CN100500554C - Production of carbon nano-tubes - Google Patents
Production of carbon nano-tubes Download PDFInfo
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- CN100500554C CN100500554C CNB2005101000531A CN200510100053A CN100500554C CN 100500554 C CN100500554 C CN 100500554C CN B2005101000531 A CNB2005101000531 A CN B2005101000531A CN 200510100053 A CN200510100053 A CN 200510100053A CN 100500554 C CN100500554 C CN 100500554C
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- carbon nanotube
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Abstract
Production of carbon nano-tube is carried out by providing a basis, forming multiple micro sprue on basis, forming a catalyst at one end of each micro-sprue, forming a electrode at another end of each micro-sprue, applying voltage between the catalyst and electrode, growing carbon nano-tube in micro-sprue along electrode by chemical gas-phase depositing method, forming a protective layer on carbon nano-tube, covering the protective layer a preset length of carbon nano-tube in micro sprue, oxidation removing uncovered carbon nano-tube, removing protective layer and obtaining the final product.
Description
[technical field]
The present invention relates to a kind of preparation method of carbon nano-tube, especially utilize chemical Vapor deposition process to carry out the preparation method of carbon nano-tube of carbon nano tube growth.
[background technology]
Since the Iijima of Japanese NEC Corporation in 1991 finds carbon nanotube, optics, electricity and the mechanical properties of uniqueness because carbon nanotube has many excellences, it presents very application prospects.Carbon nanotube has good electronic emission performance, thermal conductivity and special mechanical properties, utilize carbon nanotube as field electron emission materials, and, all become the important directions that the research carbon nanotube is used as weighting material and engineering materials compounding technology.
An important applied field of carbon nanotube is a feds.Generally speaking, the desired carbon nanotube collimation of feds is higher, and need have homogeneous length, so that the characteristic of carbon nanotube emitting electrons is more consistent, makes feds produce more uniform brightness and good display effect.In addition, often need a large amount of carbon nanotubes as the matrix material of packing material, have uniform mechanics or other physical properties, require carbon nanotube to have single character, for example have uniform length and diameter for making the matrix material after the filling with carbon nanotube.
At present a large amount of processing methodes of making carbon nanotubes have a variety of, comprise laser method of evaporation and arc discharge method etc., and the carbon nanotube of right aforesaid method gained or more mixed and disorderly, or length is inhomogeneous is difficult to satisfy an emission and the demand in rice material field how.
In view of this, be necessary to provide a kind of preparation method of carbon nano-tube, it can prepare isometric collimation carbon nanotube.
[summary of the invention]
To a kind of preparation method of carbon nano-tube be described with specific embodiment below, it can prepare isometric collimation carbon nanotube.
A kind of preparation method of carbon nano-tube, it may further comprise the steps:
One substrate is provided, in this substrate, forms a plurality of fluid channel;
End in each fluid channel forms a catalyzer;
The relative the other end forms an electrode in each fluid channel;
Between this catalyzer and electrode, apply a voltage, utilize chemical Vapor deposition process in fluid channel, to give birth to
Long carbon nanotube, this carbon nanotube will be grown to electrode direction;
Form a protective layer on carbon nanotube, this protective layer covers one of the interior carbon nanotube of fluid channel and is scheduled to
Length;
Oxidation removal is the carbon nanotube of protected seam covering not;
Remove protective layer, obtain carbon nanotube.
With respect to prior art, described preparation method of carbon nano-tube, form fluid channel at substrate surface, and catalyzer and electrode are set respectively at the two ends of this fluid channel, in the chemical vapor deposition growth carbon nanotube, provide the growing environment of carbon nanotube with fluid channel, and with its direction of growth of electric field leading, thereby guarantee the collimation of carbon nanotube; Again with a predetermined length of protective layer coated carbon nanotube, the carbon nanotube partial oxidation reaction of protected seam covering protection is not fallen, thereby make carbon nanotube isometric, finally realize the preparation of isometric collimation carbon nanotube.
[description of drawings]
Fig. 1 is the embodiment of the invention is formed with fluid channel in substrate a synoptic diagram.
Fig. 2 is the synoptic diagram that the end of the embodiment of the invention in fluid channel forms catalyzer.
Fig. 3 is the synoptic diagram that the embodiment of the invention relative the other end in fluid channel forms electrode.
Fig. 4 is the synoptic diagram of embodiment of the invention carbon nano-tube in fluid channel.
Fig. 5 is the synoptic diagram that forms protective layer on the carbon nanotube of the embodiment of the invention in the substrate fluid channel.
Fig. 6 is that the embodiment of the invention is removed protective layer, prepares the synoptic diagram of isometric collimation carbon nanotube.
[embodiment]
Below in conjunction with accompanying drawing the embodiment of the invention is described in further detail.
A kind of preparation method of carbon nano-tube that the embodiment of the invention provides, it may further comprise the steps:
(1) referring to Fig. 1, a substrate 10 is provided, in this substrate 10, form a plurality of fluid channel 20.This substrate 10 can be selected materials such as Silicon Wafer, glass wafer for use, and present embodiment adopts Silicon Wafer.The formation method of this fluid channel 20 can adopt electric paste etching, wet etching and reactive ion etching etc., present embodiment adopts the electric paste etching method to form a plurality of fluid channel 20 in substrate 10, the width of described fluid channel is less than 1 millimeter, and preferred, the width of fluid channel is 1～50 micron.
(2) referring to Fig. 2, the end in fluid channel 20 forms catalyzer 30.The material of this catalyzer 30 can be selected iron, cobalt, nickel or its alloy for use, and its formation method can adopt ion plating method, radio frequency magnetron sputter, vacuum vapor deposition method, chemical Vapor deposition process etc. to cooperate mask to form.Present embodiment adopts the radio frequency magnetron sputtering method, and the end in fluid channel 20 forms an iron catalyst.
(3) referring to Fig. 3, in fluid channel 20, the catalyzer 30 relative the other ends form electrode 40.The material of this electrode 40 can be selected metals such as copper, aluminium, silver for use, and its formation method can adopt sedimentation to cooperate a mask to form, and present embodiment utilizes mask deposited copper electrode 40 in fluid channel 20.
(4) referring to Fig. 4, between this catalyzer 30 and electrode 40, apply a voltage to produce an electric field, utilize chemical Vapor deposition process (as, hot-filament cvd reactor method, plasma enhanced chemical vapor deposition method etc.) carbon nano-tube 50.This carbon nanotube 50 will be grown to electrode 40 directions in fluid channel.Specific descriptions are:
The above-mentioned substrate 10 that is formed with catalyzer 30 and electrode 40 is placed in a CVD (Chemica1 VaporDeposition, the chemical vapour deposition) reactor 70, heat 10 to 500～1000 degrees centigrade of this substrates; And in this CVD reactor 70, feed carbon source gas (as, ethene, methane, acetylene etc.) carbon nano-tube; When carbon nano tube growth begins, between catalyzer 30 and electrode 40, apply a voltage.At this moment, will produce an electric field (figure does not show), its direction is parallel to substrate 10 surfaces and consistent with the direction of fluid channel 20, and carbon nanotube 50 will be grown along direction of an electric field, promptly grow to electrode 40 directions along fluid channel 20.
(5) referring to Fig. 5, treat that carbon nanotube 50 growth finishes after, form a protective layer 60, a predetermined length of coated carbon nanotube 50.The material of this protective layer 60 can be selected from polysilicon, silicon nitride etc., and present embodiment is selected silicon nitride for use; The formation method of protective layer 60 can adopt spin coating method, dip process etc., and present embodiment adopts spin coating method.Described predetermined length is the length of last gained carbon nanotube, can decide according to concrete length requirement.
(6) part of not protected seam 60 coverings of oxidation removal carbon nanotube.Above-mentioned substrate 10 is inserted in the High Temperature Furnaces Heating Apparatus, heat 10 to 400～600 degrees centigrade of this substrates; And in this High Temperature Furnaces Heating Apparatus, feed oxidizing gas, the present embodiment aerating oxygen.Under described temperature environment, the part that the not protected seam 60 of carbon nanotube covers will be oxidized to CO
2Or CO and removing.
(7) referring to Fig. 6, remove protective layer 60, obtain carbon nanotube 501.Remove material difference that etching solution that protective layer 60 adopted chooses according to protective layer 60 and different, as, when the protective layer material is polysilicon, can select etching solutions such as potassium hydroxide or Tetramethylammonium hydroxide for use; When the protective layer material is silicon nitride, then can select etching solutions such as phosphoric acid for use.Present embodiment uses phosphoric acid to remove the protective layer 60 of material as silicon nitride, and then can obtain isometric collimation carbon nanotube 501.
Preparation method of carbon nano-tube in the present embodiment, form fluid channel at substrate surface, and catalyzer and electrode are set respectively at the two ends of this fluid channel, in the chemical vapor deposition growth carbon nanotube, the growing environment of carbon nanotube is provided with fluid channel, and with its direction of growth of electric field leading, thereby guarantee the collimation of carbon nanotube; Again with a predetermined length of protective layer coated carbon nanotube, the carbon nanotube partial oxidation reaction of protected seam covering protection is not fallen, thereby make carbon nanotube isometric, finally realize the preparation of isometric collimation carbon nanotube.
In addition, those skilled in the art also can do other and change in spirit of the present invention, as the formation method of the width of suitable change fluid channel and queueing discipline, catalyzer etc., as long as it does not depart from technique effect of the present invention and all can.The variation that these are done according to spirit of the present invention all should be included within the present invention's scope required for protection.
Claims (11)
1. preparation method of carbon nano-tube may further comprise the steps:
One substrate is provided, in this substrate, forms a plurality of fluid channel;
End in each fluid channel forms a catalyzer;
The relative the other end forms an electrode in each fluid channel;
Between this catalyzer and electrode, apply a voltage, utilize chemical Vapor deposition process in fluid channel, to grow
Carbon nanotube, this carbon nanotube will be grown to electrode direction;
Form a protective layer on carbon nanotube, this protective layer covers a predetermined length of carbon nanotube in the fluid channel;
Oxidation removal is the carbon nanotube of protected seam covering not;
Remove protective layer, obtain carbon nanotube.
2. preparation method of carbon nano-tube as claimed in claim 1 is characterized in that described substrate is Silicon Wafer or glass wafer.
3. preparation method of carbon nano-tube as claimed in claim 1 is characterized in that the formation method of described fluid channel comprises electric paste etching, wet etching or reactive ion etching.
4. preparation method of carbon nano-tube as claimed in claim 1, the width that it is characterized in that described fluid channel is 1～50 micron.
5. preparation method of carbon nano-tube as claimed in claim 1, the material that it is characterized in that described catalyzer are iron, cobalt, nickel or its alloy.
6. preparation method of carbon nano-tube as claimed in claim 1 is characterized in that the formation method of described protective layer comprises spin coating method or dip process.
7. preparation method of carbon nano-tube as claimed in claim 1 is characterized in that the not carbon nanotube of protected seam covering of described oxidation removal, may further comprise the steps:
The carbon nanotube that will be formed with protective layer is inserted in the High Temperature Furnaces Heating Apparatus together with substrate;
Heat this substrate to 400～600 degree centigrade, and in this High Temperature Furnaces Heating Apparatus, feed oxidizing gas, to remove the carbon nanotube that protected seam not covers.
8. preparation method of carbon nano-tube as claimed in claim 1, the material that it is characterized in that described protective layer is a polysilicon.
9. preparation method of carbon nano-tube as claimed in claim 8 is characterized in that the etching solution that described removal protective layer is adopted comprises potassium hydroxide or Tetramethylammonium hydroxide.
10. preparation method of carbon nano-tube as claimed in claim 1, the material that it is characterized in that described protective layer is a silicon nitride.
11. preparation method of carbon nano-tube as claimed in claim 10 is characterized in that the etching solution that described removal protective layer is adopted comprises phosphoric acid.
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| CNB2005101000531A CN100500554C (en) | 2005-09-29 | 2005-09-29 | Production of carbon nano-tubes |
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| CNB2005101000531A CN100500554C (en) | 2005-09-29 | 2005-09-29 | Production of carbon nano-tubes |
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| CN100500554C true CN100500554C (en) | 2009-06-17 |
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| CN110055625B (en) * | 2019-03-28 | 2022-03-22 | 西南科技大学 | Method for preparing carbon nano-fiber by using halloysite as catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433962A (en) * | 2002-01-25 | 2003-08-06 | 中国科学院化学研究所 | Process for preparing strip type array carbon nano tube |
| JP2005158686A (en) * | 2003-11-26 | 2005-06-16 | Samsung Sdi Co Ltd | Carbon nanotube forming method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433962A (en) * | 2002-01-25 | 2003-08-06 | 中国科学院化学研究所 | Process for preparing strip type array carbon nano tube |
| JP2005158686A (en) * | 2003-11-26 | 2005-06-16 | Samsung Sdi Co Ltd | Carbon nanotube forming method |
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