TWI252562B - Pattern formation method of carbon nanotube - Google Patents

Abstract

This invention provides a pattern formation method of a carbon nanotube for manufacturing a patterned electron emitter layer with high resolution. A mask rib with high resolution is manufactured by patterning a negative photoresist material applicable for micro-lithographic process. A carbon nanotube layer is formed by spray-coating a spray-coating liquid of carbon nanotube. The mask rib is removed and at the same time the patterned carbon nanotube is made to securely adhere to a cathode conductive layer to form the electron emitter layer through a sintering process. The electron emitter layer prepared based on the invented method can satisfy the requirement of high resolution pattern. Moreover, because the carbon nanotube is manufactured by spray-coating and thus the coating thickness is thin, the generation efficiency and uniformity of electrons are high.

Description

!252562

V. INSTRUCTIONS OF THE INVENTION (1) 技术 The technical field to which the invention pertains] d The present invention relates to a field emission display (FED) cathode panel electron source for producing a cathode plate by spraying a carbon nanotube: Two special: a production technology. Totem of the electron emission source layer of the prior art] The hair is a kind of electric field 俾 to make the cathode electricity: the phosphor powder of the anode plate is excited, and the phosphor powder is generated by the light: by: the size of the area can be According to the process and production: and do not want to do, in addition to the perspective of the flat-panel LCD display.降# The conventional field emission display 1 a has at least the structure between the anode 3 and the vacuum region between the cathodes 15 and between the anode and the cathode: Referring to the first embodiment, the anode 3 is extended to contain an anode glass. Base, 3la' an anode conductive layer 32a, a phosphor powder layer 33a; and a cathode 3 to a cathode glass substrate 4ia, a cathode conductive layer ^ emission source layer 43a; wherein the anode 3a and the cathode 4a are spaced apart It is configured by the barrier wall "a, so the function of the barrier wall can be rationalized by the structure of the first figure. The site is to maintain the vacuum region between the cathode plate and the anode plate, and one of them is applied, and an electric field is applied. The electron source on the cathode plate generates electrons and is excited by the phosphor powder on the anode plate to cause the phosphor powder to emit light. In addition, the cathode plate and the anode plate are electrically connected during the generation of the applied electric field, and the wall is blocked. The material needs to be an insulating material.

1252562 V. DESCRIPTION OF THE INVENTION (2) Formed by the electric field CE), the intensity of the electric field (£) is proportional to the voltage supplied by the unit anode 51a and the unit cathode 52a of each unit structure 5a, and The distance between the anode 5 1 a of the unit structure and the cathode 5 2 a of the unit structure is inversely proportional; therefore, the distance between the unit anode 5 1 a of the unit structure and the unit cathode 52a directly affects the adjacent area. The intensity of the electric field (E); the uniformity of the thickness of the coating on each of the anode and cathode plates, and the uniformity of the thickness of the barrier wall 53a is decisive for the uniformity of illumination exhibited by the field emission display 1a. factor.

In recent years, a new carbon nanotube material (Carbon nanQtubeM was proposed by Iijima in 1991 (Nature 354, 56 (1991)), because the material has high aspect ratio, high mechanical strength, and is not easily poisoned (high chemical Characteristics such as resistance), low-resistance electric field, etc., have become a material for field-emitting electrons (Science 269, pl550 (1995); SID, 98 Digest, Pl052 (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 make the energy barrier (energy b=rier) The reduction in thickness causes electrons to detach from the surface of the material into free electrons by the Quantum- mechanical tunneling effect (J. Appl. phys· 39, 7, pp 3 504 ~~ 3504 (1 9 6 8 ) Therefore, the current emitted by the field electrons can be enhanced by the surface of one of the materials having a low work function, and the electron generation method is performed by applying an electric field to the material. To achieve, there is no need to provide some heat to the material.

V. INSTRUCTIONS (3) Therefore, such field electron emission devices have a cold cathode scale. Therefore, such carbon nanotubes have been used as electron emitters for the plates of the electrodes. ~, 曰i%, for the field emission display, such as the carbon nanotubes containing carbon nanotubes, the method of chemical vapor deposition to sink carbon atoms ";: the production method; Tube, the side J = the catalytic metal layer required for the cathode of the cathode plate, and then the Xingyu totemized growth carbon nanotube long carbon nanotubes 'the current m: to the catalyst metal layer Nano carbon tube in the conductive sound: "Although it has been able to grow steadily - the average length of the electron emission source has been analyzed by the totem. The Yin is in the end of the carbon nanotubes. The efficiency of multi-source electron generation must be;:=匕j belongs to ♦This will affect the efficiency of the electron emission. In addition, the process is completed: the surface treatment method is used to enhance the electrons, and the type can be: m: type The size of (2 〇 leaf) is limited by τ, and the film processing method is used to make the film of the 4th-generation field emission display with a thickness of 5 0 2 3 9 5 ). Taiwan’s invention patent announcement number dimension, one of which is provided by the screen printing//thick film production electron emission source to provide a new thought, and is constantly being proposed. That is, each patent or period source layer 6 that produces a cathode electron emission source still has a part, a part, and the electrons printed by the screen printing method are to be overcome due to the printing of the carbon nanotubes containing the carbon nanotubes. First, the first, to maintain the viscosity of the printed paint is usually at least 100,000 cps to brush the process, limited by ', appearance and accuracy. Second, in line with the network printing, so the production The basic structure of the cold anti-mesh structure and the thickness of the latex is at least greater than 70//m, which is difficult to satisfy 1252562. 5. The invention shows that the high-resolution production is high, and the difference in the degree of density distribution is good. The amount of nano-carbon nanotubes in the ink-in-process system shows that the difference between the demand and the mesh of the multi-(4) product is usually the same, and the aspect ratio of the influence is nano, for carbon. Ming, the screen printing carbon tube 6 2 will be buried in the solid production layer of the nano-field (E) 4V / # m under the job, a source layer and combined with a shadow process, combined: Yi Long The cover is said to be a barrier layer for making electricity and has high efficiency. The height of Tenghua is to make a high solution, a micro-barrier layer can be attached to the spray layer of the spray-coated layer of the barrier layer. In addition, the network is also easy to 4~8" m, the light-emitting carbon tube long carbon tube The length of the distribution tube needs to be after the totem is coated by the coating agent or the efficiency of the carbon tube to the grid current density can be made electronically produced by the person who knows the spray nanometer molecular polyester totemization process of the process of Tenghua production Sintered carbon tube; Third, the thickness of the printed coating can be increased by at least 1 m to form the surface of the totem after printing, which is easy to cause electrons generated by the electron emission source. Third, the tube is broken by 62 degrees. The ratio of the diameter to the double tube is usually up to 40% in the paint, and does not affect the limitation of the screen printing. However, because the second point is limited to JJ1, it is easy to cause a large overlap, even if there is still some electricity after sintering. Within the material 61, it can be greatly reduced with reference to the second figure. For example, the inventors set up an electron-emitting source layer which is printed at a normal level of electricity = 10 mA/cm2 or less. 2 Lei Qiao analysis of the electronic emission of the totemization invention ^. (4) Human carbon tube spraying, / h case number 9 2 1 3 1 5 9 0 ) Negative type layer - kind of micro electron emission source: polymer rabbit 咕 阻 阻 阻 , , , , , , , , , The electric pre-negative photoresist layer is oxidized and transferred to the source; the second is combined with the second spray, and is removed from the cathode of the shadow mask cathode electrons.

Page 9 1252562

Five 'invention descriptions (5) efficiency. The above requirements can be met. [Invention] In view of the conventional cathode emission electron emission source layer of the field emission display, the "steam" bond directly generates a carbon nanotube tube on the cathode electrode, and: the n-analyzed cathode electron The source layer is emitted, but it is still limited to the release of the equipment, and the required equipment cost is expensive. The process is complicated, and the other round carbon bases are still buried and the majority of the carbon nanotubes are still buried. 'Influencing luminescence: lowering, lowering the current density, and benefiting the production of the layer by the scorpion, 阴极 阴极 琢 之 之 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极 : : : : : : : : : : : : : : : : : : The thickness of the shouting layer is uniform and can control and increase the emission current density of the electron emission. The method, the purpose, the purpose is to provide a too half-potential high-resolution electron emission source. The law, mention # purpose, is to provide a kind of gamma y. In addition, the kind of meal cover barrier layer m:::: The number of the sun and the moon I method, still can be used again - the purpose of the Department provides a kind of Nai Shishanshan I launch von Spraying carbon nanotubes, The night, the two-two totem forming side can increase the current density. The electrons produced by the characteristics of the liquid are for the above-mentioned so-called purposes, and the X-Ming system provides a kind of carbon nanotubes. ίο Page-- 1.- 1252562 V. Description of the invention (6) _ ___ Totem forming method to fabricate the electron emission source layer 43; the polymer liquid is close to the high-molecular polyacetate negative-type light, and the nano-carbon tube spray-type negative-type photoresist layer 80, &quot The three figures show two high-polymer polystyrene poles, the totemization of the cathode conductive layer of the plate 4LL = the vine cover barrier structure 7'〇 shown in the fourth figure of Yin Rudi, the second: the cover barrier The layer 70, k two totemized cathode electron emission source layer 43 is a 镂介: ^ hood design system to: JJ: rice carbon tube spray liquid and cathode electrode layer two Γ domain Γ 7 domain; The tube spray liquid is in the area, in the complex area or, as shown in the fifth figure, after a simple dry soldering procedure J ^ spacer 70 surface, such as a vacuum sintering, oxidation or vaporization cover high temperature sintering 'process totemization area The inner layer is the same as the C structure 70. The hollow layer i79 ϊ compartment 70 is analyzed by the source layer, as shown in the sixth and seventh figures. The shadow process can be as high as the totem, and the adjacent non-electricity is sealed. [The domain area can be at least less than 2〇x2〇am or less. The spray process can be less than 20//in, and the electron emission source is _ The current density of the electron emission source can be extracted, and the electron emission uniformity of the present invention can be maintained. The micro///····························· The thickness of the second planting layer is at least 10" is superior to the film, and the agent can be completely oxidized or vaporized to remove the i =, , , , °; the shadow mask is formed to prevent chipping, and the polyester is still negative. The type of photoresist (dry film) in the lithography process solvent composition can be used as a shadow agent; the carbon nanotube spray solution, the solution is dispersed in the temperature range of i, volatilized, has a carbon nanotube suspension ', Temple' solution contains the necessary fixative to make the Nai

Page 11 1252562 V. INSTRUCTION DESCRIPTION (7) The carbon nanotube is connected to the cathode of the electronic device by a fixing agent to spray the surface, and a dispersing agent to disperse the powder material in the spraying solution. The method for forming a totem of a carbon nanotube of the present invention comprises the following steps: (1) forming a high molecular polyester negative photoresist layer 80 on one side of the cathode (glass) substrate 41 containing a cathode conductive layer; (2) using a lithography process totemize the hollowed out region 7 2 of the electron emission source layer to be fabricated as a so-called shadow mask barrier layer 70; (3) spraying a carbon nanotube spray solution, The carbon nanotube filling is adhered to the hollow region 7 2 to be the so-called electron emission source layer 4 3 in the future; (4) removing the shadow mask barrier layer 70 by high temperature sintering or vacuum sintering and attaching it to the non-effective one The carbon nanotubes, and in this sintering process, can fix the carbon nanotube layer in the hollow region 7 2 on the cathode conductive layer 42 to form the electron emission source layer 43. The detailed description of the present invention and the accompanying drawings are to be understood by the accompanying claims . [Embodiment] The present invention provides a totem forming method of a carbon nanotube to produce a high-resolution totemized electron emission source layer; and a high-resolution shadow mask barrier layer by utilizing a negative-type photoresist material totem in a lithography process, Then, the carbon nanotube layer is formed by spraying the carbon nanotube spray liquid, and then the shadow mask barrier layer is removed by the sintering process, and at the same time, the totemized carbon nanotube layer is fixed on the cathode conductive layer to form an electron emission source layer. The electron emission source layer implemented by the method of the invention can meet the requirement of high-resolution totem, and the carbon nanotube layer is prepared by spraying, and the coating thickness is thin.

Page 12 1252562

Both electron generation efficiency and uniformity are high. Please refer to the third figure to the fourth «tube totem formation method to make the ancient:: Kim shows the implementation of the present invention, the nano-blocking polymer polyacetate negative light totemization electron emission source layer; the selection of the cathode conductive layer - (4) The 匕:: method is applied to the cathode substrate to dry the photoresist dry-type resist dry film on the side of the thermal transfer method to form the negative-type photoresist layer 8. Cover:; extremely; there is a cathodic conductive layer - preferably less than the lower jaws and avoiding the thickness of the coating of the carbon nanotubes around the non-essential f# & electron-emitting source formed after the knot The thickness of the layer resist layer is greater than: 〇Ϊ: upper V?, so the formed negative light 10 is not limited to more than 100 m; however, although the thickness of the photoresist layer is at least greater than that of the dashed area 72 Too thick the main layer of the solar layer will cause the area and thickness to be limited due to the shadowing effect. The area layer 80 of the electron emission source layer 43 of the carbon tube is made into a shadow mask. The so-called negative type photoresist is used in the lithography process. The so-called hollow area 72: the second supply: the toluene formation area on the pole conductive layer 42, and then the surface of the 70 coated with the spray coating: ΐ米^ spray coating forms the nano tube#, = = coating liquid ^ Barrier layer, can be a kind of high temperature heart or 曰 ΐ ΐ: sintering, appropriate adjustment of the sintering strip oxidation or vaporization shift, two lower mouth remaining knot, 俾 make the shadow mask barrier layer 70 electron emission source layer 43'. The totem in the hollow region 72 is a nano-particle source layer for illustrating the present invention. Produced by a method of forming electrically conductive cathode ^ DETAILED has produced a representation example embodiments; a cathode (broken glass) layer 42 of the substrate is selected from semi-finished products to be implemented

1252562 V. Inventive Note (9) ' " ------ The object of the film, and designed on the cathode conductive layer 4 2 to make a „ square area of the electron emission source layer 43, each ^ ^ 2 m X 2仏 keeps the coffee m, refer to the seventh figure to read the electric T emission... The ORDYL BF series of the polymer produced by the gap is taken, and the east side, the thickness of the chemical layer can be m, with thermal transfer V 曰 dry film negative photoresist / material, the exposure conditions required for the lithography process will be, the substrate is kept at 5 (rc is better, followed by exposure, exposure s # / ± mouth intestinal I 冤The source layer totem area is shadowed ί ί * find; 2, J light area of the negative resist layer is retained, and not exposed to remove, forming a so-called seat cover barrier layer 7 〇, after exposure 'exposure to carbonic acid The nano-aqueous solution is applied to the electro-sensing layer to the red layer, and the coated electron-emitting source layer region is hollowed out, and the cathode is guided at: the plate 夕 镂 镂 hollow region 72, and then the substrate is treated with dilute hydrochloric acid on the residual plate of sodium citrate solution. After neutralization, apply a simple dry bake-out hollow area 72 '胄 This can make a number of 2 〇"mx 2〇"m i too, followed by spraying the carbon nanotube program to repeatedly spray the spray == m carbon tube spray to form the carbon nanotube layer; fourth, the cathode (glass) after the soil is not stone The substrate is subjected to high-temperature sintering, adjusting the temperature and temperature distribution of the appropriate enthalpy, and adjusting the supply gas of the sintering process, and #I Ming system is introduced into the air 〇 below the 4烧结c in the sintering process. 2Μ(10)以充二,,隆The cover barrier layer 7 2,400 °C or more gradually reduces the supply of air to change the electricity:: π π carbon ... quality 'and the carbon nanotubes are fixed on the water, the electric layer, in addition to the high temperature layer can be borrowed The gas L in the high temperature furnace is moved to remove the oxide and non-cathode electron emission of the oxide mask barrier layer 7 2

Page 14 i^2562 V.^Ϊ^(1〇) — ~s - Source I or inner carbon nanotubes. According to the process of the production of carbon nanotubes electronic power generation = 曰 each of the structure can maintain a plurality of totems of about 18 / / mx 丨 8 / / m, the thickness of the hair-shooting source layer can be about 1 ~ 2 / / m Each of the carbon nanotubes emits electrons, and there is still a part of the oxidation mask barrier layer remaining in some areas, but it is dissolved and removed by a simple solvent, and does not affect the fabricated high resolution image coupled with the nanoelectronic emission. The quality of the source layer, according to the invention: the electron generation characteristics of the cathode: the initial electric field is 2_lv///m (current density 〇.5//cm2), and the electric field is more than 3. 0 V///m. The density can exceed 1 〇 mA / cm 2 .

Herein, the method of the present invention needs to be summarized. The present invention comprises the following steps: (1) coating a negative-type photoresist layer on one side of the cathode substrate containing the cathode conductive layer, which may be a polymer-containing polyacetate; (2) forming a shadow mask layer 7 by the exposure and development process to form a shadow mask layer 7 of the electron emission source layer; (3) spraying the nano slave spray solution, so that the carbon nanotube 6 2 is filled and attached to the hollow In the region 72, to become the initial electron emission source layer; and (4) to remove the shadow mask barrier layer 70 and the non-effective carbon nanotubes attached thereto by high temperature sintering or true sintering, and in the sintering process The carbon nanotube layer in the hollow region is fixed on the cathode conductive layer to form the electron emission source layer 43.

In view of the many changes of the present invention, it will be described in detail, wherein the negative photoresist layer may be a high molecular polyacrylate negative resist layer and may be spin coating or thermal transfer. Laminated on the cathode; and wherein the negative photoresist layer can be a high molecular polyester, the negative photoresist layer can comprise polyvinyl alcohol and dichromate; and wherein the carbon nanotube The spraying solution may comprise a fixing agent, such that the carbon nanotube is connected to the cathode of the electronic device by a fixing agent, and the dispersing agent may be disposed.

1252562 V. INSTRUCTIONS (11) Dispersing the powder materials in the spray solution appropriately; when specifying the conditions in detail, the carbon nanotube spray solution may comprise silver powder, indium salt or indium tin oxide. Powder, and the fixing agent may be glass powder or nitrocellulose; in order to meet the general requirements of development and sintering, the thickness of the polymer polyester negative photoresist layer may be 1 〇# m to 30// m. In order to facilitate the process and the spraying effect, the film formed by spraying the sprayed carbon nanotube spray solution may have a thickness of 8//m-ο· 5 // m; During the sintering process, air 〇 can be passed below = 〇 °c. Bu 0 3 Mpa, to fully oxidize the vine cover barrier 2 knot = at 4 〇〇 t: -50 (rc gradually reduce the supply of air to change the nitrogen to borrow The above detailed disclosure proves that the advantages of the present invention are as follows: 1 . According to the invention, the sprayed nanocarbon tube can be sprayed with 'analytical totemized electron emission source layer'. The shellfish is in the rain ^ according to the invention The high-resolution carbon nanotube electric tube electronic circuit made can still retain the Dafeng Mountain made by the original spraying technology. More, greatly improve the thickness of the surface of the electron emission source of the electron emission source, and the thickness of the surface emission source layer is also favorable for the increase of the current density, and the implementation of the scorpion X-ray layer of the ray/barrier layer produced according to the present invention. , lithography Totem Huashi two target technology into a simple heat, spray Tenghua shadow mask easy;: coating materials, can be implemented in commercial applications Tuluo liquid preparation system is limited to the limit of the invention For example, the reason for (4) content: t Guanwei's description of the application of the invention: that is, the equivalent structure changes, are all included in the scope of 曰 and schema, 奂明

1252562 V. In the description of the invention (12), to protect the rights and interests of the inventors, Chen Ming.

Iim Page 17 1252562 Brief Description of the Drawings - The picture shows the structure of the field emission display element. The second figure shows the structure of the electron emission layer of the conventional screen printing technology. The figure is the fourth step of the step of coating the photoresist layer of the present invention. The figure is a schematic view of the steps of the exposure and development process of the present invention. The fifth figure is a schematic diagram of the steps of the sprayed nanometer anti-tube spraying solution of the present invention, and the sixth figure is a schematic diagram of the totem forming structure of the carbon nanotube of the present invention; The totem of the invention of the carbon nanotubes is formed as a top view. [Description of component symbols] Field emission display 1 a Anode 3 a Anode glass substrate 31a Anode conductive layer 32a Phosphor powder layer 3 3 3 Cathode 4a Cathode glass substrate 41a Cathode conductive layer 42a Electron emission source layer 43a Unit structure 5 a Unit anode 51a unit cathode 5 2a barrier wall 5 3a cathode substrate 41 cathode conductive layer 42 electron emission source layer 43 electron emission source layer 60 fixing agent or conductive material 61 nano carbon tube 62 shadow mask barrier layer 70 hollow region 72

Page 18

Claims (1)

1252562 VI. Patent application scope 1. A method for forming a totem of a carbon nanotube, which is used for an electronic device having a display function, comprising the following steps: (1) coating a negative side of a cathode substrate with a cathode conductive layer (2) forming a shadow mask barrier layer by exposing the development process to the hollow region of the electron emission source layer; (3) spraying the carbon nanotube spraying solution, so that the carbon nanotube filling is adhered to In the hollow region, to become the initial electron emission source layer; and (4) removing the shadow mask barrier layer and the non-effective carbon nanotubes attached thereto by high temperature sintering or vacuum sintering, and in the sintering process The carbon nanotube layer in the hollow region is fixed on the cathode conductive layer to form an electron emission source layer. 2. The method for forming a tonnage of a carbon nanotube according to claim 1, wherein the negative photoresist layer is a high molecular polyester negative photoresist layer and is spin coated or hot. A laminate is applied over the cathode. 3. The method for forming a tonnage of a carbon nanotube according to claim 1, wherein the negative photoresist layer is a high molecular polyester negative photoresist layer and comprises polyvinyl alcohol and dichromate. . 4. The method for forming a tonnage of a carbon nanotube according to claim 1, wherein the carbon nanotube spraying solution comprises a fixing agent, so that the carbon nanotube is connected to an electron by a fixing agent. The cathode of the device is constructed with a sprayed surface, and a dispersant to properly disperse each of the powder materials in the spray solution. 5. The totem formation of the carbon nanotubes as described in item 4 of the patent application scope Page 19 1252562 VI. Patent Application The method, wherein the carbon nanotube spraying solution comprises a powder of silver powder, indium salt or indium tin oxide, and the fixing agent is glass powder or nitrocellulose. 6. The method for forming a tonnage of a carbon nanotube according to claim 1, wherein the negative photoresist layer is a high molecular polyester negative photoresist layer and the film thickness is 10 // m to 3 0 // m between. 7. The method for forming a tonnage of a carbon nanotube according to claim 1, wherein the film formed by spraying the sprayed carbon nanotube spray solution has a thickness of 8//m-0.5 // m between. 8. The totem formation of the carbon nanotubes as described in item 1 of the patent application scope The method, wherein the sintering process is carried out at a temperature below 400 ° C, air 〇 1 - 〇 · 3 Mpa, to fully oxidize the shadow mask barrier layer, and at 40 ° C -50 (TC gradually reduces the supply of air Change to nitrogen into the sintering chamber. Page 20