CN1541185A - Crystals comprising single-walled carbon nanotubes - Google Patents
Crystals comprising single-walled carbon nanotubes Download PDFInfo
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- CN1541185A CN1541185A CNA01818829XA CN01818829A CN1541185A CN 1541185 A CN1541185 A CN 1541185A CN A01818829X A CNA01818829X A CN A01818829XA CN 01818829 A CN01818829 A CN 01818829A CN 1541185 A CN1541185 A CN 1541185A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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- C01B32/162—Preparation characterised by catalysts
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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- C30B1/00—Single-crystal growth directly from the solid state
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/002—Controlling or regulating
- C30B23/005—Controlling or regulating flux or flow of depositing species or vapour
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/605—Products containing multiple oriented crystallites, e.g. columnar crystallites
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
Abstract
The invention is directed to a method of manufacturing single-walled carbon nanotubes comprising the steps of providing on a substrate at least one pillar comprising alternate layers of a first precursor material comprising fullerene molecules and a second precursor material comprising a catalyst, and heating the at least one pillar in the presence of a first magnetic or electric field. It further is directed to a precursor arrangement for manufacturing single-walled carbon nanotubes comprising on a substrate at least one pillar comprising alternate layers of a first precursor material comprising fullerene molecules and a second precursor material comprising a catalyst. A third aspect is a nanotube arrangement comprising a substrate and thereupon at least one crystal comprising a bundle of single-walled carbon nanotubes with essentially identical orientation and structure.
Description
Technical field
The present invention relates to a kind of method of making Single Walled Carbon Nanotube, this method promotes the self-assembly of Single Walled Carbon Nanotube monocrystalline by the thermolysis of the parent of nano-patterned.Compared with prior art, the growing nano-tube that uses method disclosed by the invention to obtain has the higher degree of order, simultaneously the synthetic extended configuration that causes having micron dimension of the Single Walled Carbon Nanotube monocrystalline of these high-sequentials.These extended configuration are formed by nanotube, and the nanotube in each monocrystalline has identical diameter and chirality, but these nanotubes can be different between each crystal.Use the method for the present invention's suggestion, Single Walled Carbon Nanotube can be fabricated to the block materials of the high-sequential on the micron dimension, this is the block macroscopic view crystalline material synthetic the first step.Therefore, just comprise the crystal synthetic technology of a large amount of Single Walled Carbon Nanotube neat and orderly, the physical properties unanimity, the present invention is a major progress.
Background technology
Carbon nanotube was found the theme that beginning just becomes ardent research since 1991.Make carbon nanotube and want that one of target of reaching is to form very make peace an orderly nanostructure and a micrometer structure most, and finally form block materials.
The potential application of Single Walled Carbon Nanotube from structured material with outstanding mechanical property to nanoelectronic element with the potential that can break through More's rule.Single Walled Carbon Nanotube can be with the probe tip of the end that acts on Scanning Probe Microscopy, and it has the additional capabilities that makes this summit have certain function on chemical analysis.These nanostructures also can be used for making microbalance, gas detector or energy storage device even.Equally, the use in the Single Walled Carbon Nanotube emission display format on the scene, or, all have bright and clear forward-looking technology meaning as the electrode of electron beam source in photolithography and the microscopy or Organic Light Emitting Diode.
Prior art has been used exacting terms to the growth of Single Walled Carbon Nanotube, the for example laser ablation of the carbon-point in inert gas environment or the direct current arc between carbon dioxide process carbon electrode discharge is as " the fullerene nanotube: C of American Scientist (American Scientist) the 7-8 month in 1997 number the 85th volume the 4th phase 324-337 page or leaf Ya Kebuxun (Yakobson) and Si Moli (Smalley)
1,000,000And above (FullerenceNanotubes:C
1,000,000And Beyond) " described in.For above-mentioned two kinds of methods, add the little metal catalyzer, as Co, Ni, Fe or Mo, can increase the output of Single Walled Carbon Nanotube.Up to the present, although every nanotube can have the hundreds of micron long, the material that is synthesized can only be made of the Single Walled Carbon Nanotube group of the order difference that is intertwined.In addition, coexistence has the multiple structural changes that is known as sawtooth form, handrail form or chirality form in material.United States Patent (USP) the 5424054th has been introduced a kind of method of making tubular fibre, and the cylindrical wall of this fiber comprises the monolayer carbon atom.But the fiber of its production does not have controlled direction yet.
Recently, in the article " carbocyclic ring and cage (Carbon Rings and Cages in the Growth of Single-WalledCarbon Nanotubes) in the Single Walled Carbon Nanotube growth " of the Jin Xihe (Ching-Hwa Kiang) of the 113rd volume o. 11th publication in " Acta PhySico-Chimica Sinica " (Journal of Chemical Physics) on September 15th, 2000, based on the analysis of the experimental result of the Single Walled Carbon Nanotube that electric arc growth and laser are grown, the growth model of Single Walled Carbon Nanotube has been proposed.
Appoint in (Ren) people's of etc.ing " growth (Growth of a Single Freestanding Multiwall CarbonNanotube on Each Nanonickel Dot) of single free-standing multi-walled carbon nano-tubes on each nanometer nickel point " at the 75th volume the 8th phase 1086-1088 page or leaf in " applicating physical communication " (Applied Physics Letters) on August 23rd, 1999, chemical vapour deposition, the growth that has been used to guide separate single wall carbon nano tube in the substrate are used in catalysis composition that combining nano is made or moulding.Yet, also do not produce the oldered array that can surmount the orderly Single Walled Carbon Nanotube of forming by tens of nanotubes of short section.Equally, chirality and diameter do not have controlled.For many application, chirality and diameter have very important importance, because the physical property of nanotube such as specific conductivity etc. are to be tetchy to structure.
Summary of the invention
According to a first aspect of the invention, a kind of method of making Single Walled Carbon Nanotube is provided, this method comprises the steps: to provide at least one post in substrate, this post comprises the alternative first fertile material layer and the second fertile material layer, first fertile material comprises fullerene molecule, and second fertile material comprises catalyzer; Heat described at least one post.In heat-processed, comprise the crystal growth of Single Walled Carbon Nanotube.Fertile material can provide by thermal evaporation.As fullerene molecule, C60 and C82 molecule can preferably be used.
5 to 10 layers of fertile material that post had be deposited on from level to level together prove a favourable selection.Every layer thickness is between 5 to 30nm.
Fertile material can deposit by the baffle that comprises one or more holes.The advantage of this baffle is not only to be suitable for the hole that forms a post is provided, and can make a large amount of such posts abreast by such baffle.In addition, by for example photoetching process, also can make the hole on the baffle abreast.
Selected substrate comprises and is grid configuration or is arranged on thermal oxidation silicon or molybdenum on the silicon wafer as solid film.Selected substrate also can have coarse polyhedron surface, so just can provide crystallization position, promptly plants brilliant position, is the position that crystal or nanotube grow.
It is desirable to, the surface tissue of selected substrate helps post still to be restricted in heating steps.The inventor finds, limits well more to lip-deep post, and accurately the crystalline output of arranging is high more.If the chemical reaction that this substrate does not participate in the chemical reaction that takes place in the heating steps or only participates in taking place in the heating steps on insignificant degree, then this substrate is optimal selection.Substrate also should have and keeps post to be restricted superincumbent performance effectively.Rod structure diffusion from the teeth outwards can reduce crystal yield.The inventor finds that molybdenum or silicon-dioxide are the base materials that satisfies above-mentioned two requirements.Especially, find that molybdenum can provide a large amount of crystallization positions on its whole surface tissue.Except the block substrate, can also use any laminate structure that comprises differing materials.For this production method, the superiors are the layers that influence technology and be called as substrate herein.
Can be about 10
-9Carry out the evaporation of fertile material under the pressure of Torr (torr), substrate simultaneously can remain on room temperature.By using dynamo-electric shutter and online balance to monitor the sedimentation rate of fertile material, can control evaporation.When the control evaporation, the thickness of each layer reduces with the distance of leaving substrate.Thickness reduce to have increased once more output, and it is believed that the effect that the minimizing of thickness directly causes is, have still less catalyzer to be transported to crystalline tip in the growth.In addition, the evaporation of catalyzer such as Ni is very difficult technically, and this just requires the usage quantity minimum of these catalyzer necessity in manufacturing processed.Therefore, become thinner, just can reduce the amount of catalystic material by the thickness that makes layer.Start from the base portion of post because it is believed that crystalline growth, so, can transport still less material and form layer away from substrate, make the less thick of these layers.
Roughly 10
-6The vacuum of Torr or in being essentially inert gas atmosphere, the temperature about can being heated to up to 950 ℃, and continue 3 minutes to 1 hour.Thereby, can obtain better result.Think that in principle the heat-up time of several minutes is just enough, this means to make longlyer can not improve the result significantly heat-up time.
According to a further aspect in the invention, a kind of parent tectosome that is used to make Single Walled Carbon Nanotube is provided, this tectosome comprises and is positioned at suprabasil at least one post, this post comprises the alternative first fertile material layer and the second fertile material layer, first fertile material comprises fullerene molecule, and second fertile material comprises catalyzer.The thickness of these layers can reduce with its distance of leaving substrate.Substrate can comprise thermal oxidation silicon or the molybdenum that is arranged on grid configuration or as solid membrane on the silicon wafer.Catalyzer can comprise magneticsubstance, preferably, is a kind of metal of choosing from Ni, Co, Fe, Mo group.
According to a further aspect in the invention, provide a kind of nanotube architecture body, this tectosome comprises a substrate and suprabasil at least one crystal, and this crystal comprises a branch of Single Walled Carbon Nanotube that orientation is identical with structure.This nanotube architecture body can be integrated in indicating meter, circuit, switching element or the sensor element.
Another aspect of the present invention provides a kind of nanotube crystal, and this crystal comprises orientation and the essentially identical a branch of straight Single Walled Carbon Nanotube of structure.
Description of drawings
Examples more of the present invention are represented in the accompanying drawings, and are described in detail by way of example below.Wherein:
Fig. 1 is the synoptic diagram of device in evaporation step of making Single Walled Carbon Nanotube;
Fig. 2 is the synoptic diagram of device in heating steps of making Single Walled Carbon Nanotube;
Fig. 3 is the synoptic diagram as the single post of the precursor structure of making Single Walled Carbon Nanotube;
Fig. 4 a is crystalline transmission electron microscope (TEM) Photomicrograph that comprises a branch of Single Walled Carbon Nanotube;
Fig. 4 b is the amplifier section of the TEM Photomicrograph of Fig. 4 a;
Fig. 4 c is the synoptic diagram of a branch of Single Walled Carbon Nanotube;
Fig. 5 is scanning electronic microscope (SEM) Photomicrograph by the typical structure of described method manufacturing; And
Fig. 6 is the electron diffraction pattern of carbon nanotube bundles.
For cause clearly, institute's drawings attached shows with physical size that all the relation between size does not show with substantial proportion yet.
Embodiment
Below, different embodiments of the invention are described.
Making the employed method of Single Walled Carbon Nanotube crystal comprises solid-state fertile material is carried out composition on the nanometer scale.By the hole on nanometer scale on the evaporation template of composition, (be C with soccerballene herein
60Molecule) and as the controlled mixture of the nickel of catalyzer be evaporated in the molybdenum substrate.The structure that obtains of pyrolysis in a vacuum then.Electron diffraction investigation and electron energy loss spectroscopy (EELS) (EELS) combine, and have confirmed, the structure that is produced is perpendicular to the almost ideal styloid of the Single Walled Carbon Nanotube of substrate surface orientation.
First synoptic diagram of making the device of Single Walled Carbon Nanotube has been shown among Fig. 1.
The mode of evaporation is to make alternative fertile material 15,16 be deposited upon substrate 4.Therefore, evaporation source 10 provides all different fertile materials 15,16, the evaporation of these fertile materials is controlled with the alternative form, evaporation source 10 is only as a kind of in the fertile material 15,16 of deposition, changes another evaporation source 10 that has in the fertile material 15,16 another then into.In the illustrated scheme two kinds of fertile materials 15,16 are arranged on the vaporizer simultaneously, two kinds of fertile materials 15,16 are placed side by side on evaporation source 10, and a divider wall is arranged between them.The present invention is provided with a closing mechanism 18, alternately constantly only allows a kind of hole 14 of passing through in the fertile material 15,16 to arrive substrates 4 at each.Thereby below each hole 14, owing to deposited the layer of the fertile material 15,16 of evaporation successively, post 8 can be grown in substrate 4.For the thickness of key-course, in evaporation step, specimen holder 9 withdrawals, and vibration quartzy 6 is moved to the position of settling substrate 4.In the frequency of monitoring quartz, carry out on-line measurement.So, can record sedimentation rate accurately, be used to determine to be deposited on the layer thickness of the fertile material 15,16 in the substrate 4 then.
In case finished required deposition, and after carrying out composition with 8 pairs of substrates of resulting post 4, manufacturing installation changed to shown in Figure 2.
What show among Fig. 3 is synoptic diagram as the single post 8 of the precursor structure that is used to make Single Walled Carbon Nanotube 19.Here, the precursor structure of growing nano-tube 19 is made of heterojunction structure, and this heterojunction structure comprises the C of alternative, thermal evaporation
60Molecular layer and nickel dam.C
60Molecule is as first fertile material 15, and nickel is as second fertile material 16.6 or 7 layers of layer that 10-20nm is thick are arranged approximately, be deposited on together from level to level.Fertile material 15,16 deposits by baffle 7.This template is represented a kind of nanometer sieve, and having several thousand diameters is the hole 14 of 300nm, interval 1 μ m.This deposition method has produced very little nucleus position, and these positions make Single Walled Carbon Nanotube crystal 20 can carry out self-assembly subsequently.Though except using baffle 7, fertile material also can be deposited in the substrate 4 with coarse polyhedron surface,, the nanotube 19 that can have precedence over unordered crystals growth has tailed off.Generally speaking, some plants brilliant position, and promptly nucleus position or crystallization position are the initial positions of crystal growth.
The contriver finds, in the structure of nucleus position near post 8, post 8 is only as near the material supply source of the crystal 20 of growth.Post 8 herein has the diameter of 300nm, but it has been generally acknowledged that the lateral dimension of post 8 can select in wideer scope.Though can obtain good result with the diameter that is roughly 300nm, 500nm or above bigger diameter also should obtain acceptable result.The lateral dimension of post 8 has determined the total amount of fertile material 15,16 in the growth of corresponding crystal 20.Therefore, the crystal 20 of each growth has the warehouse of fertile material 15,16, and crystal obtains its materials supply from this warehouse.The effect that pre-determines the material supply is to pre-determine corresponding crystal 20 in growth, the consumption and the position of different fertile materials 15,16.Therefore, the molecule of fertile material 15,16 moves and be subjected to sizable restriction in the zone of post, so disordered motion has tailed off, and has formed more definite process of growth.In addition, the relative concentration of fertile material 15,16 has conclusive effect, this means to grow into the second parent total amount of required nanotube shape with helping first fertile material 15, neither should too much also should be not low excessively.In addition, fertile material 15,16 is constrained on and has caused 15,16 of two kinds of fertile materials ratio more accurately in the post 8, and this ratio accurately helps the crystal growth of monocrystalline 20.
Because post 8 also has certain predetermined distance each other, so the mutual interference effect of crystalline in the growth is lower than block fertile material system.Therefore, each monocrystalline 20 growth on its ctystallizing point is not subjected to or only can be subjected to with ignoring the influence of the process of growth of contiguous crystal 20.Therefore, post 8 has a distance each other, and this distance has reduced the phase mutual interference of each crystal or nanotube 19 process of growth.
The lateral dimension of post 8 has limited the amount of fertile material 15,16, and provides material for the monocrystalline 20 as a branch of nanotube 19.Post shapes needn't one be decided to be round or side, but can have any suitable shape that is considered to.Yet for symmetric cause, circle is preferred.Nanotube bundle can comprise several to hundreds of, several thousand millions of nanotubes 19 even.
The nucleus position of can manually growing in substrate 4 is can control the location of crystal growth.For example, the formation of this nucleus position can obtain by the material through evaporation template 7 evaporation such as tungsten, and this material can be as the nucleus position in the substrate 4.Because evaporation template 7 has masking action, so the host material vaporizer enough far away apart from the vaporizer of fertile material 15,16 forms the nucleus position automatically near post 8.On the contrary, the vaporizer of fertile material 15,16 should lean on very closely, to avoid laterally misalignment of different layers edge in the post 8.In the case, these two vaporizers are arranged in reaction chamber 1 simultaneously.
In room temperature, 10
-9Under the pressure of Torr, carry out in the evaporating course on solid substrate 4 of thermal oxidation silicon or molybdenum TEM aperture plate, dynamo-electric switching combines with online quartz crystal microbalance and monitors sedimentation rate, can guarantee C
60Can both in turn evaporate to produce required structure with Ni.
As shown in Figure 3, on the particular surface position of determining by the relative position of hole 14 and substrate surface, produced the post 8 of fertile material 15,16.The fact that influences the selection of substrate 4 is C
60All can at high temperature spread with Ni.So the purpose here is that two kinds of materials all are limited in the initial 300nm evaporating area.Though can obtain a good result with silicon-dioxide substrate 4, but, can obtain better result with molybdenum substrate 4, the aperture plate form that this molybdenum substrate or employing are used for follow-up transmission electron microscopy method, or as being splashed to a solid membrane on the silicon wafer.In substrate 4, evaporate C
60Behind/Ni the post 8,10
-6In the vacuum of Torr this tectosome is heated to 950 ℃, the time length is chosen as several minutes to a hour.
In order on the JEOL2010 of 200kV type microscope, to carry out detailed diffraction analysis, carried out high resolution TEM (HRTEM) research on the JEOL 4000FX type microscope of 400kV working in.Studies show that its diameter of the nanotube bundle that presents is between 40nm and 900nm, its length is greatly to 2 μ m.These nanotubes 19 are straight, and preferentially are parallel to Mo aperture plate planar registration.All nanotubes 19 all are Single Walled Carbon Nanotube, have formed long and straight bundle.Very consistent at an intrafascicular wall diameter, each intrafascicular from about 1.4nm to 2.3nm.The relation that has inverse ratio between wall and beam diameter, intrafascicular what detect mainly is little wall diameter in major diameter, and what detect in small diameter beam mainly is big wall diameter.Multi-walled carbon nano-tubes both do not occur, do not occurred isolated Single Walled Carbon Nanotube yet.From wall thickness that is detected and the situation that does not have the central section, can get rid of multi-walled carbon nano-tubes.
The typical HRTEM pictorial display of a branch of nanotube 19 in Fig. 4 a, among Fig. 4 b the pictorial display of higher enlargement ratio the internal structure of nanotube bundle.The about 750nm of this nanotube bundle is long, and diameter is about 50nm, and has a curved surface termination.
Fig. 4 b has shown the perfect regular tectosome of the 1.6nm diameter Single Walled Carbon Nanotube 19 of pencil, does not have inhomogeneous and sign defective.This significant structural perfection is the feature with all nanotubes 19 of method production described here.
Fig. 4 c illustrates the synoptic diagram of the bundle of 7 nanotubes 19, and is the same with the result shown in Fig. 4 a, the 4b, and the diameter of each nanotube 19 is 1.6nm.
Fig. 5 shows scanning electronic microscope (SEM) Photomicrograph of the typical structure of making by described method.Shown the club shaped structure that length and diameter are roughly the same among the figure, and a curved surface termination has all been arranged.These club shaped structures are grown perpendicular to substrate surface.This result utilizes only excellent length and width that the feature of the structure of variable method manufacturing is arranged.In order to confirm that this rod is exactly a carbon nanotube 20, can under being grown in situation on the molybdenum gate screen, they both carry out the EELS that provides chemical ingredients, carry out electron diffraction again.EELS spectrum carbon-K edge in VG 501HB type STEM of rod obtains.VG 501HB type STEM is operated in 100kV, every channel offset 0.1eV.This EELS spectrum shows just being lower than the main 285eV place that absorbs thresholding, a high-intensity preposition peak is arranged.This preposition peak is to p in the carbon of sp2 bonding
*The feature of the transformation of attitude has hinted to have the graphite-like sheet in nanotube 19.This composes with the EELS spectrum of previous carbon nanotube 19 very approximate, has therefore confirmed that these nanotubes are made of carbon really.The important point is, only detects the existence of nickel in the EELS spectrum in the growth phase of nanotube 19, both do not had the sign of nickel also not have the sign of molybdenum in the nanotube 19 that grows up to fully.
The electron diffraction pattern of the difference bundle of the Single Walled Carbon Nanotube 19 of diameter 1.98nm is presented among Fig. 6.Can draw the perfection of structure apparently immediately from the acutance of diffraction spot.This pattern demonstrates the periodicity owing to the regularly arranged height rule that causes of intrafascicular nanotube 19.In fact, say more properly that nanotube bundle should be considered to the periodicity " crystal " of Single Walled Carbon Nanotube 19.Because this periodicity is reflected in the diffracting spectrum forcefully, almost cannot see so comprise about the weak diffraction spot and the striped of independent nanotube 19 information.
With reference to Fig. 6, shown two principal directions, wide and corresponding to the semi-simple wall carbon nano-tube tube wall of 0.99nm perpendicular to this wall cross direction, corresponding to the spacing of the 0.28nm of graphite hexahedron spacing.Weak super reflection has the spacing corresponding to the 0.28nm twice.
(n between the spirality of formal description m), has simple relation at the diameter of independent nanotube 19 with the coiling vector.The proposition of this relation is to come from consideration how the graphite flake of atomic thickness to be rolled to form nanotube.Diameter d and hand are levied angle q and are provided by following formula:
d＝0.078(n2+nm+m2)
1/2
With q=arc tan (m/ (m+2n)).
In Fig. 6, it is 90 ° that hand is levied angle q, thereby m=n.The measuring result of d is 1.98nm, and like this, n=m=15 is corresponding to so-called armrest.For any crystal of Single Walled Carbon Nanotube 19, diffraction pattern shows, it is made of physical properties Single Walled Carbon Nanotube 19 identical, chirality or armrest.Final structure is surveyed and is related to each crystalline shape.The front has shown to the detection of nanotube bundle, sees over to the end of bundle, and Single Walled Carbon Nanotube 19 is piled into hexagonal structure.The balanced shape of cross section of considering nanotube bundle may be circular, sexangle or complex cross-sectional more, based on the simple discussion of the hexagonal packed structures of identical Single Walled Carbon Nanotube 19, the structure of approving of a kind of each surface to constitute by closelypacked Single Walled Carbon Nanotube 19.This structure comprises hexagonal transverse cross section, but any cross section of being made up of 120 ° of facets is good too.Contrast in the projection of shape of nanotube bundle and the HRTEM image shows that the formation of Single Walled Carbon Nanotube 19 crystal facet has taken place really.Therefore, construct by reactant being carried out nanometer, and, just can the characteristic of self-assembled material be designed in conjunction with the environmental change of setting by three-dimensional dimension.
Based on previous result, the perfection of the crystal 20 of Single Walled Carbon Nanotube 19 can't imagine, detected in containing the given crystal 20 that reaches millions of nanotubes 19, nanotube 19 is in full accord on physical properties, also can't imagine.However, the stable structure of the bundle of nanotube 19, also with the extension array of the tight nanotube that contacts 19 on the thermodynamics expected value that distributes of least energy conform to.The minimizing of energy means that also all nanotubes 19 are consistent with straight, this make Van der Waals interact maximum, strain is minimum, and can access desirable hexagonal lattice.The evidence that crystal 20 facet forms is another the expection content that is shown by the gained result.
With nanotube 19 or the nanotube bundle that method as described herein grows into, can be used on the multiple device, for example switching arrangement, indicating meter or transmitter.Deposition one deck ITO and/or organic LED material can be used in the manufacturing indicating meter on one deck nanotube 19.Other embodiment comprises nanoelectronic circuits.In sort circuit, nanotube is as active part or leads such as FET.Also can make nano tube based vacuum tube amplifier and triode that nanotube serves as emtting electrode, thereby with the provide end of nanotube as the stabilizing low voltage operation.Nano-machine transmitter and AFM (atomic force microscope) needle point can be with nanotube as the transmitter tip.Only needing that ctystallizing point is positioned at later needle point will localized position, just can obtain required structure.Nanotube can be used as the moveable part in the switching arrangement or is integrated in the GMR head.
Any embodiment disclosed herein can with shown in and/or among described other embodiment one or several make up.One or more features among each embodiment also can be carried out such combination.Obviously, the structure shown in those skilled in the art can revise here in many ways, and can not break away from the main idea of the present invention that claims limit.
Claims (20)
1. method of making Single Walled Carbon Nanotube (19) comprises step:
A) provide at least one post (8) in substrate (4), this post comprises alternative first fertile material (15) layer and second fertile material (16) layer, and first fertile material (15) comprises fullerene molecule, and second fertile material (16) comprises catalyzer; And
B) heating described at least one post (8).
2. method according to claim 1 is characterized in that, selects substrate (4), for growing single-wall carbon nano tube (19) provides at least one crystallization position.
3. method according to claim 1 and 2 is characterized in that, selects substrate (4), is the aperture plate form on the silicon wafer or as the thermal oxidation silicon or the molybdenum of solid membrane to comprise being arranged on.
4. according to each described method in the claim 1 to 3, it is characterized in that described at least one post (8) is deposited on together from level to level by 5 to 10 layers of fertile material (15,16), every layer thickness is 5 to 30nm.
5. according to each described method in the claim 1 to 4, it is characterized in that described fertile material (15,16) deposits by a baffle (7) that comprises one or more holes (14).
6. according to each described method in the claim 1 to 5, it is characterized in that described fertile material (15,16) provides by thermal evaporation.
7. method according to claim 6 is characterized in that, carries out the evaporation of described fertile material (15,16) under the pressure about the 10-9 torr, and described substrate (4) remains on room temperature.
8. according to claim 6 or 7 described methods, it is characterized in that,, control the evaporation of fertile material (15,16) by using online day gentle closing mechanism (18) of monitoring fertile material (15,16) sedimentation rate.
9. according to each described method in the claim 6 to 8, it is characterized in that the control evaporation makes the thickness of described layer reduce with the distance that it leaves substrate (4).
10. according to each described method in the claim 1 to 9, it is characterized in that, in the vacuum of 10-6 torr roughly or roughly in the environment of rare gas element, be heated to 950 ℃ temperature always, continue 3 minutes to one hour.
11. parent tectosome that is used to make Single Walled Carbon Nanotube (19), comprise at least one post (8) that is positioned in the substrate (4), this post comprises alternative first fertile material (15) layer and second fertile material (16) layer, first fertile material (1 5) comprises fullerene molecule, and second fertile material (16) comprises catalyzer.
12. parent tectosome according to claim 11 is characterized in that, the thickness of described layer reduces with the distance that it leaves substrate (4).
13. according to claim 11 or 12 described parent tectosomes, it is characterized in that, described substrate (4) has the crystallization position that at least one is used for growing single-wall carbon nano tube (19), and described substrate (4) preferably includes to be arranged on and is the aperture plate form on the silicon wafer or as the thermal oxidation silicon or the molybdenum of solid membrane.
14. according to each described parent tectosome in the claim 11 to 13, it is characterized in that second fertile material (16) comprises magneticsubstance, preferably be selected from a kind of metal in Ni, Co, Fe, the Mo group.
15. a nanotube architecture body comprises a substrate (4) and is positioned at this suprabasil at least one crystal (20) that this crystal comprises the Single Walled Carbon Nanotube (19) of a branch of orientation and structure basically identical.
16. nanotube architecture body according to claim 15, it is characterized in that, described substrate (4) has a surface that comprises crystallization position, Single Walled Carbon Nanotube (19) grows out from described crystallization position, and this surface preferably includes to be arranged on and is the aperture plate form on the silicon wafer or as the thermal oxidation silicon or the molybdenum of solid membrane.
17., it is characterized in that under the situation that a plurality of crystal (20) are arranged, described these crystal (20) are parallel basically according to claim 15 or 16 described nanotube architecture bodies.
18. arrange according to each described nanotube in the claim 15 to 17, it is characterized in that described Single Walled Carbon Nanotube (19) is straight along its length direction basically.
19. a nanotube crystal comprises the straight Single Walled Carbon Nanotube (19) of a branch of orientation and structure basically identical.
20. an indicating meter, circuit, switching element or sensor element comprise that at least one is according to each described nanotube architecture body in the claim 15 to 18 or at least one nanotube crystal according to claim 19 (20).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| EP00124766 | 2000-11-13 | ||
| EP00124766.7 | 2000-11-13 | ||
| EP01100543.6 | 2001-01-10 | ||
| EP01100543 | 2001-01-10 |
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| Publication Number | Publication Date |
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| CN1541185A true CN1541185A (en) | 2004-10-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA01818829XA Pending CN1541185A (en) | 2000-11-13 | 2001-11-12 | Crystals comprising single-walled carbon nanotubes |
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| Country | Link |
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| US (1) | US20040115114A1 (en) |
| EP (1) | EP1337461A1 (en) |
| JP (1) | JP2004513054A (en) |
| KR (1) | KR20040010558A (en) |
| CN (1) | CN1541185A (en) |
| AU (1) | AU2002214190A1 (en) |
| WO (1) | WO2002038496A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457609C (en) * | 2000-11-13 | 2009-02-04 | 国际商业机器公司 | Manufacturing method and application of single wall carbon nano tube |
| CN101578666B (en) * | 2006-10-19 | 2012-02-29 | 佛罗里达大学研究基金公司 | Transparent and electrically conductive single wall carbon nanotube |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100490472B1 (en) * | 2002-06-04 | 2005-05-19 | 충남대학교산학협력단 | Carbon nanotubes synthesis method using magnetic fluids |
| JP4642658B2 (en) * | 2003-02-07 | 2011-03-02 | 茂夫 丸山 | Method for producing single-walled carbon nanotubes with uniform diameter |
| US7947247B2 (en) | 2005-03-29 | 2011-05-24 | Hyperion Catalysis International, Inc. | Method for preparing single walled carbon nanotubes from a metal layer |
| JP2008534425A (en) * | 2005-03-29 | 2008-08-28 | ハイピリオン カタリシス インターナショナル インコーポレイテッド | Method for producing single-walled carbon nanotubes from a metal layer |
| EP2001795A4 (en) | 2006-03-29 | 2012-06-27 | Hyperion Catalysis Int | Method for preparing uniform single walled carbon nanotubes |
| CN101454242B (en) * | 2006-03-29 | 2012-04-11 | 海珀里昂催化国际有限公司 | Method for preparing single walled carbon nanotubes from a metal layer |
| US20100117764A1 (en) * | 2006-04-17 | 2010-05-13 | Board Of Regents, The University Of Texas System | Assisted selective growth of highly dense and vertically aligned carbon nanotubes |
| JP5125195B2 (en) * | 2007-04-13 | 2013-01-23 | トヨタ自動車株式会社 | Quantum dot manufacturing method |
| CN101409962B (en) | 2007-10-10 | 2010-11-10 | 清华大学 | Surface heat light source and preparation method thereof |
| CN101400198B (en) | 2007-09-28 | 2010-09-29 | 北京富纳特创新科技有限公司 | Surface heating light source, preparation thereof and method for heat object application |
| CN102019039B (en) * | 2009-09-11 | 2013-08-21 | 清华大学 | Infrared physiotherapy apparatus |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5805431A (en) * | 1996-01-17 | 1998-09-08 | Synergy Microwave Corporation | Surface Mountable transformer |
| US6683783B1 (en) * | 1997-03-07 | 2004-01-27 | William Marsh Rice University | Carbon fibers formed from single-wall carbon nanotubes |
| JP2003092218A (en) * | 2001-09-18 | 2003-03-28 | Hitachi Cable Ltd | Coil for electric/electronic equipment, and manufacturing method therefor |
-
2001
- 2001-11-12 EP EP01982648A patent/EP1337461A1/en not_active Withdrawn
- 2001-11-12 AU AU2002214190A patent/AU2002214190A1/en not_active Abandoned
- 2001-11-12 KR KR10-2003-7006426A patent/KR20040010558A/en not_active Application Discontinuation
- 2001-11-12 JP JP2002541040A patent/JP2004513054A/en active Pending
- 2001-11-12 CN CNA01818829XA patent/CN1541185A/en active Pending
- 2001-11-12 US US10/416,553 patent/US20040115114A1/en not_active Abandoned
- 2001-11-12 WO PCT/IB2001/002123 patent/WO2002038496A1/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457609C (en) * | 2000-11-13 | 2009-02-04 | 国际商业机器公司 | Manufacturing method and application of single wall carbon nano tube |
| CN101578666B (en) * | 2006-10-19 | 2012-02-29 | 佛罗里达大学研究基金公司 | Transparent and electrically conductive single wall carbon nanotube |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1337461A1 (en) | 2003-08-27 |
| AU2002214190A1 (en) | 2002-05-21 |
| JP2004513054A (en) | 2004-04-30 |
| US20040115114A1 (en) | 2004-06-17 |
| KR20040010558A (en) | 2004-01-31 |
| WO2002038496A1 (en) | 2002-05-16 |
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