CN100416740C - A cathode preparation method for improving field emission stability of printed carbon nanotube films - Google Patents

Abstract

The invention discloses a cathode preparation method for improving the field emission stability of a printed carbon nanotube film, which is characterized in that the method carries out co-sintering treatment on the silver paste printing layer and the carbon nanotube printing layer to increase the printed carbon nanotube film and The contact area between the conductive substrates, thereby improving the ohmic contact and thermal conductivity between the printed carbon nanotube film and the conductive substrate, and making the luminescence stability and lifespan of the field emission display manufactured with the co-sintered cathode under high brightness Significantly improved compared with ordinary cathode devices.

Description

A cathode preparation method for improving field emission stability of printed carbon nanotube films

technical field

The invention belongs to the intersecting field of vacuum microelectronics technology and nanotechnology, and specifically relates to improving the printing of carbon nanotubes by co-sintering the silver paste printing layer and the carbon nanotube printing layer so that the cathode forms a nested structure of silver/carbon nanotubes A method for ohmic contact and thermal conductivity between a film and a conductive substrate, in particular to a method for preparing a cathode for improving the field emission stability of a printed carbon nanotube film, which uses a silver/carbon nanotube co-sintered cathode The luminescence stability and lifespan of the emissive display under high brightness are significantly improved compared with common cathode devices.

Background technique

At present, the cathode preparation technology of carbon nanotube field emission display mainly includes screen printing technology and direct growth technology. The screen printing method has the advantages of low cost, simple operation and good uniformity in a large area. In this method, carbon nanotubes are usually mixed with pulping materials to make a slurry that can be screen-printed, and then printed on the substrate. superior. After annealing and roasting, most of the pulping materials are removed, so as to prepare the carbon nanotube cathode film. Since the carbon nanotubes are wrapped by pulping materials in the printing layer and do not directly contact the conductive substrate, although most of these pulping materials are decomposed after the heat treatment process, the pulping materials at the bottom of the printing layer are decomposed. Insufficient, this will cause a large contact resistance between the carbon nanotubes and the conductive substrate, and also affect the conduction of the heat generated by the cathode during the process of emitting current. When the device works at a higher brightness, the emission current density of the tip of the carbon nanotube is very large, and the larger current density will inevitably cause huge Joule heat in places with higher resistance, and these places are often poor in thermal conductivity. Therefore, excessive heat accumulation will further deteriorate the contact between the carbon nanotubes and the conductive substrate, and eventually lead to the destruction of the contact, thereby attenuating the light emission of the device. Therefore, the problem of luminescence stability or lifetime is a subject that must be solved for printing carbon nanotube films and partially directly growing carbon nanotube films.

Contents of the invention

In view of the defects or deficiencies in the above-mentioned prior art, the purpose of the present invention is to propose a cathode preparation method for improving the field emission stability of printed carbon nanotube films, so as to solve the problems in the stability of existing printed carbon nanotube films. The problem.

The technical solution adopted in the present invention is: a cathode preparation method for improving the field emission stability of printed carbon nanotube films, which is characterized in that the method increases the The contact area between the printed carbon nanotube film and the conductive substrate, thereby improving the ohmic contact and thermal conductivity between the printed carbon nanotube film and the conductive substrate, so that the luminescence stability and The service life is significantly improved compared with ordinary cathode devices, which specifically includes the following steps:

(1) Pretreatment of substrate and carbon nanotubes

The pretreatment of the substrate is to clean the substrate and then dry it with compressed gas;

The pretreatment of carbon nanotubes is the purification of carbon nanotubes to remove the catalyst; the purification process is as follows:

Prepare an acid solution with concentrated nitric acid: concentrated sulfuric acid = 4:1, and pickle the carbon nanotubes with the acid solution, wash with water to neutrality after pickling, and then further rinse with deionized water, and filter out the carbon nanotubes after washing. tube and dry;

(2) Preparation of carbon nanotube slurry

Get carbon nanotubes, ethyl cellulose and terpineol to form carbon nanotube slurry, wherein ethyl cellulose is a pulping agent, terpineol is a solvent; the ratio of carbon nanotubes to ethyl cellulose is 1:5 -3:5, the ratio of ethyl cellulose and terpineol is to add 1.5g ethyl cellulose in every 20ml terpineol, and its technological process is:

Weigh the dried carbon nanotubes, place them in a solvent for ultrasonic dispersion for 4-8 hours, pass the carbon nanotubes through a sieve larger than 300 mesh after they are dispersed into a paste in the solvent, then add ethyl cellulose, and Stir at 120°C for 30 minutes, stir well and then cool to room temperature;

(3) Printing of silver paste and carbon nanotube paste

The printing process adopts the ordinary screen printing process. First, the silver paste layer is screen-printed with silver paste, and after drying, the carbon nanotube paste is printed on the silver paste layer, and then dried, and pre-fired at 300 ° C. 120 minutes;

(4) Co-sintering treatment of silver paste printing layer and carbon nanotube printing layer

Put the printed and pre-fired cathode into a vacuum sintering furnace or an atmosphere sintering furnace for co-sintering, and use the sintering temperature of the silver paste as the co-sintering temperature (for example, the silver paste produced by Guiyan Platinum Industry Co., Ltd. is 570-620°C ), the specific sintering process is carried out according to the instructions provided by different silver paste manufacturers. If vacuum sintering is used, the vacuum degree should be better than 1 Pa. When using atmosphere protection sintering, 30-40 sccm of inert gas (such as nitrogen, etc.) or hydrogen (purity higher than 99.99%) is passed through the sintering process;

After evacuating to a vacuum degree of 1Pa, pass 30-40sccm of the above-mentioned gas while evacuating. At this time, the pressure in the furnace will be slightly higher than 1Pa, but the protection effect is better than that of simple vacuum sintering or atmosphere sintering;

(5) Post-treatment of carbon nanotube films

The post-treatment method is as follows: cover the surface of the carbon nanotube film with a plastic film, and use a rubber scraper to scrape and press the carbon nanotube film through the surface of the plastic film, so that the inorganic residues adhered to the surface of the carbon nanotube are broken and detached. After removing the plastic film, use high-pressure gas with a pressure of 5-8 atmospheres to pass through the high-speed airflow generated by the nozzle to blow off the debris and floating dust that are broken or peeled off from the surface of the carbon nanotube film, and the finished product can be obtained.

The printed carbon nanotube film prepared by the method of the present invention can increase the contact area between the printed carbon nanotube film and the conductive substrate, thereby improving the ohmic contact and thermal conductivity between the two, and finally improving the field of the carbon nanotube cathode. launch stability.

Description of drawings

Fig. 1 is the schematic diagram that adopts co-sintering process to prepare carbon nanotube field emission cathode;

The symbols in the above figures respectively indicate: 1 is the substrate, 2 is the printing layer of silver paste, 3 is the printing layer of carbon nanotubes, and 4 is the co-sintering layer.

Detailed ways

In order to understand the present invention more clearly and demonstrate the beneficial effects of the present invention, the present invention will be further described in detail below in conjunction with the accompanying drawings and the embodiments given by the inventor. It should be noted that these embodiments are some better examples of the present invention, and are not limited to these embodiments.

Example 1:

The first embodiment of the present invention that the inventor provides is to manufacture the monochrome carbon nanotube field emission flat panel display with X-Y addressing of dipole structure, and its manufacturing process is as follows:

1. Substrate selection and pretreatment

In this embodiment, ordinary soda-lime glass is used as the substrate 1 . Use detergent to wash off the oil stains on the glass, then use pure water to clean the detergent, and finally use compressed air to dry the glass for later use.

2. Purification of Carbon Nanotubes

The carbon nanotubes used in this embodiment are multi-walled carbon nanotubes prepared by CVD, which contain a lot of impurities mainly including catalyst particles (mainly iron and its oxides). Purification is mainly to remove these impurities. Since the catalyst used in the preparation of carbon nanotubes will exist in carbon nanotubes, it should be removed during use. The carbon nanotube purification process is as follows:

Prepare an acid solution with concentrated nitric acid: concentrated sulfuric acid = 4:1, use the acid solution to pickle the carbon nanotubes, wash the carbon nanotubes to neutrality after pickling, and then rinse them with deionized water, and filter out the carbon nanotubes after washing. nanotubes and dried.

3. Carbon nanotube slurry preparation

Get carbon nanotubes, ethyl cellulose and terpineol to form carbon nanotube slurry, the ratio of carbon nanotubes to ethyl cellulose is 1: 5-3: 5, and the ratio of ethyl cellulose to terpineol is Add 1.5g ethyl cellulose in every 20ml of terpineol, wherein ethyl cellulose is a pulping agent, and terpineol is a solvent; its technological process is:

Weigh the dried carbon nanotubes, place them in a solvent for 4-8 hours of ultrasonic dispersion, sieve the carbon nanotubes into a paste after they are dispersed in the solvent, then add ethyl cellulose, and heat at 120°C Stir for 30 minutes, stir evenly and cool to room temperature;

4. Printing of silver paste and carbon nanotube paste

The printing process can adopt ordinary screen printing process, as follows:

To adjust the working state of the printing machine, first apply the silver paste screen plate, print the silver paste layer 2 after the plate alignment, and dry; after drying, print the carbon nanotube paste 3 on the silver paste layer, then dry it, and finally dry it at 300°C Pre-burn for 120 minutes under certain conditions;

5. Co-sintering treatment of silver paste printing layer and carbon nanotube printing layer

Put the printed and pre-fired cathode into a vacuum sintering furnace for co-sintering, and use the sintering temperature of the silver paste (580°C) as the co-sintering temperature (the silver paste used here is produced by Guiyan Platinum Industry Co., Ltd.). In order to enhance the protective effect, 30-40 sccm of nitrogen gas (purity higher than 99.99%) is passed through after the vacuum degree of 1 Pa is pumped. After the sintering is completed, the co-sintered layer 4 can be obtained;

Practice has proved that the above-mentioned co-sintering process can also be completed by using argon or hydrogen as the shielding gas.

6. Post-processing of carbon nanotube films

The post-treatment method is as follows: cover the surface of the carbon nanotube film with a plastic film, and use a rubber scraper to scrape and press the carbon nanotube film through the surface of the plastic film, so that the inorganic residues adhered to the surface of the carbon nanotube are broken and detached. After removing the plastic film, use high-pressure gas with a pressure of 5-8 atmospheres to pass through the high-speed airflow generated by the nozzle to blow off the debris and floating dust that are broken or peeled off from the surface of the carbon nanotube film, and the finished cathode can be obtained.

So far, the cathode preparation process has been completed, and the anode fabrication and device packaging process of the device will be described below.

7. Fabrication of anode plates

The glass used for the anode is soda lime glass with ITO coating. Anode plate manufacturing process:

Firstly, the glass is cleaned, photolithography of ITO film is carried out on the cleaned glass, then silver paste pins are printed and dried, and insulating support is printed and then dried, and then sintered, and then phosphor powder is printed and dried;

8. Device packaging

The packaging of the device is to buckle the cathode and anode plates and seal the surrounding with low-melting glass powder, and then use vacuum exhaust equipment to pump the inside of the device to a high vacuum state better than 10 ^-4 Pa. After the device is sealed, evaporate the getter The ultra-high vacuum degree better than 10 ^-6 a can be obtained inside the device. The specific packaging process is:

First apply low-melting-point glass powder on the anode substrate, and pre-fire it at a temperature 10°C to 15°C lower than the packaging temperature (the packaging temperature is provided by the low-melting-point glass powder manufacturer), and then buckle the cathode and anode substrates and install the degasser After clamping, put it into the sintering furnace for formal sintering. During the sintering process, an inert gas (such as nitrogen) should be passed to protect the carbon nanotubes from being oxidized. After the sintering process is completed and cooled to room temperature, connect the device to the exhaust system and vacuumize it. Seal the device when it reaches 1×10 ^-6 orr, and then use high-frequency heating equipment to evaporate the getter. The heating time generally does not exceed 15 seconds to prevent the glass from bursting. A monochromatic carbon nanotube field emission flat-panel display with XY addressing of a diode structure can be obtained, and so far, the entire device has been fabricated.

Example 2:

The second embodiment of the present invention that the inventor provides is to manufacture the color carbon nanotube field emission flat panel display with X-Y addressing of the dipole structure, and its preparation process is exactly the same as embodiment 1, and the difference is that in the anode plate In the manufacturing step 7, the phosphor powders are three colors, and the phosphor powders of the three colors are printed separately. A color carbon nanotube field emission flat panel display with X-Y addressing can be obtained.

Example 3:

The third embodiment of the present invention that the inventor provides is to manufacture the electron source of high-power microwave device, and its manufacturing process is as follows:

1. Substrate production

According to the design requirements and selecting the appropriate material to make the conductive base of appropriate shape. For example, stainless steel or graphite materials are processed into disc-shaped cathode substrates with circular joints (the joints are used to connect with the device and are located at the bottom of the disc), and then the surface is ground and cleaned before entering other Production process;

2. Other production processes

Other manufacturing processes are the same as steps 2-6 in Example 1. The electron source of the high-power microwave device can be obtained.

Claims (3)

1. A cathode preparation method for improving the field emission stability of printed carbon nanotube films, characterized in that, the method increases the printed carbon nanotube films and the conductivity by co-sintering the silver paste printed layer and the carbon nanotube printed layer The contact area between the substrates, and then improve the ohmic contact and thermal conductivity between the printed carbon nanotube film and the conductive substrate, so that the luminous stability and life of the manufactured field emission device under high brightness are significantly improved compared with ordinary cathode devices , including the following steps: (1) Pretreatment of substrate and carbon nanotubes The pretreatment of the substrate is to clean the substrate and then dry it with compressed gas; The pretreatment of carbon nanotubes is the purification of carbon nanotubes to remove the catalyst; the purification process is as follows: Prepare an acid solution with concentrated nitric acid: concentrated sulfuric acid = 4:1, and pickle the carbon nanotubes with the acid solution, wash with water to neutrality after pickling, and then further rinse with deionized water, and filter out the carbon nanotubes after washing. tube and dry; (2) Preparation of carbon nanotube slurry Get carbon nanotubes, ethyl cellulose and terpineol to form carbon nanotube slurry, wherein ethyl cellulose is a pulping agent, terpineol is a solvent; the ratio of carbon nanotubes to ethyl cellulose is 1:5 -3:5, the ratio of ethyl cellulose and terpineol is to add 1.5g ethyl cellulose in every 20ml terpineol, and its technological process is: Weigh the dried carbon nanotubes, place them in a solvent for ultrasonic dispersion for 4-8 hours, pass the carbon nanotubes through a sieve larger than 300 mesh after they are dispersed into a paste in the solvent, then add ethyl cellulose, and Stir at 120°C for 30 minutes, stir well and then cool to room temperature; (3) Printing of silver paste and carbon nanotube paste The printing process adopts the ordinary screen printing process. First, the silver paste layer is screen-printed with silver paste, and after drying, the carbon nanotube paste is printed on the silver paste layer, and then dried, and pre-fired at 300 ° C. 120 minutes; (4) Co-sintering treatment of silver paste printing layer and carbon nanotube printing layer Put the printed and pre-fired cathode into a vacuum sintering furnace or an atmosphere sintering furnace for co-sintering treatment. The sintering temperature of the silver paste is used as the co-sintering temperature. The specific sintering process is carried out according to the instructions provided by different silver paste manufacturers; For vacuum sintering, the vacuum degree should be better than 1Pa. When using atmosphere protection for sintering, 30-40 sccm of inert gas or hydrogen is used as the protection gas during the sintering process; (5) Post-treatment of carbon nanotube films The post-treatment method is as follows: cover the surface of the carbon nanotube film with a plastic film, and use a rubber scraper to scrape and press the carbon nanotube film through the surface of the plastic film, so that the inorganic residues adhered to the surface of the carbon nanotube are broken and detached. After removing the plastic film, use high-pressure gas with a pressure of 5-8 atmospheres to pass through the high-speed airflow generated by the nozzle to blow off the debris and floating dust that are broken or peeled off from the surface of the carbon nanotube film, and the finished cathode can be obtained. 2. the method for claim 1, is characterized in that, said inert gas in step (4) is nitrogen or argon, and its purity is higher than 99.99%, and the purity of said hydrogen is higher than 99.99%. 3. the method as claimed in claim 1 or 2, it is characterized in that, when said adopting atmosphere protection sintering in step (4), pass with the inert gas of 30-40sccm or Hydrogen was used as a shielding gas.

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