TWI284116B - A spray coating liquid of carbon nanotube and its spray coating method - Google Patents

Abstract

This invention relates to a spray coating liquid of carbon nanotube and its spray coating method, which provides a spray coating method to prepare the cathode electron emitter layer of field emission display. An appropriate and volatile spray coating solvent is chosen to make the carbon nanotube easily suspend and disperse therein. Carbon nanotube and the necessary binder or additive are added to prepare a low-viscosity spray coating solution. The spray-coating manner is to utilize high-pressure air as driving media to spray-coat the spray coating solution with carbon nanotube onto the cathode conductive layer or the cathode glass substrate, so that the thickness of coated layer can be controlled by adjusting number of times of coating. In addition, the method of spray coating can make the thickness of the generated electron emitter layer uniform.

Description

1284116 ' _ ——. V. INSTRUCTION DESCRIPTION (1) [Technical Field to Be Invented by the Invention] The present invention relates to a singularity, a r · · m η, & 琢 』 』 ( (f 1 e 1 demissi ο η d ^ p ^ y, FED) > The fabrication technology of the cathode panel electron source layer, especially an I technology. Formula I as the electron emission source layer of the cathode plate u = t This method uses a low viscosity and volatile solvent after coating I? It can be quickly volatized, and the carbon nanotubes are easily exposed on the surface of the coating. The physical effect of the spraying process is relatively easy to deposit on the cathode compared to the nanocarbon tube, the powder particles of the solid or the additive. The surface layer of the conductive layer or the cathode glass substrate is more favorable for the exposure of the carbon nanotubes, and the output of the electrons is increased to increase the current density. [Previous Technology] [The field emission display of the present invention is an electric field generating electrons generated by a cathode electron emitter, and the phosphor powder of the anode plate is excited by the one electron, and the phosphor powder is generated. Light ^, its " | Features 疋 light, thin, effective display area size can be made according to the process and product requirements, in addition to the perspective of the flat-panel LCD display. A conventional field emission display 1a has at least an anode 3 iodine cathode 4a, and a rib 53a is provided between the anode and the cathode to provide a space between the anode and the cathode, and as an anode and a cathode. For the I support, as shown in the first figure, an anode 3a includes at least an anode glass base plate 31a, an anode conductive layer 32a, and a phosphor powder layer 33a; and a cathode 2a contains at least one cathode glass. The substrate 41a, a cathode conductive layer 42&, an electron emission source layer 4 3 a, wherein the interval between the anode 3 a and the cathode 4 a is blocked by the barrier wall, page 6 1284116

V. Description of the invention (2) 53a configuration, so for the work of the barrier wall, the helmet position is from A, not U: unique, rational, and, "holding the vacuum area between the cathode plate and the anode plate, and An electric field is applied to the anode, and the electron source on the cathode plate generates electrons and the phosphor powder on the 4 1 / plate is excited to cause the phosphor powder to emit light. In addition, the cathode plate and the anode are required to be generated by an applied electric field. The plate is turned on, and the resistance C is two kinds of insulating materials f. The mode of generating the electrons is formed by the occurrence of the second electricity % (E), and the intensity of the electric field (E) is determined by the structure of each of the early structures 5a. The unit anode 51a has a proportional relationship with the voltage supplied from the unit cathode 52a, and is inversely proportional to the distance between the unit anode 5 la and the cathode 52a of each unit structure; therefore, the unit anode of each unit The distance between 51a and the cathode 52& of the unit directly affects the strength of the pen %(E) in the vicinity; the thickness of the coating on each of the anode and cathode plates, and the thickness of the barrier wall 53a Uniformity is determined by the uniformity of illumination exhibited by the $' display 1a Sex factor. In recent years, a new carbon nanotube material (Carbon nan (3tube) has been proposed by iijiffla since 1991 (Nature 354, 56 (1991)), because the material has a high aspect ratio, high mechanical Characteristics such as strength, high chemical resistance, non-abrasive, and electric field have become a material for field-emitting electrons (Science 269, pl550 (Science 269, pl550 ( 1995); SID, 98 Digest, ρ1052 (1998); SID'01 Digest, p316 (2001)). The so-called field electron emission system utilizes a high electric filed applied to the surface of the material to block the material. Energy barrier

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5. The invention reduces the thickness of the invention (3) so that electrons can be detached from the surface of the material into free electrons by the Quantum-mechanical tunneling effect (J. Appl. phys. 39, 7, pp 3504 - 3504 (1 9 6 8 )), so that the current emitted by the field electron can be enhanced by the surface of one of the materials having a low work function, and the electron generation method is achieved by applying an electric field to the material. There is no need to provide some heat to the material, so such field electron emission devices are known as cold cathodes (c〇ld cath〇de). Therefore, such carbon nanotubes have been used as an electron emission source commonly used in the field emission display cathode panels. ^ This type of seed is made up of a uniform length on the chemical layer. The patented source of the invention provides the printing method of the source, and the above contains the necessary powder, including nano-vapor deposition. The formation of nanometer nanometers is limited by the number of productions issued by the bulletin No.: A new thinking patent or a period of electronic containing nanocarbon to maintain the printed fixative, especially in this carbon tube electronic hair style The carbon atom carbon sequestration tube is made of a carbon tube on the conductive layer display cathode plate for the thick film process (502395), and the one is continuously proposed to be used as a printing totem for the emission source layer 60 a tube. The outer shape (glass powder, etc.) and the local viscosity of the local viscosity source layer are formed before the formation, the size can still reduce the anode and cathode for the industry to screen printing, then there is still a part of the material viscosity and precision interface to survive Although the process has been completed in the cathode process, the process of making the plate in the small and medium-sized process is usually divided into a thick film process. In addition, the agent and the nano carbon method are available. This type and south (20 inches) of the field emission film according to the present foot (Taiwan produced as the cathode electron electrons to be overcome by screen; uniformly at least a conductive agent (silver pipe of at least 100,000 CP coating dispersion

Page 8 I will be produced, and the coating will be made. The process of the agent and the post-stage process can be wound around the crucible 'the second, the basic 1 〇' m. The surface is thick because it has more than the upper limit. In the second part, there is a part of the second picture of Nai Ka, which is set to be under the electricity. The t tube produces a cluster phenomenon '❿ affects the distribution of the average sentence of the electrons: 'The person adds the necessary dispersant to the method, so The complexity is: the cost is increased, and for the sintering process, these oxides are more complicated than the 南 南 南 南 南 南 俾 俾 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = : The above-mentioned poisoning of the carbon nanotubes, • The production of the electrons - ... 罔 printing process, 胄 limited to the stencil net latex thickness = no: so the thickness of the coating 60a produced at least still average distribution mit The net knot is also easy to cause the totem after printing = usually up to 4~8". Third, the nano-obstructed tube... than the ratio of the length of the tube to the diameter of the carbon tube is usually ',', the distribution of non-meterite is distributed in the paint, and does not affect the screen printing: f 'restrict the length of the carbon tube, but And because of the thickness of the second to 1 afterprint, the thickness of the totem is 10... This is also easy to make; m2a will be coated with the coating'. Even after being sintered, it is still buried in the fixing agent or conductive material 61a. The yield of ΐίί子 is greatly reduced, for example, the invention: the electron emission source of the two-layer nano-carbon nanotube I screen printing (the current density of Em/A town is usually still 1 mA/cni2): :: Can reduce the electron emission of the carbon nanotubes containing m ^ ^ _ premature one, can control or reduce the electronic hairpin, so that the screen produced by the display can be uniformly sentenced to the surface of the source layer The tube exposure is increased to improve the generation of the source layer of the material layer of the source layer, the electron

Page 9 1284116 V. Description of the invention (5) Electronic current-tight method for making electronic material components Simple electronic emission source Meter carbon tube exposed electricity to meet the above requirements by spraying method [Invention content] In view of the conventional chemical The cost of the equipment is high, and the carbon-coated tube is still buried in the low position. The job is the production of the hair layer, the thickness of the source layer, the current density, and the complexity of the operation. The electron-emitting source layer of the sub-emissive layer of the present invention is further configured by the method of the present invention, and the inventor of the present invention further designs a seven-shot source for spraying carbon nanotubes, thereby making it possible to manufacture The corpse/cost of the coating of the spray coating. First, it can control the thickness of the spray and control the thickness flatness. Third, & sub-emission 湄 Zhao Dan 曰 喷 主 主 主 喷 主 主 主 喷 喷 喷 ’ ’ 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈- the kind of demand. The cathode electron emission source layer of the poor-area display shows that the field evaporation is straight and expensive, and the thickness of the coating layer is greatly reduced by a uniformity. The display is connected to the yin of the yin, and the electricity is applied to the field. , increase the cathode electrode of the low-electron device to produce 'or produce the display with the effect of the net effect on the emission of the light-emitting homogenate, and the electron emission of the nano-carbon tube printing method of the carbon source of the carbon nanotube dew source layer And most of the reduction, the current of the cathode electronically controls and increases the coating cost of the coating and the production of the required sub-emission of the nano-density of the emission source of the electron emission, to provide the main purpose of the production technology The electrocoating method 'can control the thickness of the electron emission source layer and the flatness thereof. A purpose of providing a spray coating of an electron-emitting source layer enhances the exposure of the nanocarbon tube and increases the current density. a purpose of providing a spray coating of an electron emission source layer

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In the method of the present invention, the nozzle of the carbon nanotube is coated (2) at a specific temperature range (1) and (2) until a certain range of thickness is reached. The manufacturing method comprises the following steps: (1) spraying the spray surface on the cathode of the electronic device; volatilizing the spray solvent; and (3) repeating the step a certain number of times to reach the carbon nanotube Spray film In order to enable the technical content of the review board, please refer to the following related drawings and only the reference and the limit are provided. A further understanding of the features of the present invention, the detailed description of the present invention, and the accompanying drawings, which are not intended to be an embodiment of the present invention, the present invention provides a spraying solvent and a volatile spraying solvent. In contact with the nano tube and the need to become a low-viscosity spray solution, it drives the spraying of the carbon nanotubes onto the cathode glass substrate to make the thickness of the coating, and the spraying method is easy. The use of a low-viscosity solvent for rapid volatilization makes it easy to make the physical effect of the nano-carbon air coating process. The powder particles such as the agent or the additive are more favorable to the output and the current density than the surface layer of the glass substrate. The electron-emitting source layer is prepared by coating method; the powder preparation method for selecting the fixing agent or the additive which is easy to suspend and disperse the nano carbon tube is applied by the medium of high-pressure air to uniformly coat the thickness of the cathode conductive layer. The coating thickness adjustment is used to make the thickness distribution of the formed coating uniform, and the coated tube coated with the volatile solvent is exposed on the surface of the coating, and the height is higher than that of the carbon nanotube. Shen 7, the cathode conductive layer or the cathode shows the exposure of the carbon nanotubes, and the electron spraying source layer of the present invention is used for lifting electrons; by using a coating

1284116 V. INSTRUCTIONS (8) Spraying and spraying a high-pressure air to spray the coating on the surface of the cathode to form an electron-emitting source layer, using the coating solution and the solid content ratio of the suspension, and selecting The air injection flow rate of the spray gun is at least 200 Ι/min'. The spray solution containing the carbon nanotubes in the electron emission source layer is a solution of isoamyl acetate as a solvent, and the necessary solidification is added. After the cathode plate is sintered at a high temperature, the carbon nanotubes are fixed to the cathode plate, and the glass powder or the cotton wool is added, and the silver powder is added to reduce the lightning-proof resistance of the pen source layer. 7, Tian* Temple One ^ ^ ^ ^ ^ , add the necessary powder to make the above Naiwunu f or add powder more evenly divided into b t cpS ^; i:: r2; 17 cps for L ', and the solution of the nano Carbon tube and addition, 3 powder J powder particle size" to limit, in order to increase the nano: tube: dew or eve +, and 11 from the nano carbon tube length is too long to produce weaving phenomenon @ : & : plug, the tube length of the tube and the so-called powder particle size:; raw = 10:3' which is again 10:9~1〇 : 5 is better. I thought that 10:9 to the spray squirting solution can be applied with spray fixing agent, silver powder, etc., floating powder "such as: carbon tube 62 is lighter than other powders, Since the silver powder of the naphthalene or the additive is preferentially attached to the glass powder 42 of the back surface of the cathode 41, the carbon nanotube 62 is further involved in the fixing agent or the cathode conductive layer or surface, and is further formulated. The solution is a kind of powder 61 gap vinegar sputum agent, after spraying, most of the solvent is vaporized: the chrome of the isoprene acetate is increased, as shown in the third figure. Therefore, the carbon nanotubes / ί: produced electronic 1284116 V, the invention description (9) the thickness of the emission source layer 60 can be reversed by the mouth of the 洚 u μ 々 a, the number of gold control electron emission source layer 6 0 The snow name of the material is private, and the color is better than that of the screen printing method. The high-viscosity coating tube is still in the life of the electricity source. The source layer still contains most of the nano-carbon to the thunder and the straw is sintered.俾 oxidizing the solvent, or a further method, using the surface treatment of the exposed carbon nanotubes, such as laser or surname, such as the source layer 60, and then burning the electrons after spraying Bun, /5 ® and - Γ 丄 θ, " so that the carbon nanotubes are fixed in the cathode electron I source layer can have a large number of halved 〃 emission ^ 靥 ^ ^ # π 耵 木 木Exposed, and the thickness of the fabricated electron source layer can be used as a conventional i /2. The thickness of the electron emission source of the printing method of the present invention is described in the following description of the application of the MF of the present invention to the production of the electron emission source layer of the present invention. The spraying method of the invention is made of 泠, 6, and 6 γ 土 万 制作 制作 制作 制作 制作 f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f The diameter of 0.5# m glass powder is a fixing agent, and the added weight: the average particle diameter of 10~18% is 〇. 5 "Lu powder to reduce the electron emission = the conductive resistance of the layer 'add 5~1〇% Multi-layer tube nanotube carbon nanotubes of average length m. In addition, the necessary dispersing agent is added to prepare the desired carbon nanotube coating solution, and the viscosity of the prepared solution is controlled at 丨5~丨7 cps. In addition, a spray gun for commercial coating has a nozzle diameter of 1. 〇 mm, and the high-pressure air flow rate is controlled at 260 Ι/min' to adjust the solution discharge amount to 200 cc/min. The carbon nanotube spraying solution is sprayed on the cathode conductive layer on the cathode glass substrate to form an electron emission source layer, and the fabricated cathode glass substrate is sintered at a high temperature to fix the electron emission source layer and the conductive layer. .

Page 14 1284116 V. Description of the Invention (According to the Invention) Accordingly, the electron emission source layer formed on the cathode glass substrate has a thickness of 3 to 4//m' which is smaller than the conventional electron-emitting source layer. ^ Degree 1 0 /zm, the thickness of the electron emission source layer of the present invention can be less than 1 / / m "to greatly improve the surface uniformity of the electron emission source, in the f field (E) 4V / / / m The current density has reached more than 20 mA/cm2. The above detailed operation of the present invention for producing an electron-emitting source layer by spraying method is disclosed. Referring to FIG. 3, the structure of the present invention must be clarified. The material composition of the present invention comprises a carbon nanotube 6 2 ; The solvent can be volatilized at a specific temperature range to have the property of suspending and dispersing the nano-carboniferous tube therein; the fixing agent can be distributed in the spraying solvent, and the specific interfacial connection fixing property can be passed through a specific After the fixing process, the carbon nanotubes 62 are connected to the cathode of the electronic device by a fixing agent; the spraying liquid of the carbon nanotubes 6 2 is sprayed on the cathode of the electronic device by a plurality of times 4丨Structural spraying surface 'The solvent is volatilized under a specific temperature range, and after the specific fixing process is performed, the effect of fixing the carbon nanotube on the cathode 4 丨 structure is achieved. The spray liquid of the carbon nanotubes 6 2 of the present invention may further comprise the following detailed characteristics; the spray liquid of the carbon nanotubes 6 2 may further have an additive to reduce the conductive impedance characteristics of the sprayed surface layer, and may further The dispersing agent is provided so that the additive, the fixing agent and the carbon nanotube can be more evenly distributed in the spraying solvent, wherein the additive can be silver powder, and the fixing agent can be powder, the spraying solvent Is isoamyl acetate, and the viscosity of the nano carbon official spray liquid can be controlled at 15~17 cps, and wherein the specific solid

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V. Description of the Invention (11) The procedure is to heat sintering or laser heating or the like to form an electron emission source layer. Referring to the third figure, the method for fabricating the method of the present invention comprises the following steps: (1) spraying the spray coating of the carbon nanotubes 6 2 on the spraying surface of the electronic device; (2) The spray is volatilized at a specific temperature range, and (3) weight 1: steps (1) and (2) until a specific thickness of the spray film of a specific number of carbon nanotubes is reached. The method for fabricating the method of the present invention may have various details as follows. Further, the method may further include a step of causing the sprayed film of the step (3) to be subjected to a fixing process to form an electron emission source layer, wherein the fixing is performed. Process, sintering, laser heating or etching, etc., wherein the spraying of the nanometer is 7 spray liquid is a commercial coating spray gun, the operating strip is two van g two: = mouth diameter is 0 5 - 2 · 0 mm, the high-pressure air flow is controlled at 2 4 2 (10) Ι / min, the amount of the adjusted solution is controlled at 15 〇 250 cc / jj ^ n, and the electron emission source fabricated on the sprayed surface of the pot cathode structure The layer 6〇, the thickness of which is verified by the above detailed disclosure, the advantages of the invention are as follows: 1. The electron emission source layer prepared according to the invention can control the coating layer and the coating thickness distribution is more uniform, which is beneficial to the electron Production performance = 2 · According to the electron emission source layer produced by the invention, the surface of the electron emission source produced by the cypress is made of a low-cost thick film, and the surface of the carbon nanotube is exposed to the surface of the electron emission source. , greatly enhance the generation of electrons, which is conducive to current density Upgrade. '3. Emission source layer made according to the invention, simple preparation of solution

Page 16 1284116 V. INSTRUCTIONS (12) The implementation of coating materials can be implemented in commercial applications. However, the above description is only a preferred embodiment of the present invention, and thus the scope of the present invention is not limited thereto, and the equivalent structural changes of the present invention and the contents of the drawings are all included in the present invention. Within the scope of the invention, to protect the rights and interests of the inventors, Chen Ming.

Page 17 1284116 Brief description of the diagram [Simple description of the diagram] The first diagram, the structure of the field emission display component. The second figure, the electron emission layer coating structure of the conventional screen printing technology. The third figure shows the electron-emitting layer coating structure of the spray coating technique of the present invention. [Explanation of Symbols] Field emission display 1 a anode 3 a anode glass substrate 31a anode conductive layer 32a phosphor powder layer 33a cathode 4 a cathode glass substrate 41a cathode conductive layer 42a electron emission source layer 43a unit structure 5a unit anode 51a Unit cathode 5 2a barrier wall 5 3a electron emission source layer 60a conductive material 61a carbon nanotube 6 2a cathode 41 cathode conductive layer 42 electron emission source layer 60 powder 61 carbon nanotube 62

Claims (1)

1284116 _ case number 92131590 fr year f month s correction _ six, the scope of application for patents] 1, a carbon nanotube spray solution, used to spray on the cathode structure surface of the electronic device, including: nano a carbon tube; a spray solvent which volatilizes at a specific temperature range, and has a property of suspending and dispersing the carbon nanotube therein; the fixative is a powder material which can be distributed in the spray solvent, The specific interface connection fixing property may be such that after the specific fixing process, the carbon nanotube is connected to the cathode of the electronic device by the fixing agent to construct the spraying surface; the additive is a powder material with a reduced t coating surface. The conductive impedance characteristic of the layer; and a dispersing agent, so that the additive, the fixing agent and the carbon nanotube can be uniformly distributed in the spraying solvent; wherein the exposure effect of the carbon nanotube is enhanced, and the additive is free from The length of the carbon nanotube tube is too long to cause weaving, and the average tube length of the nano tube is larger than the particle size of the powder; wherein the ratio of the tube length of the carbon tube to the particle size of the powder is 10 ·· 9~ 10:3; The spraying surface of the carbon nanotube is sprayed on the cathode of the electronic device by a plurality of times, and the spraying solvent is volatilized under a specific temperature range, and after the specific fixing process is performed, the fixing is achieved. The carbon nanotubes are sprayed on the surface of the cathode structure. 2. The spray liquid of the carbon nanotube according to claim 1, wherein the additive is silver powder, and the weight percentage is 10 to 18%, and the solid is Page 19 1284116 _ Case No. 92131590_ Year Month 曰 Amendment _ VI. The patent application scope is glass powder, the weight percentage is 2 0~2 5 %, the spraying solvent is isoamyl acetate, carbon nanotube The weight percentage is 5~10%, and the necessary dispersant is prepared as the desired carbon nanotube spraying solution, and the viscosity of the carbon nanotube spray liquid prepared is controlled at 15~17 CPS. 3. The spray coating of the carbon nanotubes described in claim 1 wherein the average length of the carbon nanotubes is 1 // m, and the average particle size of the powder 0. 5 // m. 4. A spraying method for a spray coating of a carbon nanotube, which comprises using a spray coating of a carbon nanotube according to claim 1 of the patent application, comprising the following steps: ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ _ (1) spraying the spray coating of the carbon nanotube on the cathode of the electronic device to construct a spray surface; (2) volatilizing the spray solvent at a specific temperature range; and (3) Steps (1) and (2) are repeated until a certain number of times is reached to achieve a specific range thickness of the sprayed film of the carbon nanotubes. 5. The method for spraying a spray coating of a carbon nanotube according to claim 4, further comprising a step of subjecting the sprayed film of step (3) to a specific fixing process to form an electron emission source Floor. 6. The method of spraying a spray coating of a carbon nanotube according to claim 5, wherein the fixing procedure is sintering or laser heating. 7. The method for spraying a spray coating of a carbon nanotube according to claim 4, wherein the spray coating of the carbon nanotube is a commercial spray gun, and the operation thereof The condition range is: the nozzle diameter is 0. 5-2. 0 mm, the high pressure air flow is controlled at 2 4 0 - 2 8 0 1 / mi η, and the adjustment solution is ejected. Page 20 1284116 _ Case No. 92131590_Yearly 曰 Amendment _ VI. Patent application range The quantity is controlled at 1 50 - 25 0 cc / min. 8. The spraying method of the coating liquid for a carbon nanotube according to claim 5, wherein the electron emission source layer formed on the surface of the cathode structure is 3 to 6/m. . Page