CN1129168C - Process for preparing film cathode of nm carbon tubes used for generating catalyst particles - Google Patents
Process for preparing film cathode of nm carbon tubes used for generating catalyst particles Download PDFInfo
- Publication number
- CN1129168C CN1129168C CN 00135476 CN00135476A CN1129168C CN 1129168 C CN1129168 C CN 1129168C CN 00135476 CN00135476 CN 00135476 CN 00135476 A CN00135476 A CN 00135476A CN 1129168 C CN1129168 C CN 1129168C
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- substrate
- reative cell
- preparation
- colloidal sol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a process for preparing film cathodes of carbon nano tubes used for generating catalyst particles, which comprises colloidal sol preparation, substrate pretreatment, carbon nano tube film cathode preparation, inspection and packaging. The growth density of a carbon nano tube of the present invention can be regulated by the concentration of colloidal sol. Because a catalyst can be introduced to the surface of a substrate by a coating method, large-area growth can be realized. The colloidal sol can be converted into gel or dispersed to other jelly media, so the colloidal sol can be printed onto the substrate bh a silk screen printing technology. Most of carbon nano tubes grown by the present invention are multi-layer carbon nano tubes with opening structures which have good field emission characteristics and stability.
Description
One, technical field
The invention belongs to technical field of semiconductors, be specifically related to use the reduction of gaseous compound or decompose the preparation of semiconductor device of the device that has a potential-jump barrier or surface potential barrier at least that produces solid condensate or the manufacturing or the processing of its parts.
Two, background technology
The preparation method of carbon nanotube cathod has grafting at present, and this method is normally mixed carbon nano-tube with pulping material, make the slurry of available silk screen process, is printed on the substrate then.Most of pulping material is removed in annealed roasting, thereby makes the carbon nanotube cathod film.The carbon nano-tube thin film cathode of this method gained owing to have only the fraction carbon nano-tube to expose its tip from backing material and remaining pulping material, is difficult to obtain big field emission.Remaining pulping material is the objectionable impurities that influences field transmitting uniformity, owing to be subjected to the restriction of silk screen printing precision, these class methods are difficult to realize high-precision cathode pattern.
Three, summary of the invention
The objective of the invention is to overcome above-mentioned carbon nanotube cathod preparation method's shortcoming, the preparation method who provide that a kind of technology is simple, cost is low, utilization that can large area deposition generates the carbon nano-tube thin film cathode of catalyst granules.
For achieving the above object, it is to be prepared into by following technical process for the solution that the present invention adopts:
(1), colloidal sol preparation
Join the aqueous solution of making above-mentioned salt in the water of 100～250 times of weight ratios with the hydrochloride of iron or cobalt or nickel or sulfate or nitrate or acetate.
Remove ionized water and be heated to boiling, add the aqueous solution of the above-mentioned salt that has prepared while stirring, the weight ratio of the aqueous solution of deionized water and above-mentioned salt is 1/100～2/100, is heated with stirring to boiling again and makes colloidal sol;
(2), substrate preliminary treatment
With silicon chip or titanium dioxide silicon chip or potsherd as substrate, substrate is put into supersonic wave cleaning machine, add absolute ethyl alcohol and soaked substrate, connect the power supply of ultrasonic cleaning machine, use ultrasonic waves for cleaning, pour out absolute ethyl alcohol then, add deionized water again, connect the power supply of supersonic wave cleaning machine to the submergence substrate, there is not grease with ultrasonic waves for cleaning to surperficial no-sundries, substrate is immersed in the colloidal sol, take out, dry at normal temperatures.
(3) preparation of carbon nano-tube thin film cathode
To be placed on the quartz boat through pretreated substrate; the power supply of connecting low pressure chemical gas aggradation stove heats up; when reaction chamber temperature near reduction temperature required 650 °～850 ℃ the time; under nitrogen protection, quartz boat is pushed the reative cell of this stove; quartz boat with meet airflow direction and become 15 °～30 ° the gradient, iron or the cobalt or the nano nickel particles of the oxidation state that is formed by sol particle on the reduction substrate carry out high temperature reduction then; when reaction chamber temperature is 650 ℃～850 ℃, feed H
2With N
2Gaseous mixture, H
2/ N
2The volume ratio of gaseous mixture is 4/1～10/1, and flow is 20ml/min, and the reative cell internal gas pressure is 20～30 torrs, reduces 0.5～2 hour, gets iron or the cobalt or the nano nickel particles of simple substance, then is 650 ℃～800 ℃ in the reative cell furnace temperature and feeds C down
2H
2With N
2Mist, C
2H
2/ N
2Volume ratio be 1/10～1/2, reative cell air pressure was grown 1～2 hour at 40～80 torrs; on substrate, generate one deck black carbon nano-tube thin film cathode, behind the growth ending, under nitrogen protection; obtained carbon nano-tube thin film cathode is pulled to the reative cell mouth, and cooling is taken out then.
(4), check, packing
Obtained product is carried out quality inspection, qualified after, the packing, the warehouse-in.
In the preparation technology's of the present invention formulations prepared from solutions, wherein the hydrochloride of iron or cobalt or nickel or sulfate or nitrate or acetate join the aqueous solution of making above-mentioned salt in the water of 180～220 preferred weight ratios, and the preferred weight ratio of the aqueous solution of deionized water and above-mentioned salt is 2/100 to make colloidal sol; In the preparation of carbon nano-tube thin film cathode, wherein preferred reduction temperature is 700 °～750 ℃, feeds H
2With N
2Preferred volume ratio be 4/1～6/1 gaseous mixture, the reative cell internal gas pressure preferably reduced 1～1.5 hour at 20～30 torrs, was 650 °～750 ℃ in the preferred temperature of reative cell then and fed C down
2H
2With N
2Preferred volume ratio be 1/5～1/4 gaseous mixture, the preferred air pressure of reative cell is at 50～60 torrs, preferred growth 1～1.5 hour.
In the preparation method's of the present invention formulations prepared from solutions, wherein the hydrochloride of iron or cobalt or nickel or sulfate or nitrate or acetate join the aqueous solution of making above-mentioned salt in the water of 200 times of optimum weight ratios, and the optimum weight ratio of the aqueous solution of deionized water and above-mentioned salt is 1/100 to make colloidal sol; In the preparation of carbon nano-tube thin film cathode, wherein best reduction temperature is 720 ℃, feeds H
2With N
2Optimum volume ratio be 7/1 gaseous mixture, optimum gas is pressed in 25 torrs in the reative cell, best reduction 1 hour is 720 ℃ in the reative cell optimum temperature then and feeds C down
2H
2With N
2Optimum volume ratio be 1/6 gaseous mixture, the best air pressure of reative cell is 60 torrs, optimum growh 1.5 hours.
The present invention and existing carbon are received to plant for the title of pipe film cathode and are compared, carbon nano tube growth density can be regulated by collosol concentration, utilize colloidal sol then not need the porous surface substrate, because catalyst is introduced substrate surface by coating method, can realize large area deposition, colloidal sol can change gel into or be distributed to other and freeze in the shape medium, can be printed on substrate by silk-screen printing technique, adopt carbon nanotubes grown great majority of the present invention for having the multilayer carbon nanotube of hatch frame, have good field emission characteristic and stability.
Four, description of drawings
Fig. 1 is a carbon nano-tube thin film cathode field emission characteristic curve.
Five, embodiment
In order to show beneficial effect of the present invention, the present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
It is as follows that the inventor has provided first embodiment of the invention:
1. colloidal sol preparation
Solution preparation: take by weighing 2 gram FeCl
3, it is dissolved in the 200 gram water, make FeCl
3The aqueous solution.
Colloid preparation: deionized water merit heat to boiling, is splashed into deionized water then while stirring and prepares FeCl
3The aqueous solution, again agitating heating 3 minutes red tan solution promptly join Fe (OH)
3Solution.
Also available cobalt chloride or cobalt nitrate or cobaltous sulfate or cobalt acetate or nickel chloride or nickel nitrate or nickelous sulfate or nickel acetate are made the solution of these salt.
2. substrate preliminary treatment
Substrate cleans: with N type silicon chip is substrate, substrate is put into supersonic wave cleaning machine, absolute ethyl alcohol is joined in the supersonic wave cleaning machine till the submergence substrate, connect the power supply of supersonic wave cleaning machine, use ultrasonic waves for cleaning, bleed off absolute ethyl alcohol and again deionized water is joined in the supersonic wave cleaning machine till the submergence substrate, connect the power supply of supersonic wave cleaning machine, use ultrasonic waves for cleaning, do not have grease to surperficial no-sundries and end.
Colloidal sol coated and dry: with ready silicon chip at the Fe for preparing (OH)
3Soak in the colloidal sol, tiling is dried in the shade, and makes Fe (OH)
3Sol particle is evenly distributed on silicon chip surface.
Also available titanium dioxide silicon chip of the substrate of present embodiment or potsherd are as substrate.
3. carbon nano-tube thin film cathode preparation
Go into stove: will place quartz boat through pretreated silicon chip, and when reaction chamber temperature reaches 650 ℃, under nitrogen protection, silicon chip substrate be pushed in the reative cell, quartz boat becomes 15 ° of gradients meeting airflow direction.
High temperature reduction: when reaction chamber temperature is 800 ℃, feed H
2With N
2Mist, H
2/ N
2 Volume flow ratio 4/1, flow is 20l/min, reative cell air pressure is 20 torrs, reduces 30 minutes.
Carbon nano tube growth: the temperature in reative cell is 650 ℃ and feeds C
2H
2With N
2Gaseous mixture, C
2H
2/ N
2Volume ratio be 1/10, reative cell air pressure is 40 torrs, grows 1 hour.
Come out of the stove: behind the growth ending, under nitrogen protection, obtained carbon nano-tube thin film cathode drawn cause reative cell mouth cooling, take out then.
4. check, packing
With the quality inspection of carrying out of obtained product, qualified after, the packing, the warehouse-in.
The inventor has provided second embodiment of the present invention.In the present embodiment, the used raw material of preparation colloidal sol is 2 gram FeCl
3, join the aqueous solution of making this salt in the 500 gram water.Remove ionized water and be heated to boiling, add deionized water and the aqueous solution weight ratio that has prepared salt and be 2/100 FeCl
3The aqueous solution is made colloidal sol.To be placed on the reative cell of putting into low pressure chemical gas aggradation stove on the quartz boat through pretreated substrate, quartz boat with meet airflow direction and become 30 ° the gradient, be that 850 ℃, air pressure are 30 torrs in the temperature of reative cell, feed H
2With N
2Volume ratio is 10/1 gaseous mixture, carry out reductase 12 hour earlier after, be to feed C under 800 ℃ again at reaction chamber temperature
2H
2With N
2Volume ratio is 1/2 gaseous mixture, and reative cell air pressure is 80 torrs, grows 2 hours, is prepared into carbon nanotube cathod.The material that present embodiment is used and other technical process are identical with first embodiment.
The inventor has provided the 3rd embodiment of the present invention.In the present embodiment, the used raw material of preparation colloidal sol is 2 gram FeCl
3, join the aqueous solution of making this salt in the 400 gram water.Remove ionized water and be heated to boiling, add deionized water and the aqueous solution weight ratio that has prepared salt and be 1/100 FeCl
3The aqueous solution is made colloidal sol.To be placed on the reative cell of putting into low pressure chemical gas aggradation stove on the quartz boat through pretreated substrate, quartz boat with meet airflow direction and become 30 ° the gradient, be that 720 ℃, air pressure are 25 torrs in the temperature of reative cell, feed H
2With N
2Volume ratio be 7/1 gaseous mixture, after reducing earlier 1 hour, be to feed C under 720 ℃ again at reaction chamber temperature
2H
2With N
2Mixed volume than the gaseous mixture that is 1/6, reative cell air pressure is 60 torrs, grows 1.5 hours, is prepared into carbon nanotube cathod.The material that present embodiment is used and other technical process are identical with first embodiment.
FeCl among the embodiment one, two, three
3, also available ferric sulfate or ferric nitrate or ferric acetate are mixed with the aqueous solution.Also available cobalt chloride or cobalt nitrate or hydrochloric acid cobalt or cobalt acetate or nickel chloride or nickel nitrate or nickelous sulfate or nickel acetate are made the aqueous solution of these salt.Also available titanium dioxide silicon chip of substrate or potsherd are as substrate.
The carbon nanotube cathod that adopts first embodiment of the invention to make through scanning electron microscopy and tem study result is: the carbon nano-tube diameter is that 20 to 50 nanometers, tens microns of pipe ranges, the overwhelming majority are for many walls carbon pipe, when the carbon nano-tube arranging density meets or exceeds 10
9/ cm
2The time, carbon nano-tube begins to align.The carbon nano-tube field emission performance is seen Fig. 1, as seen from the figure, the field emission is opened when field strength pattern is 1.0v/ μ m, can find out that by I-V curve and Fowler Nordheim curve the gained electric current is an emission current in the measurement, the voltage that the field emission is opened is very low, illustrates that the prepared carbon nano-tube of this technology has good field emission characteristic.
Adopt the carbon nanotube cathod of first embodiment of the invention preparation to show: at 50 μ A/mm through life test
2Emission under, continuous firing is after 4000 hours, field emission performance does not have obvious decay.
Claims (3)
1. preparation method who utilizes the carbon nano-tube thin film cathode that generates catalyst granules is characterized in that it is to be prepared into by following technical process:
(1), colloidal sol preparation
Join the aqueous solution of making above-mentioned salt in the water of 100～250 times of weight ratios with the hydrochloride of iron or cobalt or nickel or sulfate or nitrate or acetate;
Remove ionized water and be heated to boiling, add the aqueous solution of the above-mentioned salt that has prepared while stirring, the weight ratio of the aqueous solution of deionized water and above-mentioned salt is 1/100～2/100, is heated with stirring to boiling again and makes colloidal sol;
(2), substrate preliminary treatment
With silicon chip or titanium dioxide silicon chip or potsherd as substrate, substrate is put into supersonic wave cleaning machine, add absolute ethyl alcohol and soaked substrate, connect the power supply of ultrasonic cleaning machine, use ultrasonic waves for cleaning, pour out absolute ethyl alcohol then, merit is gone into deionized water to the submergence substrate again, connects the power supply of supersonic wave cleaning machine, there is not grease with ultrasonic waves for cleaning to surperficial no-sundries, substrate is immersed in the colloidal sol, take out, dry at normal temperatures;
(3) preparation of carbon nano-tube thin film cathode
To be placed on the quartz boat through pretreated substrate; the power supply of connecting low pressure chemical gas aggradation stove heats up; when reaction chamber temperature near reduction temperature required 650 °～850 ℃ the time; under nitrogen protection, quartz boat is pushed the reative cell of this stove; quartz boat with meet airflow direction and become 15 °～30 ° the gradient, iron or the cobalt or the nano nickel particles of the oxidation state that is formed by sol particle on the reduction substrate carry out high temperature reduction then; when reaction chamber temperature is 650 ℃～850 ℃, feed H
2With N
2Gaseous mixture, H
2/ N
2The volume ratio of gaseous mixture is 4/1～10/1, and flow is 20ml/min, and the reative cell internal gas pressure is 20～30 torrs, reduces 0.5～2 hour, gets iron or the cobalt or the nano nickel particles of simple substance, then is 650 ℃～800 ℃ in the reative cell furnace temperature and feeds C down
2H
2With N
2Mist, C
2H
2/ N
2Volume ratio be 1/10～1/2, reative cell air pressure was grown 1～2 hour at 40～80 torrs, on substrate, generate one deck black carbon nano-tube thin film cathode, behind the growth ending, under nitrogen protection, obtained carbon nano-tube thin film cathode is pulled to the reative cell mouth, and cooling is taken out then;
(4), check, packing
Obtained product is carried out quality inspection, qualified after, the packing, the warehouse-in.
2. generate the preparation method of the carbon nano-tube thin film cathode of catalyst granules according to the described utilization of claim 1, it is characterized in that: in formulations prepared from solutions, wherein the hydrochloride of iron or cobalt or nickel or sulfate or nitrate or acetate join the aqueous solution of making above-mentioned salt in the water of 180～220 times of weight ratios, and the weight ratio of the aqueous solution of deionized water and above-mentioned salt is 2/100 to make colloidal sol; In the preparation of carbon nano-tube thin film cathode, wherein reduction temperature is 700 °～750 ℃, feeds H
2With N
2Volume ratio be 4/1～6/1 gaseous mixture, the reative cell internal gas pressure reduced 1～1.5 hour at 20～30 torrs, was 650 °～750 ℃ at reaction chamber temperature then and fed C down
2H
2With N
2Volume ratio be 1/5～1/4 gaseous mixture, reative cell air pressure was grown 1～1.5 hour at 50～60 torrs.
3. generate the preparation method of the carbon nano-tube thin film cathode of catalyst granules according to claim 1 or 2 described utilizations, it is characterized in that: in formulations prepared from solutions, wherein the hydrochloride of iron or cobalt or nickel or sulfate or nitrate or acetate join the aqueous solution of making above-mentioned salt in the water of 200 times of weight ratios, and the weight ratio of the aqueous solution of deionized water and above-mentioned salt is 1/100 to make colloidal sol; In the preparation of carbon nano-tube thin film cathode, wherein reduction temperature is 720 ℃, feeds H
2With N
2Volume ratio be 7/1 gaseous mixture, the reative cell internal gas pressure reduced 1 hour at 25 torrs, was 720 ℃ at reaction chamber temperature then and fed C down
2H
2With N
2Volume ratio be 1/6 gaseous mixture, reative cell air pressure was grown 1.5 hours at 60 torrs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00135476 CN1129168C (en) | 2000-12-28 | 2000-12-28 | Process for preparing film cathode of nm carbon tubes used for generating catalyst particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00135476 CN1129168C (en) | 2000-12-28 | 2000-12-28 | Process for preparing film cathode of nm carbon tubes used for generating catalyst particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1320952A CN1320952A (en) | 2001-11-07 |
| CN1129168C true CN1129168C (en) | 2003-11-26 |
Family
ID=4596746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00135476 Expired - Fee Related CN1129168C (en) | 2000-12-28 | 2000-12-28 | Process for preparing film cathode of nm carbon tubes used for generating catalyst particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1129168C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100582033C (en) * | 2004-08-04 | 2010-01-20 | 鸿富锦精密工业（深圳）有限公司 | Ceramic mould core |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3935479B2 (en) * | 2004-06-23 | 2007-06-20 | キヤノン株式会社 | Carbon fiber manufacturing method, electron-emitting device manufacturing method using the same, electronic device manufacturing method, image display device manufacturing method, and information display / reproducing apparatus using the image display device |
| CN100416740C (en) * | 2005-02-03 | 2008-09-03 | 西安交通大学 | A cathode preparing method for improving field emission stability of printed carbon nanotube film |
| FR2927062B1 (en) * | 2008-02-04 | 2011-07-01 | Arkema France | METHOD FOR SECURELY FILLING CARBON NANOTUBES, FILLING SYSTEM AND INDUSTRIAL PLANT USING THE METHOD |
| CN101377991B (en) * | 2008-10-09 | 2010-06-16 | 东华大学 | Method for improving cathode field-induced electron emission performance of carbon nanometer tube prepared by printing method |
| CN102013371B (en) * | 2009-09-04 | 2012-11-21 | 清华大学 | Surface treatment method for cold cathode |
| CN102249216A (en) * | 2011-06-10 | 2011-11-23 | 电子科技大学 | Method for affecting growth morphology of carbon nanotubes by controlling hydrolysis degree |
| CN102433732A (en) * | 2011-08-02 | 2012-05-02 | 华东理工大学 | Method for synthesizing carbon nanotube array on quartz fiber surface |
| CN106328964B (en) * | 2015-06-25 | 2019-04-23 | 清华大学 | Metal-air battery anode and metal-air battery |
-
2000
- 2000-12-28 CN CN 00135476 patent/CN1129168C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100582033C (en) * | 2004-08-04 | 2010-01-20 | 鸿富锦精密工业（深圳）有限公司 | Ceramic mould core |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1320952A (en) | 2001-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1189390C (en) | Method for synthetizing vertical arrangement high-purity carbon nanometre tube in large-scale on large size substrate using hot CVD method | |
| US6752977B2 (en) | Process for purifying single-wall carbon nanotubes and compositions thereof | |
| KR101287891B1 (en) | Method for manufacturing catalyst for fuel cell | |
| US20070020167A1 (en) | Method of preparing catalyst for manufacturing carbon nanotubes | |
| US20090272490A1 (en) | Method for manufacturing carbon nanotubes | |
| WO2006060476A2 (en) | Fibers comprised of epitaxially grown single-wall carbon nanotubes, and a method for added catalyst and continuous growth at the tip | |
| JP2008195599A (en) | Platinum nano catalyst-carrying carbon nano-tube electrode and its manufacturing method | |
| US20060067872A1 (en) | Method of preparing catalyst base for manufacturing carbon nanotubes and method of manufacturing carbon nanotubes employing the same | |
| CN1129168C (en) | Process for preparing film cathode of nm carbon tubes used for generating catalyst particles | |
| CN103754878B (en) | The method of the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ | |
| CN108118378B (en) | In-situ growth and doping modification method of metal oxide nano catalyst | |
| Hu et al. | Fabrication and characterization of vertically aligned carbon nanotubes on silicon substrates using porous alumina nanotemplates | |
| Maruyama et al. | Generation of single-walled carbon nanotubes from alcohol and generation mechanism by molecular dynamics simulations | |
| KR101994766B1 (en) | Graphene-Carbon Nanotube Composites and Manufacturing Method Thereof | |
| CN1424250A (en) | Process for growing and purifying carbon nano tube by thermolysis with resistor furnace with single temperature zone | |
| KR102081661B1 (en) | Graphene-Carbon Nanotube Composites and Manufacturing Method Thereof | |
| KR100596676B1 (en) | Massive synthesis method of single-walled carbon nanotubes using the vapor phase growth | |
| Tabatabaei et al. | Low-temperature preparation of a carbon nanotube–ZnO hybrid on glass substrate for field emission applications | |
| KR100741762B1 (en) | Method of synthesizing carbon nanotubes on graphite thin plate | |
| CN100386257C (en) | Process of mono temperature area resistance furnace pyrolysis for growing and purifying carbon nanotube | |
| US20050207964A1 (en) | Method for synthesizing carbon nanotubes | |
| CN111620340B (en) | Method for in-situ growth of TiC nanotube | |
| JP2010042942A (en) | Method for manufacturing substrate for forming carbon nanotube and method for manufacturing carbon nanotube using the substrate | |
| CN114411191B (en) | Preparation method of high-dispersion graphene oxide supported ruthenium catalyst | |
| CN113684458B (en) | Membrane electrode prepared by utilizing multi-wall disordered structure carbon nano tube for proton exchange membrane fuel cell, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |