CN1303260C - Process for preparing carbon nano tube film through electrophoresis deposition - Google Patents
Process for preparing carbon nano tube film through electrophoresis deposition Download PDFInfo
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- CN1303260C CN1303260C CNB2004100341089A CN200410034108A CN1303260C CN 1303260 C CN1303260 C CN 1303260C CN B2004100341089 A CNB2004100341089 A CN B2004100341089A CN 200410034108 A CN200410034108 A CN 200410034108A CN 1303260 C CN1303260 C CN 1303260C
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Abstract
The present invention relates to an electrophoretic deposition preparation method for a thin film of a carbon nanometer tube, which belongs to the technical field of nanometer material. The present invention comprises the steps of purification treatment and surface modification of a carbon nanometer tube, formation of stable suspension of the carbon nanometer tube, electrophoretic deposition of a thin film of the carbon nanometer tube, thin film drying and secondary electrophoretic deposition. The present invention has the advantages of simple production equipment, high film forming speed, controllable film thickness, unlimited substrate shapes, etc. The technology is simple, and a thin film of the carbon nanometer tube is suitable for mass production.
Description
Technical field
The present invention relates to the preparation method of carbon nano-tube film, electrophoretic deposition preparation method particularly, metal nanometer material technical field.
Background technology
Carbon nanotube is a kind of ideal monodimension nanometer material of present artificial preparation, because itself forms the uniqueness of structure, carbon nanotube shows the physical properties of many uniquenesses, has obtained at aspects such as transmitter, flat-panel monitor, ultracapacitor, matrix materials using widely.Wherein, macroscopical membrane structure that carbon nanotube is formed according to certain rule is in the prospect of application facet desirable more.
At present, the preparation method of carbon nano-tube film mainly contains two kinds of direct growth method and post treatment methods.
The direct growth method is to utilize preparation methods such as arc-over, laser ablation, chemical vapour deposition, direct growth carbon nano-tube film in the substrate of certain material.Its advantage is that structure, the size of carbon nanotube can be regulated by processing condition, and can realize the graphical of carbon nanotube by the figure of substrate or catalyzer; Its shortcoming is to need various treatment processs to improve the performance of carbon nano-tube film, more intense to the selectivity of substrate, and owing to state-of-the-art is limit, these technological processs mostly need hot conditions, therefore can't use low-melting material as substrate, synthetic glass for example, this has limited the application of carbon nano-tube film at aspects such as transmitter, field emission displays greatly.Simultaneously, because hot conditions can be destroyed microelectronic circuit, the preparation technology of carbon nano-tube film and the non-compatibility of microelectronic technique have therefore been caused.
Post treatment method is that the several method of mentioning is in front prepared on the basis of carbon nanotube, and carbon nanotube is modified and improvement in performance, obtains unified, uniform carbon nano-tube film by certain post-processing technology then.The characteristics of post treatment method maximum are less demanding to substrate, have avoided occurring in the technology high temperature, might realize the compatibility with microelectronic technique.The method that present common post treatment method prepares carbon nano-tube film comprises spraying method, method of evaporation etc., though these method technologies are simple, film forming speed is slower, and the difficult control of film thickness, be not suitable in enormous quantities, automatic production, industry is promoted and is realized difficulty.
Electrophoretic deposition is meant the dependence effect of electric field, and the charged solia particle in the suspension takes place by directed moving, and is deposited on and has opposite charges and have phenomenon on the definite shape electrode.It comprises electrophoresis and two steps of deposition: electrophoresis is named electromigration again, refers to that the physical chemical phenomenon of orientation movement takes place because of electric field action in certain medium charged particle; Deposition is meant particle aggregation film forming or block.At present, the applied research of electrophoretic deposition aspect application techniques is very deep,, no environment harm, operational safety, process automation good, be applicable to characteristics such as streamlined production, obtained application very widely in industries such as automobile, household electrical appliances, light industry, metals with its uniform film thickness, outward appearance.
At present, the subject matter that the preparation that utilizes electrophoretic deposition to carry out carbon nano-tube film faces is the film thickness poor controllability, uniformity of film difference etc.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who obtains the uniform carbon nano-tube film of film thickness.Present method relates to a kind of method of utilizing electrophoretic deposition to prepare carbon nano-tube film, comprises following five steps:
1. the purification process of carbon nanotube and finishing
With the carbon nanotube prepared and concentration is that 30% superoxol mixes, and 10～120 minutes after-filtration of sonic oscillation go out carbon nanotube; Use dithiocarbonic anhydride washing carbon nanotube 3～5 times; Use anhydrous methanol washing carbon nanotube 3～5 times; Oven dry; Above-mentioned carbon nanotube is mixed the back 70～150 ℃ of reflux 10～120 minutes with concentrated acid, said concentrated acid is meant any in these three kinds in 98% the vitriol oil, 69% concentrated nitric acid and both mixing acid; Filter out carbon nanotube; Use the deionized water wash carbon nanotube 3～10 times and oven dry;
2. the formation of carbon nanotube stable suspension
Above-mentioned carbon nanotube is dispersed in water or the organic solvent, and said organic solvent can be any in ethanol, acetone or their mixture; Add inorganic salt, said inorganic salt can be any in magnesium chloride, magnesium nitrate, aluminum chloride, the aluminum nitrate; Sonic oscillation 10～120 minutes left standstill 10～120 minutes, formed the suspension electrophoresis liquid of various steady concentration;
3. electrophoretic deposition carbon nano-tube film
With the negative electrode of the required substrate of growing film as tiselius apparatus, said negative electrode can be any electro-conductive material that is not corroded in electrophoresis process, also can be the electro-conductive material that the isolator that is not corroded in the electrophoresis process or semiconductor surface have certain figure; As anode, said anode can be any one in platinum electrode, gold electrode, the copper electrode with metal electrode; With carbon nano tube suspension as electrophoresis liquid; Depress at direct current 10～100 voltaisms, according to required film thickness electrophoresis 30 seconds～20 minutes;
4. film oven dry
The product that negative electrode obtains was dried 1～120 minute down at 25 ℃～200 ℃ together with negative electrode;
5. secondary electrophoresis
Negative electrode is then put into above-mentioned tiselius apparatus carry out the secondary electrophoresis; The product that again negative electrode is obtained after 30 seconds～20 minutes takes out oven dry, can obtain carbon nano-tube film.
The present invention's implementation condition preferably is:
The carbon nanotube diameter is less than 80 nanometers.
Length of carbon nanotube is less than 30 microns.
Concentrated acid was mixed by 98% vitriol oil and 69% concentrated nitric acid in 3: 1 by volume.
The reflux time was less than 30 minutes.
Dispersion solvent is a dehydrated alcohol.
Inorganic salt are magnesium chloride or magnesium nitrate.
Anode is a platinum electrode.
Electrophoretic voltage is 50～80 volts of direct currents.
Electrophoresis time is 1～20 minute.
Dry or bake out temperature is 10～50 ℃.
Dry or drying time is 1～30 minute.
The secondary electrophoresis time is 1～20 minute.
Characteristics of the present invention:
1. the carbon nano-tube film that method provided by the present invention obtains is compared with other existing method, has fabrication cycle weak point, carbon nano-tube film even compact, carbon nanotube and can modify characteristics such as processing in advance;
2. the present invention can come the thickness of controlling carbon nanotube film by change deposition voltage, depositing time;
3. the present invention can come the graphical of controlling carbon nanotube film by changing electrode pattern;
4. electrophoretic deposition method of the present invention is implemented convenient and simple, and is less demanding to instrument, and deposition process is easy to outside regulation and control;
5. it is short that the present invention has electrophoresis time, and electrophoresis process can carry out in multiple solvent, particularly can carry out in water and organic solvent commonly used, and environmental pollution is little, and low price, is applicable to suitability for industrialized production.
The present invention has plurality of advantages such as production unit is simple, film forming is fast, film thickness is controlled, be used for deposit film shapes of substrates is unrestricted, and complete processing is simple, is fit in enormous quantities, automatic production, is easy to industry and applies.
Embodiment
Embodiment 1
1. select the multi-walled carbon nano-tubes black powder of the poly-group of nanometer technology preparation for use, purity is greater than 80%, internal diameter 2～30 nanometers, external diameter 5～60 nanometers, big or small tens microns of poly-group.This carbon nanotube is mixed 10 minutes after-filtration of sonic oscillation with 30% superoxol; Use dithiocarbonic anhydride repetitive scrubbing carbon nanotube three times; Use anhydrous methanol repetitive scrubbing carbon nanotube three times; Oven dry.Above-mentioned carbon nanotube is mixed with 75 milliliter of 98% vitriol oil, 25 milliliter of 69% concentrated nitric acid,, filter out carbon nanotube 75 ℃ of reflux 10 minutes; Use deionized water wash carbon nanotube and oven dry.
2. take by weighing 50 milligrams of above-mentioned carbon nanotubes, add 100 milliliters of dehydrated alcohols and 512 milligrams of magnesium chlorides, sonic oscillation 20 minutes left standstill 30 minutes, formed black, stable carbon nano tube suspension.
With above-mentioned carbon nano tube suspension as electrophoresis liquid, and with the silicon chip of graphical gold negative electrode, with the anode of gold plaque as tiselius apparatus as tiselius apparatus; Relative spacing is 4 centimetres between negative electrode, the anode; Between the negative electrode of tiselius apparatus and anode, add 50 volts volts DS, after 4 minutes negative electrode is taken out.
4. above-mentioned negative electrode is left standstill at normal temperatures 2 minutes 30 seconds;
5. once more negative electrode is put into tiselius apparatus, the volts DS that adds 50 volts kept 1 minute; Negative electrode is taken out, dry at normal temperatures.
It is the black of substrate grown, uniform, patterned carbon nano-tube film that the result can obtain with the silicon chip.Measuring result shows that the film edge mean thickness is about 87 microns.
Embodiment 2
1. select the multi-walled carbon nano-tubes black powder of the poly-group of nanometer technology preparation for use, purity is greater than 80%, internal diameter 2～30 nanometers, external diameter 5～60 nanometers, big or small tens microns of poly-group.This carbon nanotube is mixed 10 minutes after-filtration of sonic oscillation with 30% superoxol; Use dithiocarbonic anhydride repetitive scrubbing carbon nanotube three times; Use anhydrous methanol repetitive scrubbing carbon nanotube three times; Oven dry.Above-mentioned carbon nanotube is mixed with 75 milliliter of 98% vitriol oil, 25 milliliter of 69% concentrated nitric acid,, filter out carbon nanotube 75 ℃ of reflux 10 minutes; Use deionized water wash carbon nanotube and oven dry.
2. take by weighing 50 milligrams of above-mentioned carbon nanotubes, add 100 milliliters of dehydrated alcohols and 512 milligrams of magnesium chlorides, sonic oscillation 20 minutes left standstill 30 minutes, formed black, stable carbon nano tube suspension.
With above-mentioned carbon nano tube suspension as electrophoresis liquid, and with the silicon chip of graphical gold negative electrode, with the anode of gold plaque as tiselius apparatus as tiselius apparatus; Relative spacing is 1 centimetre between negative electrode, the anode; Between the negative electrode of tiselius apparatus and anode, add 90 volts volts DS, after 4 minutes negative electrode is taken out.
4. above-mentioned negative electrode was left standstill 2 minutes at normal temperatures;
5. once more negative electrode is put into tiselius apparatus, the volts DS that adds 50 volts kept 1 minute; Negative electrode is taken out, dry at normal temperatures.
It is the black of substrate grown, uniform, patterned carbon nano-tube film that the result can obtain with the silicon chip.Measuring result shows that the film edge mean thickness is about 245 microns.
Claims (1)
1, a kind of electrophoretic deposition preparation method of carbon nano-tube film, comprise the purification process of carbon nanotube and finishing, the formation of carbon nanotube stable suspension, three steps of electrophoretic deposition carbon nano-tube film, said purification process and finishing are: the carbon nanotube that will prepare and concentration are that 30% superoxol mixes, and 10～120 minutes after-filtration of sonic oscillation go out carbon nanotube; Use dithiocarbonic anhydride washing carbon nanotube 3～5 times; Use anhydrous methanol washing carbon nanotube 3～5 times; Oven dry; Above-mentioned carbon nanotube is mixed the back 70～150 ℃ of reflux 10～120 minutes with concentrated acid, said concentrated acid is meant any in these three kinds in 98% the vitriol oil, 69% concentrated nitric acid and both mixing acid; Filter out carbon nanotube; Use the deionized water wash carbon nanotube 3～10 times and oven dry; The formation of said carbon nanotube stable suspension is: the carbon nanotube after the purification process is dispersed in water or the organic solvent, and said organic solvent can be any in ethanol, acetone or their mixture; Add inorganic salt, said inorganic salt can be any in magnesium chloride, magnesium nitrate, aluminum chloride, the aluminum nitrate; Sonic oscillation 10～120 minutes left standstill 10～120 minutes, formed the suspension electrophoresis liquid of various steady concentration; Said electrophoretic deposition carbon nano-tube film is: with the negative electrode of the required substrate of growing film as tiselius apparatus, said negative electrode can be any electro-conductive material that is not corroded in electrophoresis process, also can be the electro-conductive material that the isolator that is not corroded in the electrophoresis process or semiconductor surface have certain figure; As anode, said anode can be any one in platinum electrode, gold electrode, the copper electrode with metal electrode; With carbon nano tube suspension as electrophoresis liquid; Depress at direct current 10～100 voltaisms, according to required film thickness electrophoresis 30 seconds～20 minutes; It is characterized in that after carbon nano-tube film forms, being dried, and carry out the secondary electrophoretic deposition.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100341089A CN1303260C (en) | 2004-04-23 | 2004-04-23 | Process for preparing carbon nano tube film through electrophoresis deposition |
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| CNB2004100341089A CN1303260C (en) | 2004-04-23 | 2004-04-23 | Process for preparing carbon nano tube film through electrophoresis deposition |
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| CN1570220A CN1570220A (en) | 2005-01-26 |
| CN1303260C true CN1303260C (en) | 2007-03-07 |
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| CNB2004100341089A Expired - Fee Related CN1303260C (en) | 2004-04-23 | 2004-04-23 | Process for preparing carbon nano tube film through electrophoresis deposition |
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Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100437881C (en) * | 2005-03-14 | 2008-11-26 | 东元奈米应材股份有限公司 | Method of inproving nano-carbon tube electronic emitting performance of field emitting display |
| US7828619B1 (en) * | 2005-08-05 | 2010-11-09 | Mytitek, Inc. | Method for preparing a nanostructured composite electrode through electrophoretic deposition and a product prepared thereby |
| CN100371060C (en) * | 2005-09-30 | 2008-02-27 | 清华大学 | Method for assisting dispersal of carbonate nano tube in liquid medium by electric field |
| CN100453188C (en) * | 2005-10-14 | 2009-01-21 | 鸿富锦精密工业（深圳）有限公司 | Carbon nano-tube film depositing equipment |
| CN100396825C (en) * | 2005-11-03 | 2008-06-25 | 武汉化工学院 | Process for producing metal-base nano-composite cladding material |
| CN100427388C (en) * | 2005-11-25 | 2008-10-22 | 清华大学 | Large-area ultra-thin carbon nanotube film and its preparation process |
| TWI320432B (en) | 2006-06-16 | 2010-02-11 | Hon Hai Prec Ind Co Ltd | Apparatus and method for synthesizing carbon nanotube film |
| CN100420626C (en) * | 2006-11-27 | 2008-09-24 | 西南交通大学 | Preparation method of pure nano-carbon tube film |
| CN101284662B (en) * | 2007-04-13 | 2011-01-05 | 清华大学 | Preparing process for carbon nano-tube membrane |
| CN101255591B (en) * | 2008-04-03 | 2011-01-26 | 厦门大学 | Method for preparing carbon nano-tube/nano-nickel composite film |
| CN101320682B (en) * | 2008-06-13 | 2010-06-09 | 华中科技大学 | Method for improving ohm contact performance of metal-P type semiconductor |
| CN102181912A (en) * | 2011-04-14 | 2011-09-14 | 上海交通大学 | Method for preparing nano polymer composite material based on electrophoretic deposition |
| CN102856078A (en) * | 2012-08-31 | 2013-01-02 | 天津大学 | Method for preparing carbon nanometre tube doped titanium dioxide composite material by surface cracking method |
| CN103400933B (en) * | 2013-08-20 | 2016-08-10 | 温州大学 | The preparation method of carbon-based nano thin film thermoelectric chemical electrode based on electrophoresis method |
| CN103451708A (en) * | 2013-08-31 | 2013-12-18 | 西北工业大学 | Method for preparing carbon nanotube/carbon/carbon composite material through dielectrophoresis technology |
| CN103456581B (en) * | 2013-09-10 | 2016-08-24 | 中国科学院深圳先进技术研究院 | Carbon nanotube field emission cathode and preparation method thereof |
| CN103882499B (en) * | 2014-03-19 | 2016-06-15 | 北京工业大学 | CNT membrane electrode CNT-Ti electrode as catalyst carrier is prepared and application |
| CN105220205B (en) * | 2015-11-03 | 2018-02-02 | 哈尔滨工业大学 | A kind of method that composite electrodeposition prepares CNTs/Ni composites |
| CN106120296B (en) * | 2016-06-21 | 2018-09-11 | 郑州大学 | A kind of carbon nano-tube fibre purification process |
| CN108179294A (en) * | 2017-12-27 | 2018-06-19 | 哈尔滨工业大学 | A kind of Carbon Nanotubes/Magnesiuum Matrix Composite method for preparing layer structure |
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| JP2001020093A (en) * | 1999-07-09 | 2001-01-23 | Matsushita Electric Ind Co Ltd | Electrophoresis device, electron releasing element and image display device produced by utilizing the same as well as their production |
| JP2001110303A (en) * | 1999-08-12 | 2001-04-20 | Samsung Sdi Co Ltd | Fabrication method of carbon nanotube field emitter utilizing electrophoresis |
| WO2003052785A1 (en) * | 2001-12-18 | 2003-06-26 | Motorola, Inc. | Fed cathode structure using electrophoretic deposition |
| DE10220628A1 (en) * | 2002-05-08 | 2003-11-27 | Infineon Technologies Ag | Process for depositing nanotubes comprises preparing a solution of nanotubes bound with an electrically charged group, and applying the solution on a depositing electrode to which an electrical potential is applied |
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Patent Citations (5)
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| JP2001020093A (en) * | 1999-07-09 | 2001-01-23 | Matsushita Electric Ind Co Ltd | Electrophoresis device, electron releasing element and image display device produced by utilizing the same as well as their production |
| JP2001110303A (en) * | 1999-08-12 | 2001-04-20 | Samsung Sdi Co Ltd | Fabrication method of carbon nanotube field emitter utilizing electrophoresis |
| US6616497B1 (en) * | 1999-08-12 | 2003-09-09 | Samsung Sdi Co., Ltd. | Method of manufacturing carbon nanotube field emitter by electrophoretic deposition |
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| CN1570220A (en) | 2005-01-26 |
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