of graphite flakes; MWNT).

The excellent physical properties of carbon nanotube is applicable on the various uses it, comprises for example micro element of electrical connector, battery, high frequency antenna, scanning tunnel microscope, atomic force microscope and the Scanning Probe Microscopy of unicircuit, computer semi-conductor chip.In addition, the people's various application of carbon nanotube in many other fields that also wait in expectation.When multilayer carbon nanotube needing to be particularly useful in the nanotechnology of high definition, high accuracy etc., the ideal carbon nanotube needed discharging fitly.

Yet the length of the carbon nanotube by preparation such as arc-over, thickness etc. are inconsistent, and to produce what obtain be the subparticle that disperses; Therefore, be difficult to the carbon nanotube that obtains specifying number and it is arranged with regular spacing.

In order to overcome these difficulties, proposed to be used for the technology of production carbonaceous nanostructure, the step of this technology comprises, is the template growth carbon nanofiber, removes the carbon and molten anodised aluminium (alumina) nanoporous (seeing Japanese Patent Application Laid-Open (JP-A) No.2004-243477) that goes that are deposited on the alumina laminar surface with anodised aluminium (alumina) nanoporous by gas carburization.The advantage of these methods is the size of nanoporous under its environment that can accurately be controlled at anodizing, and the size of the carbon nanotube of producing in nanoporous.Yet, be arranged in as hexagonal closs packing structure etc. the anodised aluminium of being produced (alumina) nanoporous bidimensional, therefore, the bidimensional aggregate that resulting carbonaceous nanostructure is a carbon nanotube.Therefore, this method can not provide the carbon nanotube of proper alignment (for example, embarking on journey).

The objective of the invention is to solve above-mentioned general issues and reach following illustrative purposes.Promptly the object of the present invention is to provide by length is 1 μ m or the littler capable carbon nanotube chain that constitutes of carbon nanotube, and this carbon nanotube chain is applicable to for example as object detector or transmitter; Carbon nanotube chain production technique efficiently also is provided; Can carry out high-sensitivity detection by using carbon nanotube chain to provide, and all types of target is comprised that morbid substance, biological substance and toxic substance carry out the object detector of qualitative and quantitative analysis, it can be suitable for makes biosensor and gas sensor; And by using object detector to carry out simple and easy and object detection method high-sensitivity detection to detecting target.

Summary of the invention

The method that overcomes the above problems is narrated in the appended claims.Be that carbon nano chain of the present invention comprises a carrier and an end and a plurality of carbon nanotubes of carrier surface bonded, wherein a plurality of carbon nano-tube oriented in becoming the direction at a right angle basically with carrier surface.As mentioned above, an end of carbon nanotube combines with carrier, makes carbon nano-tube oriented in becoming the direction at a right angle basically with carrier surface thus.Therefore, when carrier is a sheet object, banded object or wire object, can form sheet carbon nanotube chain, banded carbon nanotube chain or wire carbon nanotube chain respectively.In addition, because carbon nanotube chain has adsorptive power and releasability, can comprise that morbid substance, biological substance and toxic substance detect to all types of target, and be applicable to and comprise in the various fields for example as object detector, biosensor and gas sensor.

The technology that the present invention is used to produce carbon nanotube chain relates to the production of carbon nanotube chain of the present invention, this technology is included in and forms groove in the metal level, with carry out nanoporous and form to handle to form nano-pore structure, it is capable wherein to form nanoporous in each groove, and this nanoporous is oriented to the direction (nano-pore structure formation step) that becomes a right angle with layer on surface of metal basically; In each nanoporous, form carbon nanotube (carbon nanotube formation step); Remove the lip-deep carbon of metal level basal plane (1ands) (carbon removing step) that is deposited between groove; And the molten metal level (the molten step of going of metal level) that goes.

Form in the step at nano-pore structure of the present invention, groove forms in metal level, then metal level is carried out nanoporous and forms processing.Obtain nano-pore structure thus, it is capable wherein to obtain nanoporous in groove, and described nanoporous is oriented to the direction that becomes a right angle with layer on surface of metal basically.Form in the step at carbon nanotube, in nanoporous, form carbon nanotube.Remove in the step at carbon, remove at carbon nanotube and form the lip-deep carbon of metal level basal plane that is deposited in the step between groove.Remove in the step the molten metal level that goes in that metal level is molten.By these steps, produce carbon nanotube chain of the present invention effectively.

Object detector of the present invention comprises carbon nanotube chain of the present invention and fixer, wherein carbon nanotube chain comprise can the Acquisition Detection target the part of catching.Catch part owing to the carbon nanotube chain of the present invention in the object detector comprises this, can catch part by this and catch various detection targets.In addition, because carbon nanotube chain is fixed on the fixer, this object detector can be manipulation.When two or more carbon nanotube chains is fixed on fixer, can gives each carbon nanotube chain different functions, and further give the different function of carbon nanotube of different groups in each carbon nanotube chain.Therefore, object detector of the present invention can carry out high-sensitivity detection, and all types of target comprised that morbid substance, biological substance and toxic substance carry out qualitative and quantitative analysis, it can be applicable to the transmitter that comprises in the various fields as biosensor and gas sensor.

Object detection method of the present invention comprises makes object detector of the present invention act on comprising on the sample that detects target.Use the object detector of the present invention that comprises carbon nanotube chain of the present invention because object detection method of the present invention relates to, various detection targets all act on carbon nanotube.Therefore, can carry out simple and easy and highly sensitive detection to the detection target in the sample.When object detector has two or more carbon nanotube chains, can give each carbon nanotube chain different functions, and further give the different function of carbon nanotube of different groups in each carbon nanotube chain.Therefore, different detection targets can act on carbon nanotube chain or carbon nanotube, allows thus a plurality of detection targets are carried out Synchronization Analysis.

Description of drawings

Figure 1A is a synoptic diagram, the state before capable formation of demonstration nanoporous, and its width changes with regular spacing.

Figure 1B is a synoptic diagram, the state after showing that nanoporous is capable and forming, and its width changes with regular spacing.

Fig. 2 A is a picture, shows the example on the aluminium lamination surface that has the mold imprinted pattern.

Fig. 2 B is a picture, shows the capable example of nanoporous that forms by the anodizing to the aluminium lamination that is shown in Fig. 2 A.

Fig. 3 A is used to illustrate that the present invention is used to produce the first step of the processing step of carbon nanotube chain.

Fig. 3 B is used to illustrate that the present invention is used to produce second step of the processing step of carbon nanotube chain.

Fig. 3 C is used to illustrate that the present invention is used to produce the 3rd step of the processing step of carbon nanotube chain.

Fig. 3 D is used to illustrate that the present invention is used to produce the 4th step of the processing step of carbon nanotube chain.

Fig. 3 E is used to illustrate that the present invention is used to produce the 5th step of the processing step of carbon nanotube chain.

Fig. 3 F is a synoptic diagram, shows the example of carbon nanotube chain of the present invention.

Fig. 4 is a synoptic diagram, shows that carbon that the present invention is used to produce the technology of carbon nanotube chain removes the example of step.

Fig. 5 is a picture, is presented at the example of the nanoporous arrangement that forms on the anode metal laminar surface.

Fig. 6 is a synoptic diagram, shows the example of object detector of the present invention.

Fig. 7 A is first synoptic diagram of the example of the experimental technique that shows the adsorptive power be used to assess object detector of the present invention.

Fig. 7 B is second synoptic diagram of the example of the experimental technique that shows the adsorptive power be used to assess object detector of the present invention.

Detailed Description Of The Invention

(carbon nanotube chain and production technology thereof)

The present invention comprises that for the production of the technology of carbon nanotube chain nano-pore structure forms step, CNT forms step, carbon removing step and metal level and dissolves step, and further comprises the additional step of suitably selecting when needed.

Can produce aptly carbon nanotube chain of the present invention for the production of the technology of carbon nanotube chain by the present invention. In connection with the explanation of technology of the present invention, provide the detailed description of carbon nanotube chain of the present invention hereinafter.

＜nano-pore structure forms step 〉

It is the step that forms nano-pore structure that nano-pore structure forms step, wherein forms groove in metal level, carries out thereafter nano-pore and forms to process to make to form to be oriented to layer on surface of metal in groove and basically become the nano-pore of direction at a right angle capable.

The material of metal level, shape, size etc. are not particularly limited and can suitably determine according to predetermined purpose.As long as, can use any material carrying out to form nanoporous when nanoporous forms processing; The example of material comprises metal element, its oxide compound, its nitride and its alloy, wherein, and preferred alumina (aluminum oxide) and aluminium.

Metal level can form on substrate.In the case, substrate can be by any suitable material manufacturing, and according to predetermined purpose, can have any suitable shape, structure and size.The example of material comprises metal, glass, silicon, quartz and the SiO that obtains by formation heat oxide film on silicon face ₂/ Si.Can separately or unite and use these materials.Wherein, from can the angle as electrode considering when the anodizing of nanoporous, be preferably metal.What note is that substrate can be bought ready-made or can prepare when needed.

When producing nanoporous by anodizing, electrode layer can be arranged between substrate and the metal level.

According to predetermined purpose, the material of electrode layer can be any suitable material; The example comprises Nb, Ta, Ti, W, Cr, Co, Pt, Cu, Ir, Rh and alloy thereof.These elements or alloy can separately or be united use.Can form electrode layer, for example vapour deposition or sputter according to any suitable step.

Metal layer thickness is not particularly limited and can suitably determines according to predetermined purpose.Therefore the length of the direct corresponding carbon nanotube of metal layer thickness, be 1 μ m or littler carbon nanotube in order to obtain length, and metal layer thickness is preferably 1 μ m or littler.Metal layer thickness can be required with carbon nanotube to be produced equal in length.Therefore, can easily control the length of carbon nanotube in the carbon nanotube chain of the present invention by regulating metal layer thickness.The length of equal carbon nano tube be can help like this and the quality and the physical properties of homogeneous realized.

Can form metal level, for example vapour deposition or sputter according to any suitable known steps.More specifically, preferred sputter is because it can be accurately and easily controls metal layer thickness.

Can form metal level by sputtering target is carried out sputter, this sputtering target is made by the metal identical with treating sedimentary metal level.According to predetermined purpose, sputtering target can have any suitable purity, but preferably has high purity.When metal level is manufactured from aluminium, the purity of the aluminium in the sputtering target be preferably 99.990% or more than.

Before the anodizing of metal level, need form concave surface (groove) OK in nanoporous position to be formed.It is favourable using anodizing to form nanoporous, because nanoporous can only form in groove effectively.

The cross section of groove (by the resulting groove surfaces of width cut-in groove along groove) is not particularly limited and can suitably determines according to predetermined purpose; For example, cross section can be rectangle, V-shape or semicircle.

The method that forms groove is not particularly limited and can suitably selects according to predetermined purpose; Example is: (1) a kind of method, wherein with have on the surface regular spacing basal plane (lands) row pattern mold impression (transfer) to metal level (for example, alumina or aluminium lamination) on, form line and interval (line-and-space) pattern thus thereon, this pattern comprises that the groove and the interval (basal plane (lands)) of arranging with regular spacing replace the row of arranging; (2) a kind of method wherein forms resin layer or photo-resist layer on metal level, by the normal photolithography technology and use mold to impress to make its patterning, and carry out etching and make that to form groove at layer on surface of metal capable; (3) wherein directly in the method for metal level formation groove.

By length along them, change the width that basal plane is capable in the mold, the width of photo-resist layer further groove etc. with specified spacing (regular spacing), can be correspondingly along their length, change (widen and narrow) width that nanoporous is capable with regular spacing, can advantageously make the spacing between the contiguous nanoporous when the constant of recess width changes, keep equating thus.

According to predetermined purpose, can use any suitable mold, but the mold of preferably making by silicon, silicon-dioxide or its combination, because these films are to be widely used as the material of making microtexture in semiconductor applications; In addition, for example, can use silicon carbide substrates and generally be used for the Ni pressing mold (stamper) of cd injection molding, because they are having high-durability under using continuously.Mold can be used multiple times.The method of impression is unrestricted and can be from those technology known in the art suitably select.The anticorrosive additive material that is used for the photo-resist layer not only comprises photo anti-corrosion agent material, also has the electron sensitive resist material.The used photo anti-corrosion agent material of the present invention can be selected from for example any suitable known materials in semiconductor applications; Example is near-ultraviolet light and near field of light material applicatory.

As long as it can form nanoporous at metal level, nanoporous is formed processing be not particularly limited, and can be according to predetermined purpose, suitably from for example selection such as anodizing, etching.

Therein, special preferred anodes is handled, because it can form many nanoporouss of arranging with regular spacing basically in metal level, makes nanoporous be positioned to become basically with substrate surface the direction at a right angle simultaneously.

Anodizing can be carried out under any suitable voltage, but preferably can satisfy following equational voltage: V=I/A, and wherein V is the voltage in the anodizing; I is the spacing (nm) between contiguous (adjacent) nanoporous; And A is constant (nm/V)=～2.5.

When carrying out anodizing under the voltage that is satisfying aforesaid equation, it is capable that resulting nanoporous advantageously is arranged in groove.

The time of electrolytical kind, concentration and temperature and anodizing is not particularly limited and can suitably sets according to number, size and the aspect ratio of nanoporous to be formed.For example, when the capable spacing (pitch) of contiguous nanoporous was the scope of 150nm to 500nm, ionogen was preferably the phosphoric acid solution of dilution; When spacing is the scope of 80nm to 200nm, the oxalic acid solution of preferred dilution; And when pitch is the scope of 10nm to 150nm, the sulphuric acid soln of preferred dilution.No matter which kind of situation can both for example controlled the aspect ratio of nanoporous to increase the diameter of nanoporous (alumina hole) in the phosphoric acid solution by anode metal layer is soaked after anodizing.

When carrying out nano-pore structure formation step by anodizing, can cause the bottom of each nanoporous of in metal level, forming to form undesirable barrier layer, but this barrier layer can easily be removed by using the conventional etching method of conventional etching reagent utilization, and described conventional etching reagent for example is a phosphoric acid.

Therefore, form in the step at nano-pore structure, formed nanoporous, wherein a plurality of nanoporouss are oriented to the direction that becomes a right angle with layer on surface of metal basically.

Nanoporous in the nano-pore structure is not particularly limited at vpg connection, and can use any shape according to predetermined purpose; Yet they can form hole or indenture (dents), more preferably open-work.

Spacing between contiguous nanoporous is capable is not particularly limited and can suitably determines according to predetermined purpose; Yet spacing is preferably 5nm to 500nm, more preferably 10nm to 200nm.

Be difficult to form nanoporous less than the spacing of 5nm, otherwise, be difficult to make them to arrange greater than the spacing of 500nm with regular spacing.

The ratio of the width that spacing between contiguous nanoporous is capable and nanoporous are capable is not particularly limited and can suitably sets according to predetermined purpose; For example, ratio is preferably 1.1 to 1.9 scope, and 1.2 to 1.8 scope more preferably.

Ratio less than 1.1 (spacing/width) can cause the hole of contiguous nanoporous between capable to merge (holefusion), and can cause producing discrete nanoporous, can cause that the part of nanoporous beyond groove forms when anodizing otherwise surpass 1.9 ratio.

The width that nanoporous is capable is not particularly limited and can suitably sets according to predetermined purpose; The preferred 5nm to 450nm of line width for example, and more preferably 10nm to 200nm.

Line width less than 5nm is difficult to form nanoporous, otherwise is difficult to make them to arrange with regular spacing greater than the line width of 450nm.

In addition, line width is can be along length constant or can be presented under the specified spacing and change (widen or narrow) as Figure 1A.Be preferably the latter because as shown in Figure 1B, be like this at width greater than other regional location, form nanoporous with regular spacing possibility be provided along nanoporous is capable.

The degree of depth of nanoporous is generally 10 μ m or still less, but is not particularly limited and can suitably sets according to predetermined purpose; Yet, to consider correspondingly with the length of carbon nanotube in the carbon nanotube chain of the present invention, the degree of depth of nanoporous is preferably 1 μ m or still less.

The opening diameter of nanoporous is not particularly limited and can suitably sets according to predetermined purpose; According to the voltage of anodizing, opening diameter generally is confirmed as 1/3rd of nanoporous spacing, but when needed, opening diameter can increase by handling with phosphoric acid solution.

-carbon nanotube formation step-

It is the step that forms carbon nanotube in nanoporous that carbon nanotube forms step.

Can be according to any suitable operation, for example chemical vapor deposition (CVD) forms carbon nanotube.

The example of chemical vapor deposition (CVD) operation is hot CVD (also abbreviating " CVD " as), heated filament CVD, plasma enhanced CVD (also being called " plasma assisted CVD " or " plasma CVD "), plasma body enhancing heated filament CVD and laser-enhanced CVD (also being called " laser CVD ").Wherein, preferred hot CVD and plasma CVD.

In hot CVD, the reaction tubes that comprises nano-pore structure is heated to about 400 ℃ to 2000 ℃ in electric furnace, then makes material breakdown in the pipe so that carbon or carbon nanotube deposit by material gas is introduced in nanoporous.

In plasma CVD, material gas be by with being approximately 0.1 to 1000W/cm ³The plasma body that excites of radio frequency (RF) ripple react and decompose, make carbon laydown thus.For example can using, low frequency wave, microwave (MW) or direct current (DC) etc. replace radio frequency (RF) ripple activated plasma.

The condition that forms carbon nanotube by CVD is not particularly limited and suitably selects according to predetermined purpose.For example, the flow velocity of preferred control material gas, and use the mixed gas of carbon-source gas and carrier gas to make material gas.

The example of carbon-source gas is methane, ethene, propylene, acetylene, benzene, butane, methyl alcohol, ethanol, propyl alcohol, Virahol, C ₁₀H ₁₆, CS ₂And C ₆₀Gas.The example of carrier gas is nitrogen, argon gas, hydrogen and ammonia.

Carbon-source gas and the carrier gas ratio in mixed gas is not particularly limited and can sets according to predetermined purpose.For example, when propylene as carbon-source gas, nitrogen is during as carrier gas, mixed gas is that 1:99 to 5:95 and overall flow rate are 100cm at the flow velocity ratio of propylene gas and nitrogen preferably ³/ min to 300cm ³Import under the condition of/min.At this moment, temperature is preferably 500 ℃ to 900 ℃, and most preferably is about 800 ℃.

When forming at carbon nanotube in the step when producing carbon nanotube by CVD, therefore the material of metal level does not need extra catalyzer as the catalyzer that forms carbon nanotube.For example, when metal level was made of aluminum, the aluminum oxide that is present in the layer on surface of metal of exposure was used as catalyzer, impels the formation of carbon nanotube thus.

It is basic identical on diameter, length and the number of plies to form the carbon nanotube that step produces by the carbon nanometer, and when metal layer thickness be 1 μ m or more hour, the mean length of carbon nanotube is 1 μ m or littler, an end of each nanotube is for sealing.

＜carbon is removed step 〉

It is to remove at carbon nanotube to form the step that is deposited on the lip-deep carbon of basal plane between groove in the step that carbon is removed step.

The formation of metal level further groove causes the formation of metal level basal plane between groove in nanostructure formation step.Subsequently, form in the step, in the nanoporous of groove, form carbon nanotube, and simultaneously, carbon deposits on basal plane at carbon nanotube.Carbon is removed step and is related to sedimentary carbon on the removing basal plane surface.By being carried out at the molten step of going of metal level of explanation after a while, cause the formation of carbon nanotube chain of the present invention, carbon nanotube chain can be arbitrary shapes such as sheet, band shape, rope form, each carbon nanotube chain is made of the carbon nanotube at neat interval, and this carbon nanotube combines with carbon deutero-carbon-coating on being deposited on metal level (nano-pore structure) groove.In each carbon nanotube chain, carbon nanotubes positioned is in becoming the direction at a right angle basically with the carbon-coating surface.

The method that carbon is removed is not particularly limited and can suitably determines according to predetermined purpose; For example, use by coating or chemically machinery polished (CMP) etc. and will be deposited on the method that the carbon on the basal plane of metal level etches away.More specifically, the method for removing the carbon that is deposited on the basal plane sidewall is: (1) comprises with the length of the basal plane of metal level and highly angled applies oxygen plasma is removed (comprising the undercoat making alive) deposit carbon with etching method; (2) comprise with the length of the basal plane of metal level and highly angled apply ionic fluid (for example, oxygen ion beam) to remove the method for deposit carbon; (3) comprise the control oxygen atmosphere, and with the length of the basal plane of metal level and highly angled the ionic fluid that applies with the method for removing deposit carbon etc.

It should be noted that the condition of using is not particularly limited and can suitably sets according to predetermined purpose in carbon removing step.In addition, can suitably determine in method 1, when plasma body is applied to the basal plane of metal level and their length and height angulation, and in method 2 and 3, apply the angle of ionic fluid.

The molten step of going of＜metal level 〉

The molten step of going of metal level is with the molten step of going of metal level (nano-pore structure).By carrying out this step, can access carbon nanotube chain of the present invention.

Be not particularly limited and can suitably determine in the molten condition of going to use in the step of metal level according to predetermined purpose.In the situation of alumina nanoporous, the specific examples of the operation of using in this step is to immerse in hydrogen fluoride (HF), and carries out hydrothermal treatment consists with sodium hydroxide (NaOH).

＜additional step 〉

Additional step is not particularly limited and can suitably selects according to predetermined purpose; Example is cleaning step and drying step.

Carbon nanotube chain of the present invention is produced by the technology that above-mentioned explanation of the present invention is used to produce carbon nanotube chain effectively.

Carbon nanotube chain of the present invention is made of a plurality of carbon nanotubes of delegation, and an end of described carbon nanotube combines with carrier, makes it be oriented to the direction that becomes a right angle with carrier surface basically thus.

The material of carrier, shape, structure, size, thickness etc. are not particularly limited and can suitably determine according to predetermined purpose; Yet material is preferably carbon.If carrier is made by carbon, can easily form carbon nanotube chain.More specifically, carbon-coating is deposited on the metal level (nano-pore structure) when forming carbon nanotube in nanoporous in carbon nanometer formation step, the carbon-coating that is deposited on then on the groove of metal level intactly combines with carbon nanotube, and is described carbon nano-tube oriented in becoming the direction at a right angle basically with the carbon-coating surface.Resulting single object should be the carbon nanotube chain of above-mentioned explanation mutually.

The example of support shapes comprises sheet, band shape and wire.In these shapes, carrier is preferably wire, because it can easily design and can be applied to extensive fields.

The thickness of carrier also is not particularly limited, as long as it can the fixed carbon nanotube; For example thickness is preferably 2nm to 20nm.

The number that is present in the carbon nanotube of carbon nanotube chain is not particularly limited; Its length according to spacing between the nanoporous and carbon nanotube chain in the nano-pore structure changes, and can suitably determine according to predetermined purpose.

In carbon nanotube chain, preferably each carbon nanotube and a carrier-bound end are opening, and the other end is for sealing.Carbon nanotube chain with this combination provides excellent chemical stability and never experiences oxidation etc. in time.Therefore, carbon nanotube chain can be applicable in the various uses.

Be identical one of in carbon nanotube in the carbon nanotube chain preferred length, size and the external diameter at least.When this carbon nanotube chain is used for target detect or during as transmitter, each carbon nanotube has the effect of similar degree, therefore reach the purpose of stable operation.

The length of each carbon nanotube can equate with metal layer thickness, therefore, can easily obtain having length and be the carbon nanotube chain of 1 μ m or littler small carbon nanotube.And (for example, aluminium lamination or alumina layer) thickness can pass through control metal layer thickness controlling carbon nanotube, thereby obtain required length of carbon nanotube easily, accurately, equably owing to the corresponding metal level of the length of carbon nanotube.

Carbon nanotube preferably covers with functional materials; The example comprises for example biomolecules of antibody.Although carbon nanotube itself shows adsorptive power and releasability, make with biomolecules coated carbon nanotube and to utilize the biomolecule detection all types of target to become possibility.

The purposes of carbon nanotube chain of the present invention is not particularly limited and can suitably selects according to predetermined purpose; For example, carbon nanotube chain of the present invention is preferred for the Acquisition Detection target.In this purposes, carbon nanotube chain preferably has the target acquistion body.

-target acquistion body-

The target acquistion body preferably have can with carbon nanotube chain bonded bound fraction and target acquistion part that can the Acquisition Detection target.Its reason is can have other function of branch effectively like this in same molecule.

The mode that carbon nanotube chain is bonded to the target acquistion body is not particularly limited and can suitably determines according to predetermined purpose; Yet they preferably lump together by chemical bonded refractory, because they can be combined more firmly.

The target acquistion body is not particularly limited, as long as it can be in catching part Acquisition Detection target, and can suitably select according to predetermined purpose.

The mode that the target acquistion body is caught target is not particularly limited; Can finish by physical adsorption, chemisorption etc. and catch, it can be realized by hydrogen bonded, Intermolecular Forces (Van der Waals force), dative bond combination, ionic linkage combination or covalent bonds.

The suitable example of target acquistion part comprises by enzyme, coenzyme, enzyme substrates, enzyme inhibitors, inclusion compound (can be called " host compound " or " main body " after this), metal, antibody, antigen, protein, microorganism, virus, cell debris, metabolite, nucleic acid, hormone, hormone receptor, lectin, sugar, physiologically active substance, the physiologically active substance acceptor, anaphylactogen, haemproteins, tissue protein, nucleic acid substances, virus particle, neurotransmitter, heptane, parasite, the target acquistion part that endocrine disrupter and chemical species or derivatives thereof form.

-detection target-

When target acquistion partly was enzyme, detecting target for example was the coenzyme of this enzyme; When target acquistion partly was coenzyme, detecting target for example was the enzyme of this coenzyme as coenzyme; When target acquistion partly was inclusion compound, detecting target for example was the guest compound (involved component) of this inclusion compound; When target acquistion partly was antibody, detecting target for example was protein, and it is the antigen of this antibody of antagonism; When target acquistion partly was protein, detecting target and for example be this protein identification was antigenic antibody; When target acquistion partly was nucleic acid, the detection target for example was and this nucleic acid complementary nucleic acid; When target acquistion part for example was hormone receptor such as tubulin or chitin, detecting target for example was the hormone that this hormone receptor is accepted; When target acquistion partly was lectin, detecting target for example was the sugar of being accepted by this lectin; When target acquistion partly was the physiologically active substance acceptor, detecting target for example was the physiologically active substance of being accepted by this physiologically active substance acceptor.

The sample that comprises the detection target of above-mentioned indication is not particularly limited and can suitably selects according to predetermined purpose; Example comprises for example bacterium and viral pathogenic agent; From live body separate blood, saliva, tissue slice; The movement of excrement and urine for example; When antenatal diagnosis, some embryonic cell in the amniotic fluid or some sv division ovum also can be used as sample.Before use, sample can be directly or when needed by centrifugation after being condensed into throw out, carry out cytoclasis and handle (for example enzyme processing, heat treated, tensio-active agent processing, ultrasonication or its any combination).

Inclusion compound is not particularly limited, as long as it has molecule distinguishability (being main body-object binding ability), and can suitably select according to predetermined purpose; Example comprises having right cylinder (one-dimensional) is hollow, stratiform (bidimensional) is hollow and the hollow inclusion compound of cage shape (three-dimensional).

The example that contains the hollow inclusion compound of right cylinder (one-dimensional) comprises urea, thiocarbamide, Septochol, dinitrobenzene biphenyl (dinitrodiphenyl), dioxy tritane, tritane, methylnaphthalene, spiral shell chroman (spirochroman), PHTP (peryhdrotriphenylene), Mierocrystalline cellulose, amylose starch and cyclodextrin (in solution, hollow is the cage shape).

The example of the detection target that can be caught by urea comprises positive paraffin derivative.

The example of the detection target that can be caught by thiocarbamide comprises branched-chain hydrocarbon and cyclic hydrocarbon.

The example of the detection target that can be caught by Septochol comprises paraffin, lipid acid and aromatic compound.

The example of the detection target that can be caught by dinitrobenzene biphenyl comprises biphenyl derivatives.

The example of the detection target that can be caught by the dioxy tritane comprises paraffin, positive alkene and shark alkene.

The example of the detection target that can be caught by tritane comprises paraffin.

The example of the detection target that can be caught by methylnaphthalene comprises positive paraffin and branched paraffins, and both have up to 16 carbon atoms.

The example of the detection target that can be caught by the spiral shell chroman comprises paraffin.

The example of the detection target that can be caught by PHTP (peryhdrotriphenylene) comprises chloroform, benzene and various polymer material.

Can comprise H by the example of the detection target of cellulosic acquisition ₂O ₂, paraffin, CCl ₄, dyestuff and iodine.

The example of the detection target that can be caught by amylose starch comprises lipid acid and iodine.

Cyclodextrin is the cyclodextrine that produces by the amylase starch-splitting, and three kinds of cyclodextrin of knowing are: alpha-cylodextrin, beta-cyclodextrin and γ-Huan Hujing.The cyclodextrin of Shi Yonging also comprises cyclodextrin derivative in the present invention, and wherein for example alkyl, allyl group, alkoxyl group, amide group and/or sulfonic group replace their some hydroxyls by other functional group.

The example of the detection target that can be caught by cyclodextrin comprises for example thymol, oxymethoxyallylbenzene, Resorcinol, ethyleneglycol monophenylether and 2-hydroxyl-phenol derivativess such as 4-methoxyl group-benzophenone; For example Whitfield's ointment, nipagin and benzoic acid derivatives such as aethyl parabenum and ester thereof; Steroid such as cholesterol for example; VITAMIN such as vitamins C, vitamin A, vitamin-E for example; Hydrocarbon such as Limonene, allyl mustard oil for example; Sorbic Acid; Iodine molecule; Tropeolin-D; Congo red; With 2-para-totuidine base naphthalene-6-potassium sulfonate (TNS).

The example of stratiform (bidimensional) inclusion compound comprises clay mineral, graphite, smectite, montmorillonite and zeolite.

The example of the detection target that can be caught by clay mineral comprises hydrophilic substance and polar compound.

The example of the detection target that can be caught by graphite comprises O, HSO ₄ ^-, halogen, halogenide and basic metal.

The example of the detection target that can be caught by montmorillonite comprises brucine, morphine monomethyl ether, O-Phenylene Diamine, p-diaminodiphenyl, piperidines, VITAMIN B4, guanine and riboside thereof.

The example of the detection target that can be caught by zeolite comprises H ₂O etc.

The example of cage shape (three-dimensional) inclusion compound comprises Resorcinol, gas hydrate, three-o-Zadaxin (tri-o-thymotide), flavones (oxyflavane), dintrile amine nickel, cryptand, calixarene and crown compound.

The example of the detection target that can be caught by Resorcinol comprises HCl, SO ₂, acetylene and rare gas element.

The example of the detection target that can be caught by gas hydrate comprises halogen, rare gas element and lower hydrocarbon.

The example of the detection target that can be caught by three-o-Zadaxin comprises hexanaphthene, benzene and chloroform.

The example of the detection target that can be caught by flavones comprises organic bases.

The example of the detection target that can be caught by dicyanamide nickel comprises benzene and phenol.

The example bag NH of the detection target that can catch by cryptand ₄ ⁺With each metal ion species.

Calixarene is a cyclic oligomer, and wherein phenol units is chained together by methylene radical, and it can be by phenol and prepared formaldehyde under appropriate condition; 4 to 8 yuan of polymerizations are known.Therein, can comprise chloroform, benzene and toluene by the example of the detection target that tertiary butyl calixarene (n=4) is caught.Can comprise Virahol and acetone by the example of the detection target that tertiary butyl calixarene (n=5) is caught.Can comprise chloroform and methyl alcohol by the example of the detection target that tertiary butyl calixarene (n=6) is caught.Can comprise chloroform by the example of the detection target that tertiary butyl calixarene (n=7) is caught.

The example of crown compound not only comprises having oxygen as the crown ether of giving electronic atom, also comprise and having for example as the nitrogen of ring composition and the similar macrocylc compound of giving electronic atom of sulphur, also comprise complexing ring-type crown compound, cryptand for example specific as follows: cyclohexyl-12-crown-4, dibenzo-14-hat-4, tertiary butyl benzo-15-hat-5, dibenzo-18-hat-6, dicyclohexyl-18-hat-6,18-hat-6, three benzos-18-hat-6, four benzos-24-hat-8 and dibenzo-26-hat-6 with two or more rings.

The example of the detection target that can be caught by crown compound comprises for example Li, Na and alkali-metal each metal ion species of K; The metal ion of Mg and Ca alkaline-earth metal for example; NH ₄ ⁺Alkyl phosphate ion; Guanidinium ion, aromatic diazo ion.Crown compound and these ion forming complex.Can comprise (for example having relatively large tart C-H unit by other example that detects target that crown compound is caught, acetonitrile, propane dinitrile, adiponitrile), the N-H unit (for example, aniline, benzaminic acid, acid amides and sulfamide derivatives) and the O-H unit is (for example, phenol, acetogenin) polar organic compound, crown compound also forms complex compound with these polar organic compounds.

The hollow size (diameter) of inclusion compound is not particularly limited and can suitably sets according to predetermined purpose, but in order to make inclusion compound that stable molecule distinguishability (main body object binding ability) is provided, diameter is preferably 0.1nm to 2.0nm.

In addition, inclusion compound can be categorized into for example unit molecule host compound, polymolecular host compound, polymer body compound and inorganic host compound.

The example of unit molecule host compound comprises cyclodextrin, crown compound, ring sweet smell, nitrogen heterocyclic sweet smell, calixarene, cyclotriveratrylene, spherand, hole part and oligopeptides.

The example of polymolecular host compound comprises cyclohexyl urea, thiocarbamide, Septochol, peryhdrotriphenylene and three-o-Zadaxin.

The polymer body examples for compounds comprises Mierocrystalline cellulose, starch, chitin, chitosan and polyvinyl alcohol.

That the example of inorganic host compound comprises is intercalation compound, zeolite and Huffman type complex compound.

Antibody is not particularly limited as long as itself and specific antigen carry out antigen antibody reaction; It can be polyclone antigen or mono-clonal antigen, and further example comprises the F (ab ') of IgG, IgM, IgE, Fab ', Fab, IgG ₂And avidin.

Antigen is not particularly limited and can suitably selects according to the person's character of antibody; Example comprises medicine, HLA antigen and the vitamin H in plasma proteins, tumor marker, apoprotein, virus antigen, autoantibody, blood coagulation/fibrinolytic factor, hormone, the blood.

The example of plasma proteins comprises immunoglobulin (Ig) (IgG, IgA, IgM, IgD and IgE), complementary composition (C3, C4, C5 and C1q), CRP, α ₁-antitrypsin, α ₁-microglobulin, β ₂-microglobulin, haptoglobin, Transferrins,iron complexes, ceruloplasmin and ferritin.

The example of tumor marker comprises α-Jia Taidanbai (AFP), carcinomebryonic antigen (CEA), CA19-9, CA125, CA15-3, SCC antigen, prostatic acid phosphatase (PAP), PIVKA-II, γ-refining albumen, TPA, elastoser I, neuronspecific enolase (NSE) and immunosuppressive acid protein (IAP).

The example of apoprotein is apo A-I, apo A-II, apo B, apo C-II, apo C-III and apo E.

The example of virus antigen comprises the antigen of hepatitis B virus (HBV) antigen, hepatitis C virus (HCV) antigen, HTLV-I, HIV, rabies virus, influenza virus and rubella virus.

The antigenic example of HCV comprises HCVc100-3 recombinant antigen, pHCV-31 recombinant antigen, pHCV-34 recombinant antigen and can suitably used its mixture.The antigenic example of HIV comprises viral surface antigen for example HIV-I env.gp41 recombinant antigen, HIV-I env.gp120 recombinant antigen, HIV-I gag.p24 recombinant antigen and HIV-II env.p36 recombinant antigen.

Pathogenic agent outside the virus for example is MRSA, ASO, toxoplasma gondii, mycoplasma and STD.

The example of autoantibody comprises anti-anti-microzome antibody, anti-siloglobulin antibody, antinuclear antibody, Rheumatoid factors, polyclonal, anti-mitochondrial antibody and myelin antibody.

The example of blood coagulation/fibrinolytic factor comprises Fibrinogen, fibrin degradation product (FDP) (FDP), profibr(in)olysin, α ₂-plasmin inhibitor, Antithrombin III, β-thromboglobulin, Factor IX, PROTEIN C and Protein S.

The example of hormone comprises pituitrin (LH, FSH, GH, ACTH, TSH and prolactin antagonist), Triiodothyronine (T ₃, T ₄And siloglobulin), calcitonin, Rat parathyroid hormone 1-34 (PTH), thyroliberin (aldosterone, hydrocortisone), gonadal hormone (hCG, oestrogenic hormon, testosterone, hPL) and pancreas and gastrointestinal hormone (Regular Insulin, C-peptide, hyperglycemic-glycogenolytic factor, gastrin).Other example comprises feritin, angiotensin I, Angiotensin II, enkephalin and erythropoietin.

The example of the medicine in the blood for example is the antiepileptic drug of Carbamzepine, primidone and valproic acid; It for example is the causing circulatory disease medicament of digoxin, quinidine, digoxigenin and theophylline; And for example be the microbiotic of gentamicin, kantlex and Streptomycin sulphate.

Above-mentioned proteic suitable example comprises low-molecular-weight protein, the scope of molecular weight approximately from 6000 to 13000, and it has high avidity to heavy metal, especially to zinc, cadmium, copper and mercury.These protein are present in liver, kidney and other organ or tissue of animal, and have shown also recently and be present in the microorganism.They have high-load halfcystine and comprise does not almost have the various kinds of aromatic residues amino acid.In addition, they are toxic important substance of removing interior cadmium of body and mercury, and also participate in essential trace-metal for example zinc and extremely intravital storage and distribution of copper.

The example of this heavy metal comprises mercury alkylide compound (R-Hg), mercury (Hg) or its compound, cadmium (Cd) or its compound, lead (Pb) or its compound, sexavalent chrome (Cr ₆ ⁺), copper (Cu) or its compound, zinc (Zn) or its compound, cyanogen, arsenic, selenium, manganese, nickel, iron, zinc, selenium and tin.

According to the production technique of carbon nanotube chain of the present invention, can produce carbon nanotube chain effectively.

Carbon nanotube chain of the present invention is made of above-mentioned carbon nanotube, and this carbon nanotube fitly at interval and have adsorptive power and releasability simultaneously.Therefore, can easily design and operate carbon nanotube chain of the present invention, and can be applied to extensive fields.For example, carbon nanotube chain of the present invention can detect all kinds of target substances, comprises morbid substance, biological substance and toxic substance, and is applicable to that various fields comprise as for example transmitter of object detector, biosensor and gas sensor.

(object detector)

Object detector of the present invention comprises carbon nanotube chain of the present invention and fixer, and further comprises the extention of suitably selecting when needed.

Carbon nanotube chain preferably include can the Acquisition Detection target the part of catching.

Catch part and be not particularly limited, and can suitably select according to predetermined purpose as long as it can the Acquisition Detection target; Yet, catch part and preferably form, and carbon nanotube chain and target acquistion body preferably combine with chemical bonding by above-mentioned target acquistion body.

It should be noted that carbon nanotube chain detail file, detect the identical of target and target acquistion body and above-mentioned explanation.

The material of fixer, shape, structure, size, thickness etc. are not particularly limited and can suitably determine, as long as fixer can be fixed and be manipulation, the surface of fixer is fixed with carbon nanotube chain.For example, can use the metal sheet that for example is manufactured from aluminium, by the acrylic panel that plastic cement is made, both sizes for example are that 10cm takes advantage of 1cm, and thickness is 1cm.

The position that carbon nanotube chain is fixed to fixer is not particularly limited and can suitably determines according to predetermined purpose; For example, the carrier of carbon nanotube chain is fixed on the fixer upper end face, makes carbon nano-tube oriented in becoming the direction at a right angle basically with the length of fixer thus.In the case, the number of waiting to be fixed to the carbon nanotube chain of fixer is not particularly limited; Can be according to predetermined purpose, fixing one or more carbon nanotube chains.When using two or more carbon nanotube chains, different material (for example, Shuo Ming detection target) after a while can act on carbon nanotube chain, makes thus these materials (detection target) are carried out Synchronization Analysis to become possibility.

The method that makes carbon nanotube chain be fixed to fixer is not particularly limited and can suitably determines according to predetermined purpose; For example, can utilize tackiness agent to make carbon nanotube chain be fixed to fixer, this tackiness agent can be to buy ready-made or can prepare when needed.The example of tackiness agent comprises the bi-component epoxy tackiness agent.

The method that utilization has the carbon nanotube chain detection target of target acquistion body is not particularly limited, and can suitably determine according to predetermined purpose; For example, can use the detection method that relates to ELISA, vibration or viscosity measurement transmitter, hybridization probe etc.

When utilizing ELISA to detect, the carbon nanotube of the antibodies that for example should be the target acquistion body mutually to the object detector.Fluorescently-labeled target substance is stimulated by laser beam irradiation by antibody capture, carries out light emission subsequently, measures light intensity then and differentiates.

When utilizing vibration or viscosity measurement transmitter to detect,, should be the target acquistion body mutually for example through Chemical bond or be fixed to the electrode of quartz resonator or the carrier and the carbon nanotube of surface acoustic wave (SAW) device.Allow on the target acquistion body when target substance and to do the time spent, target substance especially is bonded to the part of catching of target acquistion body, causes the weight or the viscosity change of target acquistion body thus.These variations convert frequency change to after testing and by quartz resonator or surface acoustic wave device.Therefore, by utilizing frequency recorder to detect the existence that this frequency change can be measured target substance.

In addition, the target substance in the sample can be from the calibration curve of this target substance and quantification (its concentration can be determined), and this calibration curve is obtained by the sample that previous preparation comprises the target substance of different concns.

What note is, quartz resonator means thin quartz plate, and this thin quartz plate has the metal electrode that forms by vapour deposition in its both sides, and the frequency vibration that wherein provides is to generate by the inverse piezoelectric effect after applying voltage of alternating current between the electrode.For example, can use quartz resonator with deposition of silver electrode (9MHz, AT-cut).

Surface acoustic wave (SAW) device refers to the surface and forms the solid articles with a pair of comb electrode; This device converts electric signal to surface acoustic wave (in the sound wave or the ultrasonic wave of solid surface propagation), is sent to counter electrode, and then exports with electric signal.Utilize this SAW device, can access the CF signal that stimulation is reacted.For example, can use ferroelectrics such as lithium tartrate, Lithium niobium trioxide, quartz and zinc-oxide film that piezoelectric effect can be provided material as the SAW device.

When utilizing hybridization probe to detect, the single stranded DNA that obtains by chemical modification should be the target acquistion body mutually.By allow that dna probe through mark acts on or hybridizes on the target acquistion body, might detect specific dna sequence dna, this sequence and dna probe complementation (that is, A (VITAMIN B4) to T (thymus pyrimidine) and G (guanine) to C (cytosine(Cyt))).Hybridization detection method is allowed activation (expressivity) the work systematicness analysis to the multiple gene that causes cancer, immunological disease etc.

Because target of the present invention inspection device comprises carbon nanotube chain of the present invention, various materials can be adsorbed to carbon nanotube and with its reaction, and all types of target material can be adsorbed to carbon nanotube or discharges from carbon nanotube.In addition because carbon nanotube chain is fixed on the fixer, can by by staff fixedly fixer guarantee to use highly easily.In addition, be 1 if treat the number of fixed carbon nanotube chain, carbon nanotube chain can be divided into a plurality of zones, can make different substances be bonded to the terminal of the carbon nanotube of different zones thus.If treating the number of fixed carbon nanotube chain is 2, can allow that different substances is bonded to different chains.The former example is as follows: when carbon nanotube chain is divided into two zones as transmitter, during with some pollution substance in the detection waste water, the target acquistion body that can catch heavy metal is bonded to the carbon nanotube in one of two zones especially, thus, can detect two different pollution substances at one time.Perhaps, can also reach to the purpose of two different pollution substances of synchronous detection by using two carbon nanotube chains, one of them carbon nanotube chain has and the target acquistion body bonded carbon nanotube that can catch heavy metal, and another carbon nanotube chain has and the target acquistion body bonded carbon nanotube that can catch nitrile.

Object detector of the present invention can carry out high-sensitivity detection, and all types of target comprised that morbid substance, biological substance and toxic substance carry out quality and quantitative analysis, and can be applicable to that various fields comprise the transmitter as biological example transmitter and gas sensor.

(object detection method)

Object detection method of the present invention uses the object detector of the present invention of above-mentioned explanation, and object detector is acted on comprising on the sample that detects target, and further comprises the additional step of suitably selecting when needed.

Object detector is an object detector of the present invention, and the detection target is identical with above-mentioned explanation.

Allow and on object detector, do the time spent when comprising the sample that detects target, by the target acquistion body Acquisition Detection target of object detector.

The method that object detector is acted on sample is not particularly limited and can suitably determines according to predetermined purpose; For example, can use soak method in sample of the object detector with target acquistion body.

What note is when object detector comprises a plurality of carbon nanotube chain, can reach to the purpose of a plurality of detection targets being carried out Synchronization Analysis by making different types of target acquistion body be fixed to each carbon nanotube chain.

The method of detection target that utilization has a carbon nanotube chain of target acquistion body is not particularly limited and can suitably determines according to predetermined purpose; For example, can use the detection method that relates to ELISA, vibration or viscosity measurement transmitter, hybridization probe etc.

When utilizing ELISA to detect, the carbon nanotube of the respective objects antibodies of catching body to the object detector for example.Fluorescently-labeled target substance is stimulated by laser beam irradiation by antibody capture, carries out light emission subsequently, measures light intensity then and differentiates.

When utilizing vibration or viscosity measurement transmitter to detect,, should be the target acquistion body mutually for example through Chemical bond or be fixed to the electrode of a quartz resonator or the carrier and the carbon nanotube of surface acoustic wave (SAW) device.Allow on the target acquistion body when target substance and to do the time spent, target substance especially is bonded to the part of catching of target acquistion body, causes the weight or the viscosity change of target acquistion body thus.These variations convert frequency change to after testing and by quartz resonator or surface acoustic wave device.Therefore, by utilizing frequency recorder to detect the existence that this frequency change can be measured target substance.

Surface acoustic wave (SAW) device refers to the solid articles that its surface has a pair of comb electrode; This device converts electric signal to surface acoustic wave (in the sound wave or the ultrasonic wave of solid surface propagation), is sent to counter electrode, and then exports with electric signal.Utilize this SAW device, can access the CF signal that stimulation is reacted.For example, can use ferroelectrics such as lithium tartrate, Lithium niobium trioxide, quartz and zinc-oxide film that piezoelectric effect can be provided material as the SAW device.

When utilizing hybridization probe to detect, the single stranded DNA that obtains by chemical modification should be the target acquistion body mutually.By allow through the dna probe effect of mark to or hybridize to the target acquistion body, can detect specific dna sequence dna, this sequence and dna probe complementation (that is, A (VITAMIN B4) to T (thymus pyrimidine) and G (guanine) to C (cytosine(Cyt))).Hybridization detection method is allowed activation (expressivity) the work systematicness analysis to the multiple gene that causes cancer, immunological disease etc.

Object detector of the present invention can reach to effective, high precision detection, and all types of target that is included in the sample is carried out quality and quantitative analysis.For example, enzyme, coenzyme, enzyme substrates, enzyme inhibitors, inclusion compound, metal, antibody, antigen, protein, microorganism, virus, cell debris, metabolite, nucleic acid, hormone, hormone receptor, lectin, sugar, physiologically active substance, physiologically active substance acceptor, anaphylactogen, haemproteins, tissue protein, nucleic acid substances, virus particle, neurotransmitter, heparin, parasite, endocrine disrupter and chemical species or derivatives thereof are analyzed or screened, and can carry out to gaseous fraction.Therefore object detection method of the present invention can be applicable to the mensuration etc. of diagnosis, target substance, biomolecules and gas of exploitation, the disease of medicine.

Embodiment

Hereinafter, the present invention will be described by way of example, but it should not be understood that restriction that scope of the present invention is made.

(nanostructure forms experiment)

(pitch=150nm) mold of pattern is pressed to pending anodizing with in the aluminium lamination that forms nanoporous (alumina hole), thus line (concave surface or groove) and space (convex surface or basal plane) pattern is stamped into the aluminium lamination surface to have line and space.Like this, show, form alternative groove and wire basal plane pattern (promptly neat groove pattern at interval) as Fig. 2 A.Subsequently, aluminium lamination carries out anodizing under 60V in the oxalic acid solution of dilution, only causes in groove forming along their length the nanoporous (alumina hole) (in other words, it is capable to form nanoporous) of self-organization, as shown in Fig. 2 B.

(embodiment 1)

-preparation carbon nanotube chain-

＜nano-pore structure forms step 〉

As shown in Figure 3A, use EB mask writer (ELS7000, by ELIONIX CO., LTD makes),, and paint lines and make generation concave surface and convex surface pattern (line and space), obtain SiC mold 50 by etch processes subsequently in SiC substrates coated EB resist.What note is, the spacing (pitch) in the pattern between the adjacent concave (groove) is 150nm, and the degree of depth of groove is 100nm, and the ratio of the width of the width of convex surface or basal plane and concave surface or groove (convex surface wide/concave surface is wide) is 1:1.

Shown in Fig. 3 B, vacuum moulding machine becomes 50nm thick to Nb on the silicon substrate 52 by sputtering at, form the electrode layer identical thus, and aluminium sputters at that vacuum moulding machine becomes 350nm thick on the electrode layer, the formation metal level 54 identical with above-mentioned explanation thus by the sputtered aluminum target with above-mentioned explanation.Thereafter, SiC mold 50 is pressed to metal level 54, and the pattern on SiC mold 50 surfaces is stamped on metal level 54 surfaces.Shown in Fig. 2 A, cause on metal level 54 surfaces, forming concave surface and convex surface pattern like this.Reason it should be noted that SiC mold 50 utilizes pressure to be 3000kg/cm ²Hydropress press to metal level 54.

Metal level 54 through impressing above-mentioned pattern carries out anodizing subsequently under 60V in the oxalic acid bath of dilution.Show that as Fig. 2 B and 3C cause the generation of nano-pore structure 58, wherein many nanoporouss (alumina nanohole or alumina hole) 56 only form in groove, they are oriented to the direction that becomes a right angle with metal level 54 surfaces basically thus.It should be noted that the spacing between the adjacent nanoporous 56 in groove is about 150nm, the thickness of metal level 54 (being the degree of depth or the length of each nanoporous 56) is 300nm, and the opening diameter of each nanoporous 56 is 50nm.

＜carbon nanotube forms step 〉

Use propylene gas as carbon-source gas, make the formation carbon nanotube thus, and use nitrogen, make carbon laydown in the outside surface and nanoporous 56 of nanoporous (alumina nanoporous) structure 58 by CVD as carrier gas.More specifically, the silicon substrate 52 with nanoporous 56 places crystal reaction tube, flows down in 2 hours inherent nitrogen then and is heated to 800 ℃.After this, 1.2% propylene and nitrogen (carrier gas) are introduced in the reaction tubes, carry out 2 hours CVD of 800 ℃ thereafter.Subsequently, stop the supply of propylene, and flow down at nitrogen and to make reaction tubes be cooled to room temperature.

According to above-mentioned steps, show as Fig. 3 D, nano-pore structure 58 surface depositions carbon-coating 60, and formed carbon nanotube 62 in the nanoporous 56 of nano-pore structure 58.The mean length of carbon nanotube is 300nm.

＜carbon is removed step 〉

In order to polish, with its surface deposition the nano-pore structure 58 of carbon-coating 60 be placed on the turntable, make to have abrasive coating the wrap of (particle diameter=3 μ m) is pressed to nano-pore structure 58, and in the turntable rotation, be provided for the water coolant of surface finish.Like this, show as Fig. 3 E, remove basal plane 64 surfaces that are deposited between groove carbon-coating 60 (promptly be deposited on metal level 54 basal plane 64 upper surfaces carbon-coating and be deposited on basal plane 64 lateral carbon-coatings).

The molten step of going of＜metal level 〉

Then, the nano-pore structure 58 of removing the carbon-coating 60 on basal plane 64 surfaces that are deposited between groove is stood the hydrothermal treatment consists of NaOH (condition: 10M NaOH, 150 ℃ autoclave), make and moltenly remove metal level (alumina layer) 54, and neutralize by dilute hydrochloric acid.At last, show as Fig. 3 F, cause forming wire carbon nanotube chain 68 according to the present invention, it is capable 62 that it comprises an end and wire object 66 bonded carbon nanotubes, makes them be oriented to the direction that becomes a right angle with wire object 66 surfaces basically thus.

(embodiment 2)

-preparation carbon nanotube chain-

The carbon nanotube chain of embodiment 2 is removed step except using following carbon, as embodiment 1 preparation.

＜carbon is removed step 〉

The surface deposition that forms the step acquisition by above-mentioned carbon nanotube has the nano-pore structure 58 of carbon-coating 60 to be arranged on the oxygen ion beam system, the ion source that wherein adopts in system is 20kv ECR (electron cyclotron resonace) source, and its position of putting makes the input angle of ionic fluid and sample holder at 45.Thereafter, as shown in Figure 4, with 500eV oxygen ion beam 70 irradiation nano-pore structures 58, make and remove sedimentary carbon-coating 60 on 64 surfaces of the basal plane between groove, promptly remove the carbon-coating of basal plane 64 upper surfaces that are deposited on metal level 54 and be deposited on basal plane 64 lateral carbon-coatings (seeing Fig. 3 E).

Subsequently, as embodiment 1, carry out the molten step of going of metal level according to the present invention so that wire carbon nanotube chain 68 to be provided, it is capable 62 that it comprises an end and wire object 66 bonded carbon nanotubes, makes them be oriented to the direction (seeing Fig. 3 F) that becomes a right angle with wire object 66 surfaces basically thus.

(embodiment 3)

-preparation carbon nanotube chain-

The carbon nanotube chain of embodiment 3 is removed step except using following carbon, as embodiment 1 preparation.

＜carbon is removed step 〉

The surface deposition that above-mentioned carbon nanotube is formed the step acquisition has the nano-pore structure 58 of carbon-coating 60 to be arranged on ion processing system (ion milling system, ME-1001 are made by VeecoInstruments).Then, be that 50V and current density are 20mA/cm at acceleration voltage ²Condition under, be 30 ° ar-ion beam irradiation nano-pore structure 58 with input angle, make the carbon-coating 60 of basal plane 64 surface depositions of removing between groove, promptly be deposited on metal level 54 basal plane 64 upper surfaces carbon-coating and be deposited on basal plane 64 lateral carbon-coatings.

(embodiment 4)

-preparation carbon nanotube chain-

The carbon nanotube chain of embodiment 4 forms step except using following nano-pore structure, as embodiment 1 preparation.

＜nano-pore structure forms step 〉

Use EB mask writer (ELS7000, by ELIONIXCO., LTD makes),, thus, generate the pattern (line and space) of concave surface and convex surface painting lines by being spun on to form on the glass substrate on the resist layer that thickness is 40nm.What note is, the spacing (pitch) between the contiguous concave (groove) in the pattern is 60nm, and the degree of depth of groove is 50nm, and the ratio of the width of the width of convex surface or basal plane and concave surface or groove (convex surface wide/concave surface is wide) is 1:1.Then, by formation Ni layer on the pattern that is sputtered in concave surface and convex surface, and when using Ni, the Ni layer is thickened to 0.3mm by in nickel sulfamic acid is bathed, carrying out electroforming as electrode.Then, the Ni mold is made in the polishing of Ni layer.

Thereafter, vacuum moulding machine becomes 50nm thick to Nb on the silicon substrate by sputtering at, and forms the electrode layer identical with above-mentioned explanation thus, and aluminium sputters at that vacuum moulding machine becomes 350nm thick on the electrode layer, the formation metal level identical with above-mentioned explanation thus by the sputtered aluminum target.Thereafter, the Ni mold is pressed to metal level, and the pattern of Ni mould surface is stamped on the layer on surface of metal.Cause on layer on surface of metal, forming concave surface and convex surface pattern like this.Ought to notice that the Ni mold utilized pressure to be 3000kg/cm ²Hydropress press to metal level.

Metal level through impressing above-mentioned pattern carries out anodizing subsequently under 18V in the sulfuric acid bath of dilution.Show that as Fig. 5 cause the generation of nano-pore structure like this, wherein many nanoporouss (alumina nanoporous or alumina hole) only form as open-work in groove, thus they be oriented to the layer on surface of metal base on become the direction at a right angle.It should be noted that the spacing quite tiny (for about 45nm) between the adjacent nanoporous in groove, metal layer thickness (being the degree of depth or the length of each nanoporous) is 350nm, and the opening diameter of each nanoporous is 20nm.

Subsequently, as embodiment 1, carry out carbon nanotube according to the present invention and form step, carbon removing step and the molten step of going of metal level, so that wire carbon nanotube chain 68 to be provided, it is capable 62 that it comprises an end and wire object 66 bonded carbon nanotubes, makes them be oriented to the direction (seeing Fig. 3 F) that becomes a right angle with wire object 66 surfaces basically thus.

(embodiment 5)

-preparation carbon nanotube chain-

Form in the step as the nano-pore structure of embodiment 1, when EB expose, the frequency change of exposure to provide obtained the pattern of concave surface and convex surface thus, and wherein as Figure 1A demonstration, the width of each concave surface (groove) is with the spacing variation of 100nm.Make Ni mold as embodiment 3 thereafter.Then except in dilute sulphuric acid, under 40V, carrying out anodizing, all the other steps such as embodiment 1, the carbon nanotube chain of preparation embodiment 5.Carbon nanotube chain has the structure that shows as Figure 1B, and through confirming, nanoporous (alumina hole) with the spacing in the zone of corresponding groove with big width fitly at interval.

(embodiment 6)

-preparation object detector-

Fixer as described above, to take advantage of 1cm and thickness be that the plastic cement of 1cm is prepared bar-shaped acrylic panel by being of a size of 10cm, and utilize tackiness agent (Aronalfa ^(TM), produce by Toa Gosei) and the 1cm wire object 66 of carbon nanotube chain 68 that embodiment 1 to 5 is made respectively is fixed to the upper end face of fixer 82, and makes carbon nanotube 62 be oriented to the direction that becomes a right angle with the length of fixer 82 basically.Like this, be prepared into the object detector 80 that shows as Fig. 6.

In the object detector 80 of the carbon nanotube chain with embodiment 1 to 3 preparation, carbon nanotube is with the intervals of 150nm in each carbon nanotube chain; Therefore, the number of the carbon nanotube in each carbon nanotube chain is 67000.In the object detector 80 of the carbon nanotube chain with embodiment 4 preparations, carbon nanotube is with the intervals of 45nm in each carbon nanotube chain; Therefore, the number of the carbon nanotube in each carbon nanotube chain is 222000.In the object detector 80 of the carbon nanotube chain with embodiment 5 preparations, carbon nanotube is with the intervals of 100nm in each carbon nanotube chain; Therefore, the number of the carbon nanotube in each carbon nanotube chain is 100000.

The assessment of the adsorptive power of-object detector-

It is to be undertaken by the object detector that it is adsorbed to prepare below that the detection of chemical substance is disturbed in internal secretion.

As shown in Figure 6, object detector 80 is to be fixed on fixer 82 by 100 carbon nanotube chains 68 with embodiment 5 to prepare, and these 100 carbon nanotube chains 68 respectively have the long wire object of 2cm, and carbon nanotube is with the intervals of 100nm.Shown in Fig. 7 A, the carbon nanotube chain 68 of object detector 80 soaks in the solution that comprises this internal secretion interference chemical substance of dihydroxyphenyl propane (its concentration is 1ng/mL).Shown in Fig. 7 B, object detector 80 takes out from the solution that comprises dihydroxyphenyl propane then, soaks in methanol solution again, discharges adsorbed composition in solution.The analysis that utilizes high performance liquid chromatography that solution is carried out shows the existence of dihydroxyphenyl propane.But also determine to carry out quantitative analysis, because the intensity of detection signal is directly proportional with concentration basically.

Even can determine that from above-mentioned result displayed dihydroxyphenyl propane is in micro-concentrations and also can detects, the object detector that promptly contains carbon nanotube chain has the ability of absorption dihydroxyphenyl propane, and therefore can be applicable to the absorption detection technique of utilizing selective adsorption capacity.Ought to notice that the object detector of above-mentioned explanation provided the similar adsorptive power to 4-n-nonyl phenol, 4-tert-octyl phenol, dioxin etc.

(embodiment 7)

The detection of-target-

Utilization has the object detector through the carbon nanotube of chemically modified, and (AFP) detects to α-Jia Taidanbai.

(wherein 100 of embodiment 5 carbon nanotube chains 68 are fixed on fixer 82 (see figure 6)s with the carbon nanotube chain 68 of the object detector 80 of embodiment 6, each chain has the long wire object of 2cm and the carbon nanotube intervals with 100nm,) at first in concentrated nitric acid solution, soak, and made carboxyl (COOH) be introduced into carbon nanotube 62 in 3 hours 800 ℃ of heating.Carbon nanotube 62 is modified by Streptavidin then, and it is fixed on the biotinylated anti-AFP antibody.Allow the sample and the Ru (bpy that contain AFP then ₃) ²⁺The anti-AFP antibody of mark acts on carbon nanotube 62, uses Ru (bpy subsequently ₃) ²⁺Electrochemiluminescence AFP is detected.The limit of detection of AFP is low to moderate 10ng/mL and can carries out detection by quantitative.Therefore need carry out the analysis of the biopolymer of chemically modified through determining that this object detector can be applicable to.

According to the present invention, can solve above-mentioned general issues and provide by length is 1 μ m or the littler capable carbon nanotube chain that constitutes of carbon nanotube, and this carbon nanotube chain is suitable for makes for example object detector or transmitter; Efficient carbon nanotube chain production technique also is provided; By using carbon nanotube chain can carry out high-sensitivity detection, and by using carbon nanotube chain that all types of target thing is comprised that morbid substance, biological substance and toxic substance carry out qualitative and quantitative analysis, and applicable biosensor and the gas sensor done; And by using the object detection method that object detector can easy and highly sensitive detection target.

Carbon nanotube chain of the present invention can comprise that morbid substance, biological substance and toxic substance carry out qualitative and quantitative analysis to all types of target (target compound), and is applicable to that various fields comprise for example as object detector, biosensor and gas sensor.

Object detector of the present invention also can comprise that morbid substance, biological substance and toxic substance carry out qualitative and quantitative analysis to all types of target, and is applicable to that various fields comprise for example as object detector, biosensor and gas sensor;

The technology that the present invention is used to produce carbon nanotube chain can be used in produces carbon nanotube chain of the present invention.

Object detection method of the present invention can carry out simple and easy and highly sensitive detection to target.

Claims

1. carbon nanotube chain, it comprises:

Carrier; With

One end and a plurality of carbon nanotubes of carrier surface bonded,

Wherein a plurality of carbon nano-tube oriented in becoming the direction at a right angle basically with carrier surface; Described carrier is that wire object and described carbon nanotube are arranged in rows, and wherein said carrier is made by carbon.

2. carbon nanotube chain according to claim 1 is an opening with an end of described carrier-bound each carbon nanotube wherein, and its other end is for sealing.

3. carbon nanotube chain according to claim 1 is identical one of at least in the length of wherein said a plurality of carbon nanotubes, thickness and the external diameter.

4. carbon nanotube chain according to claim 1, the mean length of wherein said carbon nanotube are 1 μ m or littler.

5. carbon nanotube chain according to claim 1, wherein said carbon nanotube covers with functional materials.

6. carbon nanotube chain according to claim 1, wherein said carbon nanotube chain is used for the Acquisition Detection target.

7. carbon nanotube chain according to claim 1, wherein said carbon nanotube chain comprises the target acquistion body, described target acquistion body contain can with carbon nanotube bonded bound fraction and target acquistion part that can the Acquisition Detection target.

8. carbon nanotube chain according to claim 7, wherein said carbon nanotube and target acquistion body are lumped together by chemical bonded refractory.

9. object detector, it comprises:

Carbon nanotube chain; With

Fixer;

Wherein said carbon nanotube chain comprise can the Acquisition Detection target the part of catching, and

Wherein said carbon nanotube chain comprises carrier and an end and a plurality of carbon nanotubes of carrier surface bonded, and is wherein said a plurality of carbon nano-tube oriented in becoming the direction at a right angle basically with carrier surface;

Described carrier is that wire object and described carbon nanotube are arranged in rows, and wherein said carrier is made by carbon.

10. object detector according to claim 9, the wherein said part of catching is formed by the target acquistion body, described target acquistion body comprise can with carbon nanotube bonded bound fraction and target acquistion part that can the Acquisition Detection target.

11. a technology that is used to produce carbon nanotube chain, it comprises:

Form groove at metal level;

Carry out nanoporous and form processing to form nano-pore structure, wherein nanoporous is capable forms in each groove, and described nanoporous is oriented to the direction that becomes a right angle with layer on surface of metal basically;

In each nanoporous, form carbon nanotube;

Remove sedimentary carbon on the basal plane surface of metal level between groove; And

The molten metal level that goes;

12. according to the described technology that is used to produce carbon nanotube chain of claim 11, wherein metal level is made of aluminum.

13. according to the described technology that is used to produce carbon nanotube chain of claim 11, the width of wherein said each groove changes with neat spacing along its length.

14. according to the described technology that is used to produce carbon nanotube chain of claim 11, wherein said nanoporous forms and is treated to anodizing.

15. according to the described technology that is used to produce carbon nanotube chain of claim 11, wherein said carbon nanotube is formed by chemical vapour deposition.

16. according to the described technology that is used to produce carbon nanotube chain of claim 11, wherein removing the lip-deep carbon of the basal plane that is deposited on metal level is by at least a the carrying out in parcel or the chemically machinery polished.

17. according to the described technology that is used to produce carbon nanotube chain of claim 11, wherein remove carbon on the basal plane side that is deposited on metal level and be by with the length of basal plane and highly angled a kind of the carrying out that applies in ionic fluid and the electron beam.

18. an object detection method, it comprises:

Object detector is acted on containing on the sample that detects target,

Wherein said object detector comprises carbon nanotube chain and fixer,

Wherein said carbon nanotube chain comprises carrier and an end and a plurality of carbon nanotubes of carrier surface bonded, wherein said a plurality of carbon nano-tube oriented in becoming the direction at a right angle basically with carrier surface, described carrier is that wire object and described carbon nanotube are arranged in rows, and wherein said carrier is made by carbon; And

Wherein said carbon nanotube chain comprise can the Acquisition Detection target the part of catching.