CN100411980C - Method for controlling growth density of carbon nanometer tube - Google Patents
Method for controlling growth density of carbon nanometer tube Download PDFInfo
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- CN100411980C CN100411980C CNB031349862A CN03134986A CN100411980C CN 100411980 C CN100411980 C CN 100411980C CN B031349862 A CNB031349862 A CN B031349862A CN 03134986 A CN03134986 A CN 03134986A CN 100411980 C CN100411980 C CN 100411980C
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- carbon nanotube
- protective layer
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- catalyst
- stand density
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Abstract
The present invention relates to a method for controlling the growth intensity of carbon nanometer tubes, which comprises the following steps: a substrate is provided; a protective layer is formed on the surface of the substrate; a catalyst layer is formed on the surface of the protective layer; the substrate formed with the protective layer and the catalyst layer is put in a reaction furnace for annealing treatment; carbon source gas is introduced so as to grow carbon nanometer tubes. One protective layer is formed on the substrate, and the present invention prevents a catalyst from reacting with the substrate in the annealing and reducing process. The uniform distribution density of catalyst particles is ensured, and thereby, the carbon nanometer tubes with uniform distribution density are grown.
Description
[technical field]
The invention relates to a kind of method of controlling carbon nanotube stand density.
[background technology]
Carbon nanotube is a kind of new carbon, is found in 1991 by Japanology personnel Iijima, sees also " Helical microtubules of graphitic carbon ", S Iijima, Nature, vol.354, p56 (1991).Because carbon nanotube has utmost point excellent specific property, its application is subjected to people's extensive concern always, especially at electronic applications, because the carbon nanotube diameter is minimum, only be a few nanometer to tens nanometers, can be under the small electric field action from its most advanced and sophisticated emitting electrons, thereby can be used as field-transmitting cathode.
In recent years, people carry out various researchs in nano material and its Application Areas, and are especially more to growth method and its applied research of carbon nanotube.The method of carbon nano-tube has arc discharge method, chemical Vapor deposition process etc. in the prior art.The advantage that wherein chemical Vapor deposition process has that cost is low, output is big, experiment condition is easy to control, and can carbon nano tube array grows, be widely used in carbon nano-tube.The chemical Vapor deposition process carbon nano-tube generally comprises the following step: a substrate is provided; Deposit a catalyst layer at substrate surface; Reaktionsofen is put in the substrate of deposited catalyst layer, and anneal makes catalyzer become nano-scale particle; Under protection of inert gas, feed carbon-source gas in the Reaktionsofen, on catalyst layer, grow carbon nanotube.
But there is following problem in the chemical Vapor deposition process carbon nano-tube: in the annealing process transition-metal catalyst easily and substrate react, cause the granules of catalyst distribution density to be not easy to control, thereby directly influence the density of carbon nano tube growth.The even carbon nanotube of density unevenness is limited on using, and for example is applied to Field Emission Display, will directly cause the display brightness inequality, even occur dim spot on the display screen.
So, provide a kind of method of controlling carbon nanotube stand density real for necessary.
[summary of the invention]
React with substrate easily and cause the granules of catalyst distribution density to be not easy to control for solving in the chemical Vapor deposition process carbon nano-tube catalyst reduction annealing process catalyzer, thereby the technical problem that causes institute's carbon nanotubes grown distribution density inequality the invention provides a kind of method of controlling carbon nanotube stand density.
The method of controlling carbon nanotube stand density provided by the present invention comprises the following steps: to provide a substrate; Form a protective layer at substrate surface, this protective layer is a metal nitride, and its thickness is 20～80 nanometers; Form a catalyst layer on the protective layer surface; Reaktionsofen is put in the substrate that will be formed with protective layer and catalyst layer, anneal; Feed carbon source gas carbon nano-tube.
The present invention has following advantage: form a protective layer in the substrate; catalyst layer is deposited on this protective layer; protective layer is isolated substrate and catalyst layer; thereby prevent that catalyzer from reacting with substrate in the annealing reduction process; make and the nm-class catalyst size distribution controllable density that annealing reduction back forms guarantee that the carbon nanotube that grows on the catalyst layer is evenly distributed.
[description of drawings]
Fig. 1 is the method flow diagram of controlling carbon nanotube stand density of the present invention.
Fig. 2 is the synoptic diagram of the used substrate of the present invention.
Fig. 3 is the synoptic diagram that forms protective layer at used substrate surface.
Fig. 4 is the synoptic diagram that forms catalyst layer on protective layer.
Fig. 5 is the carbon nanotube synoptic diagram that utilizes the inventive method to obtain.
[embodiment]
See also Fig. 1, be the method flow diagram of controlling carbon nanotube stand density of the present invention.The inventive method comprises the following steps:
Step 2 forms a protective layer at substrate surface.This step is to form certain thickness protective layer on the surface of described substrate; avoid catalyst layer directly to contact with substrate surface; thereby catalyzer and substrate generation chemical reaction when preventing to anneal reducing catalyst; make and the nm-class catalyst size distribution controllable density that annealing reduction back forms guarantee that the carbon nano tube growth density distribution is even.Protective layer material is a metal nitride, as titanium nitride or tantalum nitride.
See also Fig. 2 to Fig. 5, will describe each step of the present invention in detail with concrete embodiment below.
See also Fig. 2, the specific embodiment of the invention selects for use silicon as substrate 10, and substrate 10 has a flat surface, and to be fit to carbon nano tube growth, its planeness can realize by methods such as mechanical polishing or electrochemical etchings.Size of foundation base can be determined according to the specific requirement of required carbon nanotube.
As shown in Figure 3, plate a protective layer 11 by evaporation or jet-plating method on substrate 10 surfaces, this protective layer 11 is a metal nitride, as titanium nitride or tantalum nitride.These protective layer 11 thickness are greater than 20 nanometers, and preferred 30 nanometers～80 nanometers require surfacing.
As shown in Figure 4, at protective layer 11 surface deposition catalyst layers 12, catalyst layer 12 is a metal catalyst, generally comprises Fe, Co, Ni or its alloy, and deposition method can adopt electron beam evaporation, thermal evaporation or sputtering method.Catalyst layer 12 thickness are 1～20 nanometer, are preferably 3～5 nanometers.
Reaktionsofen is put in the substrate 10 that will be formed with protective layer 11 and catalyst layer 12, under rare gas element such as the argon shield, the reduction of annealing under 300 ℃～400 ℃ temperature, make catalyzer form nano-scale particle.
Feed carbon-source gas ethene at last in Reaktionsofen, grow carbon nanotube 16 with chemical Vapor deposition process on catalyst layer 12, wherein carbon-source gas can also be carbonaceous gass such as acetylene, methane.
The present invention has following advantage: form a protective layer in the substrate, catalyst layer is deposited on this protective layer On, protective layer makes the isolation of substrate and catalyst layer, thereby prevent catalyst in the annealing reduction process with base End reaction so that the nm-class catalyst distribution of particles density that forms after the annealing reduction is controlled, guarantees catalysis The CNT of growing on the agent layer is evenly distributed.
Claims (9)
1. the method for a controlling carbon nanotube stand density comprises the following steps:
One substrate is provided;
Form a protective layer on the surface of described substrate, this protective layer is a metal nitride, and its thickness is 20～80 nanometers;
Form a catalyst layer on the protective layer surface;
Annealing reducing catalyst layer;
Feed carbon source gas;
Generate carbon nanotube in catalyst layer surface.
2. the method for controlling carbon nanotube stand density as claimed in claim 1 is characterized in that this protective layer comprises titanium nitride or tantalum nitride.
3. the method for controlling carbon nanotube stand density as claimed in claim 1 is characterized in that this protective layer thickness is 30～80 nanometers.
4. the method for controlling carbon nanotube stand density as claimed in claim 1 is characterized in that this protective layer forms by vapour deposition method or sputtering method.
5. the method for controlling carbon nanotube stand density as claimed in claim 1 is characterized in that this substrate comprises silicon, quartz or metal.
6. the method for controlling carbon nanotube stand density as claimed in claim 1 is characterized in that this catalyst layer is a metal catalyst.
7. the method for controlling carbon nanotube stand density as claimed in claim 1 is characterized in that this catalyst layer thickness is 1～20 nanometer.
8. the method for controlling carbon nanotube stand density as claimed in claim 1, the reduction process that it is characterized in that annealing is carried out under protection of inert gas.
9. the method for controlling carbon nanotube stand density as claimed in claim 1 is characterized in that the carbon source gas bag draws together ethene, acetylene or methane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031349862A CN100411980C (en) | 2003-09-30 | 2003-09-30 | Method for controlling growth density of carbon nanometer tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031349862A CN100411980C (en) | 2003-09-30 | 2003-09-30 | Method for controlling growth density of carbon nanometer tube |
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| Publication Number | Publication Date |
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| CN1603231A CN1603231A (en) | 2005-04-06 |
| CN100411980C true CN100411980C (en) | 2008-08-20 |
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| CNB031349862A Expired - Fee Related CN100411980C (en) | 2003-09-30 | 2003-09-30 | Method for controlling growth density of carbon nanometer tube |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372327B (en) * | 2008-09-26 | 2011-03-23 | 厦门大学 | Growth method of carbon nano-tube array |
| JP5016016B2 (en) * | 2009-11-27 | 2012-09-05 | トヨタ自動車株式会社 | Surface-treated mold and manufacturing method thereof |
| CN101857460A (en) * | 2010-05-20 | 2010-10-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of carbon nano tube array for spinning |
| CN103771389B (en) * | 2013-12-20 | 2016-01-06 | 中国科学院上海硅酸盐研究所 | The carbon nano pipe array of uniform diameter and growth method thereof |
| CN103940269B (en) * | 2014-04-25 | 2017-04-26 | 上海交通大学 | Heat tube based on carbon nano tube wick and manufacturing method of heat tube |
| CN111909666A (en) * | 2020-08-12 | 2020-11-10 | 杭州英希捷科技有限责任公司 | Non-transfer type thermal interface material based on vertical carbon nanotube array and method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6232706B1 (en) * | 1998-11-12 | 2001-05-15 | The Board Of Trustees Of The Leland Stanford Junior University | Self-oriented bundles of carbon nanotubes and method of making same |
| US6261532B1 (en) * | 1998-03-25 | 2001-07-17 | Research Institute Of Innovative Technology For The Earth | Method of producing carbon |
| CN1388059A (en) * | 2002-04-17 | 2003-01-01 | 中山大学 | Controllable growth process of carbon nanotube in certain diameter and distribution density |
| CN1460638A (en) * | 2003-06-11 | 2003-12-10 | 中国科学院上海微***与信息技术研究所 | Flaky carbon nano tube, preparation method and special equipment |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261532B1 (en) * | 1998-03-25 | 2001-07-17 | Research Institute Of Innovative Technology For The Earth | Method of producing carbon |
| US6232706B1 (en) * | 1998-11-12 | 2001-05-15 | The Board Of Trustees Of The Leland Stanford Junior University | Self-oriented bundles of carbon nanotubes and method of making same |
| CN1388059A (en) * | 2002-04-17 | 2003-01-01 | 中山大学 | Controllable growth process of carbon nanotube in certain diameter and distribution density |
| CN1460638A (en) * | 2003-06-11 | 2003-12-10 | 中国科学院上海微***与信息技术研究所 | Flaky carbon nano tube, preparation method and special equipment |
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