CN100416740C - A cathode preparing method for improving field emission stability of printed carbon nanotube film - Google Patents
A cathode preparing method for improving field emission stability of printed carbon nanotube film Download PDFInfo
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- CN100416740C CN100416740C CNB200510041679XA CN200510041679A CN100416740C CN 100416740 C CN100416740 C CN 100416740C CN B200510041679X A CNB200510041679X A CN B200510041679XA CN 200510041679 A CN200510041679 A CN 200510041679A CN 100416740 C CN100416740 C CN 100416740C
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Abstract
The present invention discloses a cathode preparing method for improving field emission stability of a printed carbon nanotube film, which is characterized in that the method makes co-sintering treatment to a silver slurry printing layer and a carbon nanotube printing layer for increasing a contact area between a printed carbon nanotube film and a conducted substrate so to improve ohmic contact and heat conductivity between the printed carbon nanotube film and the conducted substrate, and the light emitting stability in high brightness and the service life of a field emission display manufactured by a co-sintering cathode are greatly higher than a normal cathode device.
Description
Technical field
The invention belongs to the crossing domain of vacuum microelectronics technique and nanometer technology, be specifically related to by the co-sintering of silver slurry printed layers and carbon nano-tube printed layers is handled, make negative electrode form the silver/carbon nanotube nested structure and improve the ohmic contact between printed carbon nanotube film and the conductive substrates and the method for heat-conductive characteristic, be particularly related to a kind of preparation method who improves the negative electrode of field emission stability of printed carbon nanotube film, this method adopts stability of photoluminescence and the life-span of Field Emission Display under high brightness of silver/carbon nanotube co-sintering negative electrode manufacturing to significantly improve than the conventional cathode device.
Background technology
Carbon nano-tube field emission display negative electrode technology of preparing mainly contains screen printing technique and direct growth technology two big groups at present.With low cost, simple to operate and advantage that large-area uniformity is good that silk screen print method has, 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.Because carbon nano-tube is wrapped in by pulping material in printed layers, directly do not contact conductive substrates, though be decomposed through these pulping material major parts after the heat treatment process, but the pulping material branch in the printed layers bottom solves insufficient, this will make the bigger contact resistance of existence between carbon nano-tube and the conductive substrates, also can influence simultaneously the conduction of the heat that negative electrode produces in the emission current process.When device is worked under higher brightness, the emission at carbon nano-tube tip is very big, bigger current density will inevitably cause huge Joule heat in the bigger place of resistance, and the relatively poor place of heat-conductive characteristic often, these places, therefore too much thermal accumlation will make carbon nano-tube further worsen with the situation that contacts between the conductive substrates, and finally cause the destruction of this contact position, thereby make the luminous generation decay of device.Thereby stability of photoluminescence or life problems be printed carbon nanotube film and part direct growth carbon nano-tube film the problem that must solve.
Summary of the invention
Defective or deficiency at above-mentioned prior art exists the objective of the invention is to, and propose a kind of cathode preparation method that improves field emission stability of printed carbon nanotube film, to solve the problem that existing printed carbon nanotube film exists aspect stable.
The technical solution that the present invention adopts is: a kind of cathode preparation method that improves field emission stability of printed carbon nanotube film, it is characterized in that, this method is by carrying out the contact area that co-sintering is handled to be increased between printed carbon nanotube film and the conductive substrates to silver slurry printed layers and carbon nano-tube printed layers, and then improve ohmic contact and heat-conductive characteristic between printed carbon nanotube film and the conductive substrates, stability of photoluminescence and the life-span of feds under high brightness of manufacturing significantly improved than the conventional cathode device, specifically may further comprise the steps:
(1) preliminary treatment of substrate and carbon nano-tube
The preliminary treatment of substrate is that substrate is cleaned, dries up with Compressed Gas then;
The preliminary treatment of carbon nano-tube is the purifying to carbon nano-tube, to remove catalyst; Its purifying process flow process is:
With red fuming nitric acid (RFNA): the concentrated sulfuric acid=4: 1 preparation acid solutions, and carbon nano-tube is carried out pickling with this acid solution, and wash with water after the pickling to neutrality, further wash with deionized water then, leach carbon nano-tube and dry after the flushing;
(2) carbon nano-tube slurry preparation
Get carbon nano-tube, ethyl cellulose and terpinol and form the carbon nano-tube slurry, wherein ethyl cellulose is a pulping agent, and terpinol is a solvent; The ratio of carbon nano-tube and ethyl cellulose is 1: 5-3: 5, and the ratio of ethyl cellulose and terpinol is to add the 1.5g ethyl cellulose in every 20ml terpinol, its technological process is:
Dried carbon nano-tube is carried out weighing, insert and carry out ultrasonic dispersion in 4-8 hour in the solvent, treat to cross greater than 300 purpose screen clothes carbon nano-tube is dispersed into pasty state in solvent after, add ethyl cellulose then, and under 120 ℃ of conditions, stirred 30 minutes, be cooled to room temperature after stirring and get final product;
(3) printing of silver slurry and carbon nano-tube slurry
Printing process adopts common silk-screen printing technique, silver slurry screen painting silver slurry layer in the elder generation, and oven dry back printed carbon nanotube slurry on silver slurry layer, and then oven dry carry out pre-burning 120 minutes under 300 ℃ condition;
(4) co-sintering of silver slurry printed layers and carbon nano-tube printed layers is handled
Put into vacuum sintering furnace or atmosphere sintering furnace and carry out co-sintering and handle finishing the printing and the negative electrode of pre-burning, as co-sintering temperature (to grind the silver slurry that platinum industry Co., Ltd produces be 570-620 ℃ as expensive), concrete sintering process is undertaken by the explanation that different silver are starched factory and provided with the sintering temperature of silver slurry.If adopt vacuum-sintering, vacuum degree should be better than 1Pa, when adopting gas-protecting sintering, passes to inert gas (as nitrogen etc.) or the hydrogen (purity is higher than 99.99%) of 30-40sccm in the sintering process;
Pass to the above-mentioned gas of 30-40sccm when after being evacuated to the vacuum degree of 1Pa, vacuumizing, the interior a little higher than 1Pa of air pressure meeting of stove this moment, but the protection effect is better than simple vacuum-sintering or atmosphere sintering;
(5) reprocessing of carbon nano-tube film
Post-processing approach is: at carbon nano-tube film surface coverage plastic film, by the plastic film surface carbon nano-tube film being scraped pressure with the colloid scraper handles, thereby the inorganic residue that adheres to carbon nano tube surface is broken away from because of broken, to remove behind the plastic film with pressure be the atmospheric gases at high pressure of 5-8 will blow away from carbon nano-tube film surface failure of rock or the chip that strips down and floating dust by high velocity air that nozzle produced, can obtain finished product.
The printed carbon nanotube film of method preparation of the present invention can increase the contact area between printed carbon nanotube film and the conductive substrates, thereby improves between the two ohmic contact and capacity of heat transmission, finally improves the field emission stability of carbon nanotube cathod.
Description of drawings
Fig. 1 is the schematic diagram that adopts co-sintering prepared carbon nano-tube field-transmitting cathode;
Symbolic representation among above-mentioned each figure divides other to be: 1 is substrate, and 2 is silver slurry printed layers, and 3 is the carbon nano-tube printed layers, and 4 is the co-sintering layer.
Embodiment
For a more clear understanding of the present invention and show beneficial effect of the present invention, the present invention is described in more detail for the embodiment that provides below in conjunction with accompanying drawing and inventor.Need to prove that these embodiment are examples preferably more of the present invention, are not limited to these embodiment.
Embodiment 1:
First embodiment of the present invention that the inventor provides is the monochromatic carbon nanotube field emission plane display with X-Y addressing of making two-level structure, and its manufacture process is as follows:
1. the selection of substrate and preliminary treatment
Present embodiment adopts common soda-lime glass as substrate 1., with pure water washing agent is cleaned up then greasy dirt flush away on glass with washing agent, glass is dried up standby with Compressed Gas at last.
2. the purifying of carbon nano-tube
The carbon nano-tube that present embodiment adopts is by the multi-walled carbon nano-tubes of CVD method preparation, wherein contains the more impurity based on catalyst granules (mainly being iron and oxide thereof).Purifying mainly is in order to remove these impurity wherein, because the catalyst that uses in the preparation process of carbon nano-tube can exist in carbon nano-tube, so it should be removed during use.Wherein carbon nano-tube purifying process flow process is:
With red fuming nitric acid (RFNA): the concentrated sulfuric acid=4: 1 preparation acid solutions, with this acid solution carbon nano-tube is carried out pickling, pickling after washing carbon nano-tube is further washed with deionized water to neutral again, leaches carbon nano-tube and drying after the flushing.
3. carbon nano-tube slurry preparation
Get carbon nano-tube, ethyl cellulose and terpinol and form the carbon nano-tube slurry, the ratio of carbon nano-tube and ethyl cellulose is 1: 5-3: 5, the ratio of ethyl cellulose and terpinol is to add the 1.5g ethyl cellulose in every 20ml terpinol, wherein ethyl cellulose is a pulping agent, and terpinol is a solvent; Its technological process is:
Dried carbon nano-tube is carried out weighing, insert and carry out ultrasonic dispersion in 4-8 hour in the solvent, treat to sieve carbon nano-tube is dispersed into pasty state in solvent after, add ethyl cellulose then, and under 120 ℃ of conditions, stirred 30 minutes, be cooled to room temperature after stirring and get final product;
4. the printing of silver slurry and carbon nano-tube slurry
Printing process can adopt common silk-screen printing technique, and is specific as follows:
Transfer the printing machine operating state, at first go up silver slurry half tone, to printing silver slurry layer 2 after the version, oven dry; Oven dry back printed carbon nanotube slurry 3 on silver slurry layer, and then oven dry, last pre-burning 120 minutes under 300 ℃ condition;
5. the co-sintering of silver slurry printed layers and carbon nano-tube printed layers is handled
Put into vacuum sintering furnace and carry out co-sintering and handle finishing the printing and the negative electrode of pre-burning, with the sintering temperature (580 ℃) of silver slurry as co-sintering temperature (silver slurry used herein is produced by the expensive platinum industry Co., Ltd of grinding).For strengthening the protection effect, pass to the nitrogen (purity is higher than 99.99%) of 30-40sccm when after being evacuated to the vacuum degree of 1Pa, vacuumizing.After finishing, sintering can obtain co-sintering layer 4;
Facts have proved that protective gas adopts argon gas or hydrogen also can finish above-mentioned co-sintering and handles.
6. the reprocessing of carbon nano-tube film
Post-processing approach is: at carbon nano-tube film surface coverage plastic film, by the plastic film surface carbon nano-tube film being scraped pressure with the colloid scraper handles, thereby the inorganic residue that adheres to carbon nano tube surface is broken away from because of broken, to remove behind the plastic film with pressure be the atmospheric gases at high pressure of 5-8 will blow away from carbon nano-tube film surface failure of rock or the chip that strips down and floating dust by high velocity air that nozzle produced, can obtain the finished product negative electrode.
So far the negative electrode preparation process finishes, and below the anode of device is made and the device package process describes.
7. the manufacturing of positive plate
The used glass of anode is the soda-lime glass that has the ITO coating.The positive plate manufacturing process:
At first glass is cleaned, the photoetching of carrying out ito thin film on glass after cleaning, seal silver slurry pin and oven dry then being printed insulation again and supporting the back oven dry, carries out sintering then, dries after printing fluorescent material again;
8. device package
The encapsulation of device is cathode-anode plate to be fastened and will seal on every side with glass powder with low melting point, by vacuum-pumping equipment device inside is evacuated to then to be better than 10
-4The high vacuum state of Pa makes device inside obtain to be better than 10 by the getter that evapotranspires after the device sealed-off
-6The ultra high vacuum degree of a.Concrete encapsulation flow process is:
On anode substrate, be coated with earlier glass powder with low melting point; and pre-burning (package temperature is provided by glass powder with low melting point manufacturer) under the temperature that is lower than 10 ℃～15 ℃ of package temperature; then the cathode and anode substrate is fastened and installs getter; put into the formal sintering of sintering furnace behind the clamping, sintering process need pass to inert gas (as nitrogen) and protect carbon nano-tube not oxidized.Process to be sintered is finished and device is received gas extraction system when being cooled to room temperature and vacuumize, to 1 * 10
-6With the device sealed-off, with the high-frequency heating apparatus getter that evapotranspires, generally be no more than 15 seconds heating time, in case glass bursts then during orr.Can obtain the monochromatic carbon nanotube field emission plane display with X-Y addressing of two-level structure, so far, entire device is made and is finished.
Embodiment 2:
Second embodiment of the present invention that the inventor provides is the colored carbon nanotube field emission plane display with X-Y addressing of making two-level structure, its preparation process and embodiment 1 are identical, difference is that its fluorescent material is three looks in the step 7 of the manufacturing of positive plate, and this three-color phosphor is printed respectively.Can obtain having the colored carbon nanotube field emission plane display of X-Y addressing.
Embodiment 3:
The 3rd embodiment of the present invention that the inventor provides is the electron source of making the High-Power Microwave device, and its manufacture process is as follows:
1. substrate fabrication
According to designing requirement and select the conductive substrates of the suitable suitable shape of material.For example stainless steel material or graphite material are processed into the discoid cathode substrate (joint is used for being connected with device, is positioned at the bottom of disk) that has circular joint, enter other manufacturing process then with surface rubbing and after cleaning up;
2. other manufacturing process
Other manufacturing process are with the step 2 among the embodiment 1～6.Can obtain the electron source of High-Power Microwave device.
Claims (3)
1. cathode preparation method that improves field emission stability of printed carbon nanotube film, it is characterized in that, this method is by carrying out the contact area that co-sintering is handled to be increased between printed carbon nanotube film and the conductive substrates to silver slurry printed layers and carbon nano-tube printed layers, and then improve ohmic contact and heat-conductive characteristic between printed carbon nanotube film and the conductive substrates, stability of photoluminescence and the life-span of feds under high brightness of manufacturing significantly improved than the conventional cathode device, specifically may further comprise the steps:
(1) preliminary treatment of substrate and carbon nano-tube
The preliminary treatment of substrate is that substrate is cleaned, dries up with Compressed Gas then;
The preliminary treatment of carbon nano-tube is the purifying to carbon nano-tube, to remove catalyst; Its purifying process flow process is:
With red fuming nitric acid (RFNA): the concentrated sulfuric acid=4: 1 preparation acid solutions, and carbon nano-tube is carried out pickling with this acid solution, and wash with water after the pickling to neutrality, further wash with deionized water then, leach carbon nano-tube and dry after the flushing;
(2) carbon nano-tube slurry preparation
Get carbon nano-tube, ethyl cellulose and terpinol and form the carbon nano-tube slurry, wherein ethyl cellulose is a pulping agent, and terpinol is a solvent; The ratio of carbon nano-tube and ethyl cellulose is 1: 5-3: 5, and the ratio of ethyl cellulose and terpinol is to add the 1.5g ethyl cellulose in every 20ml terpinol, its technological process is:
Dried carbon nano-tube is carried out weighing, insert and carry out ultrasonic dispersion in 4-8 hour in the solvent, treat to cross greater than 300 purpose screen clothes carbon nano-tube is dispersed into pasty state in solvent after, add ethyl cellulose then, and under 120 ℃ of conditions, stirred 30 minutes, be cooled to room temperature after stirring and get final product;
(3) printing of silver slurry and carbon nano-tube slurry
Printing process adopts common silk-screen printing technique, silver slurry screen painting silver slurry layer in the elder generation, and oven dry back printed carbon nanotube slurry on silver slurry layer, and then oven dry carry out pre-burning 120 minutes under 300 ℃ condition;
(4) co-sintering of silver slurry printed layers and carbon nano-tube printed layers is handled
Put into vacuum sintering furnace or atmosphere sintering furnace and carry out co-sintering and handle finishing the printing and the negative electrode of pre-burning, as the co-sintering temperature, concrete sintering process is undertaken by the explanation that different silver slurry factory provides with the sintering temperature of silver slurry; If adopt vacuum-sintering, vacuum degree should be better than 1Pa, when adopting gas-protecting sintering, passes to the inert gas of 30-40sccm or hydrogen in the sintering process as protective gas;
(5) reprocessing of carbon nano-tube film
Post-processing approach is: at carbon nano-tube film surface coverage plastic film, by the plastic film surface carbon nano-tube film being scraped pressure with the colloid scraper handles, thereby the inorganic residue that adheres to carbon nano tube surface is broken away from because of broken, to remove behind the plastic film with pressure be the atmospheric gases at high pressure of 5-8 will blow away from carbon nano-tube film surface failure of rock or the chip that strips down and floating dust by high velocity air that nozzle produced, can obtain the negative electrode finished product.
2. the method for claim 1 is characterized in that, said inert gas is nitrogen or argon gas in the step (4), and its purity is higher than 99.99%, and the purity of said hydrogen is higher than 99.99%.
3. method as claimed in claim 1 or 2 is characterized in that, in the step (4) during said employing gas-protecting sintering, passes to the inert gas of 30-40sccm or hydrogen as protective gas when being evacuated to the vacuum degree of 1Pa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101266180A (en) | 2007-03-16 | 2008-09-17 | 清华大学 | Ionization gage |
| CN101303264B (en) * | 2007-05-09 | 2010-05-26 | 清华大学 | Ionization gage |
| CN101303955B (en) | 2007-05-09 | 2010-05-26 | 清华大学 | Ion source component |
| CN101177261B (en) * | 2007-11-08 | 2010-05-19 | 上海交通大学 | Method for preparing biocompatible cellulose functionalized carbon nano tube |
| CN101794696A (en) * | 2010-03-25 | 2010-08-04 | 东华大学 | Preparation method of carbon nanotube field emission cathode for improving field emission characteristics |
| CN102974823B (en) * | 2012-12-12 | 2015-05-20 | 广汉川冶新材料有限责任公司 | Sintering method of high gravity alloy |
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| CN1320952A (en) * | 2000-12-28 | 2001-11-07 | 西安交通大学 | Process for preparing film cathode of nm carbon tubes used for generating catalyst particles |
| US20020104603A1 (en) * | 2001-02-07 | 2002-08-08 | Yu-Yang Chang | Method of improving field emission efficiency for fabricating carbon nanotube field emitters |
| JP2003100202A (en) * | 2001-09-12 | 2003-04-04 | Ind Technol Res Inst | Manufacturing method of electron emitting element with triode structure |
| CN1423247A (en) * | 2001-11-29 | 2003-06-11 | 京东方科技集团股份有限公司 | Paneldisplay device based on nano carbon tube and its manufacture method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320952A (en) * | 2000-12-28 | 2001-11-07 | 西安交通大学 | Process for preparing film cathode of nm carbon tubes used for generating catalyst particles |
| US20020104603A1 (en) * | 2001-02-07 | 2002-08-08 | Yu-Yang Chang | Method of improving field emission efficiency for fabricating carbon nanotube field emitters |
| JP2003100202A (en) * | 2001-09-12 | 2003-04-04 | Ind Technol Res Inst | Manufacturing method of electron emitting element with triode structure |
| CN1423247A (en) * | 2001-11-29 | 2003-06-11 | 京东方科技集团股份有限公司 | Paneldisplay device based on nano carbon tube and its manufacture method |
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