JP2007188662A - Method of manufacturing field emission type cold cathode - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a field emission type cold cathode allowing uniform electron emission at a low voltage. <P>SOLUTION: The field emission type cold cathode is manufactured by using a flexible substrate engageable with an uneven shape of an electrode surface and having reversible adhesiveness for a transfer process of an orientational carbon nanotube film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a method for manufacturing a field emission cold cathode using carbon nanotubes (hereinafter referred to as CNT) as an electron source. The present technology can be applied to, for example, a thin surface emitting display device such as a field emission display (hereinafter referred to as FED) or a special surface light source such as a liquid crystal backlight.

CNT was discovered by Sumio Iijima in 1991 (see Non-Patent Document 1). The general shape is 0.5-100 nm in diameter and 1-100 μm in length, and is a very elongated hollow tube. Carbon material. In recent years, CNT is expected to be applied as a field electron emission type electron source. A negative voltage is applied to the electrode on which the field electron emission type electron source is arranged, and it is called a cold cathode because it does not emit heat. In particular, when CNT is used as an electron source of a surface-emitting display device such as an FED, a large number of electrons are required because the amount of electron emission from one CNT is insufficient. Furthermore, in order to obtain uniform surface light emission, it is necessary to concentrate the electric field on the CNTs having the same number per area and the same height.

Here, in order to efficiently extract electrons from the CNT at a lower voltage, there is a means for forming a structure called a proximity gate structure or an emitter hole structure on the cold cathode surface. This employs a structure in which a two-layer structure composed of an insulating layer and a gate layer is formed in a state where holes are partially opened on the electrode surface, and CNTs adhere to the electrode surface which is a recess of the hole. The shape of the hole varies depending on the type of device in which the cold cathode is used, but is often circular or strip-shaped. In the case of a circular shape, the diameter is often 5 to 100 μm. In the case of a strip shape, the shorter side is often 5 to 100 μm, and the longer side is not particularly determined.

As a method for manufacturing a cold cathode of CNT having this proximity gate structure, there is a method in which an insulating layer and a gate layer in which holes are opened are first formed on the electrode surface, and then CNT is attached to the electrode surface which is a recess of the hole. preferable. The reason for this is that if CNTs are attached to the electrode surface first, the subsequent step of forming an insulating layer and a gate layer with holes on the electrode surface, that is, screen printing, firing, CVD, laser irradiation This is because the CNT may be damaged by an operation such as a method, a photolithography method, a sand blast method, a nozzle printing method, or an etching method.

There is a method of growing CNTs in the recesses of the holes by first forming an insulating layer and a gate layer in which holes are opened on the electrode surface, and then depositing a catalyst on the electrode surface which is the recesses of the holes and performing CVD (see FIG. For example, see Patent Document 1). However, since the electrode substrate used in this method is exposed to high temperature carbon deposition conditions, the material of the electrode substrate may deteriorate.

Also, an insulating layer and a gate layer with holes opened on the electrode surface are formed first, and then a paste containing CNT is applied to the electrode surface, which is a recess of the hole, and the entire electrode surface is covered with an emitter surface treatment body. A method is disclosed in which CNT is exposed by solidification and peeling the emitter surface treatment body from an electrode (see, for example, Patent Document 2).

Such a method of mixing separately prepared CNTs with a solvent or a binder and adhering them to the electrode increases the adhesion between the electrode and the CNTs and makes them electrically conductive. However, nanoscale materials such as CNTs tend to aggregate even if they are mixed with other fluid materials, and it is difficult to mix them uniformly. If CNT and other fluid substances are attached to the electrode in an unevenly mixed state, the density of the CNT contained in each electron source on the electrode is not constant, and irregularities occur on the surface of the electron source. Therefore, the surface emitting display device is uneven. Here, there is a means of increasing the ratio of the solvent so that it is mixed as uniformly as possible. However, if the solvent remains in the electrode, it becomes a hindrance when performing field electron emission in a high vacuum, so use of the solvent is minimized. It is desirable.

In addition, Patent Document 2 includes an element that relies on chance to divide a paste containing CNT to expose the CNT on the surface, and is not suitable for stable industrial production of a surface light source that emits light uniformly. .

As a method not using a binder, there is a method in which a CNT layer is formed on the filter surface by passing a CNT suspension through a filter, and the CNT layer is transferred to an electrode (for example, see Non-Patent Document 2). However, since the CNT aggregate on the filter is directly attached to the Teflon (registered trademark) sheet as an electrode, it is not suitable for pattern formation. There is also a problem with the adhesion between the electrode and the CNT.

As a transfer method similar to Non-Patent Document 2 described above, although a manufacturing method of a field electron emission type cold cathode is not mentioned, an oriented CNT aggregate is grown on a substrate, and the oriented CNT aggregate is A method of transferring to a second substrate is also disclosed (for example, see Patent Document 3). However, this method is also a method of batch-transferring film-like CNTs, and does not clearly show a method of finely dividing the CNTs at predetermined positions.

  A method is also known in which oriented CNTs are formed, the CNT portion is transferred to an electrode plate except for a growth support member, and an electron emission layer is opened (see, for example, Patent Document 4). However, in order to maintain the shape of a single CNT that is oriented but is isolated, a complicated operation of embedding in a matrix material is required.

Here, as CNTs for field electron emission type cold cathodes, it is known that each thinner one has better field emission capability. In addition, it is known that the CNT aggregate is oriented in the direction perpendicular to the electrode substrate, and the density is lower or the smaller the area of the CNT aggregate, the better the field emission ability. ing. In view of the current situation as described above, the present inventors have succeeded in producing an oriented CNT aggregate composed of CNTs having a height of 10 μm or more and a tube diameter of 10 nm or less (see, for example, Patent Document 5). Electron emission from CNT was also successful (see, for example, Patent Document 6).

As a method for selectively growing an oriented CNT aggregate in a minute area on the order of μm, a method of patterning and arranging a catalytic metal by a mask method (for example, refer to Patent Document 7), and a patterning etching of a catalytic metal by a mask method. And a method of forming a catalyst layer by sputtering and patterning in a stripe shape (for example, see Patent Literature 4). However, CNTs produced by these methods have a tube diameter of 10 nm or more, and the field emission capability is not necessarily sufficient.
JP 2001-236879 A Japanese Patent Laid-Open No. 2003-7201 Special table 2003-500325 gazette JP 2005-116469 A JP 2002-338221 A JP 2004-281388 A Special Table 2002-530805 gazette Special table 2003-500324 gazette S.Iijima, "Helical microtubules of graphite carbon", Nature, 354, p56-58 (1991) WAde Heer et al., "A Carbon Nanotube Field-Emission Electron Source", Science, 270, p1179-1180 (1995)

In order to operate a surface light emitting display device using a field electron emission type cold cathode, it is advantageous to emit electrons with as low voltage and uniform intensity as possible. Therefore, it is desirable that each CNT used in the field electron emission type cold cathode has as small a tube diameter as possible. However, since single-walled CNT has a problem in strength, a multilayered CNT having two or more layers is desirable.

  As the CNT aggregate used for the field electron emission type cold cathode, an oriented CNT aggregate in which a large number of CNTs are aligned in a direction perpendicular to the electrode and the density and the height are constant is preferable. If it is vertically aligned, the maximum electron emission intensity can be obtained in the vertical direction as the sum of a plurality of CNT electron sources. Further, if the density and height are constant, uniform electron emission can be obtained in the planar direction. Furthermore, in the case of field electron emission, the closer the distance between the tip of the CNT and the gate layer as the extraction electrode, the lower the voltage for extracting electrons, so if the height of the electron source is constant, it will be near the surface of the electron source. Even if a gate layer is provided, the uniformity of the distance can be maintained, and the extraction voltage can be lowered to obtain the same electron emission intensity.

  Therefore, as a field electron emission type cold cathode, a gate layer is laminated on the cathode surface via an insulating layer, holes are partially opened in these two-layer structures, and a height is formed on the electrode surface which is a recess of the hole. It is preferable that vertically aligned CNT aggregates having a constant density are upright, and each of the CNTs of the aggregate is a multilayer of two or more layers and is as thin as possible.

In order to avoid thermal, mechanical, and chemical damage to the CNT, the above-mentioned field electron emission cold cathode is prepared by forming the above-mentioned two-layered structure in which holes are opened, and then forming holes. A method of placing the CNT aggregate on the electrode surface, which is a recess, is desirable.

Here, it is said that in order to extract electrons from the entire surface of the oriented CNT aggregate, the extraction electrode needs to be separated by an aspect ratio of 1 or more. For example, in order to extract electrons from the entire oriented CNT film formed in a planar shape with a diameter of 1 mm, the extraction electrodes must be placed at least 1 mm apart, and even if the formed CNT has a threshold electric field of 1 V / micron. Even for a CNT, it is necessary to apply a voltage of 1 KV or more.

From the above considerations, in order to fabricate a high-performance field-emission cold cathode, it is necessary to find a method of opening a hole with the smallest possible area in the two-layer structure and installing the CNT aggregate in the hole with the smaller area. There is.

In view of the above, the present invention forms a two-layer structure of an insulating layer and a gate layer in which a hole with a very small area is first opened, and the electrode surface, which is a concave portion of the hole, has a vertical orientation and a constant height and density. It is an object of the present invention to provide a method for manufacturing a field emission cold cathode that enables uniform electron emission at a low voltage by installing an oriented CNT aggregate composed of CNTs having a thin tube diameter. .

As a result of intensive studies on a method of manufacturing a field emission cold cathode, the present inventors have found a method of using a flexible substrate having an adhesive surface in which the shape of an electrode surface having a hole with a small area is memorized. The present invention has been reached. That is, the present invention is as follows.
(1) A method of manufacturing a field emission cold cathode, wherein an oriented carbon nanotube film is formed in a pattern on the surface of an electrode substrate,
(A) producing an oriented carbon nanotube film on the base substrate surface;
(B) a step of sequentially laminating an insulating layer and a gate layer in a pattern on the electrode substrate surface;
(C) Protrusions on the surface of a flexible substrate having a reversible adhesive surface that can be meshed with the concavo-convex shape of the surface of the electrode substrate obtained in the step (b), and produced in the step (a). The oriented carbon nanotube film is bonded to the surface of the oriented carbon nanotube film, and then the base substrate is peeled off, leaving the oriented carbon nanotube film adhered to the convex part of the surface of the flexible substrate. Transferring to the side,
(D) a step of patterning a conductive binder in the recesses on the surface of the electrode substrate obtained in the step (b);
(E) After bonding the surface of the oriented carbon nanotube film transferred to the flexible substrate and the surface of the patterned conductive binder, the flexibility is left leaving the oriented carbon nanotube film adhered to the conductive binder. And a step of transferring the oriented carbon nanotube film to the electrode substrate side by peeling off the substrate.
(2) A method of manufacturing a field emission cold cathode in which an oriented carbon nanotube film is formed in a pattern on the electrode substrate surface,
(A) producing an oriented carbon nanotube film on the base substrate surface;
(B) After bonding the surface of the oriented carbon nanotube film produced in the step (a) to the surface of the first flexible substrate having a reversible adhesive surface, A step of transferring the oriented carbon nanotube film to the first flexible substrate side by peeling the base substrate leaving the adhered oriented carbon nanotube film; and
(C) a step of sequentially laminating an insulating layer and a gate layer on the electrode substrate surface;
(D) A convex portion on the surface of the second flexible substrate having a reversible adhesive surface that can be meshed with the irregular shape on the surface of the electrode substrate obtained in the step (c), and the first flexible After bonding the surface of the oriented carbon nanotube film transferred to the permeable substrate, the first flexible substrate is peeled off leaving the oriented carbon nanotube film bonded to the convex portion of the surface of the second flexible substrate. A step of transferring the oriented carbon nanotube film to the second flexible substrate side;
(E) a step of patterning a conductive binder in the recesses on the surface of the electrode substrate obtained in the step (c);
(F) After the surface of the oriented carbon nanotube film transferred to the second flexible substrate and the surface of the conductive binder are bonded, the second carbon nanotube film bonded with the conductive binder is left and the second possible carbon nanotube film is left. And a step of transferring the oriented carbon nanotube film to the electrode substrate side by peeling the flexible substrate.
(3) A method of manufacturing a field emission cold cathode in which an oriented carbon nanotube film is formed in a pattern on the electrode substrate surface,
(A) producing an oriented carbon nanotube film on the base substrate surface;
(B) a step of sequentially laminating an insulating layer and a gate layer in a pattern on the electrode substrate surface;
(C) Protrusions on the surface of a flexible substrate having a reversible adhesive surface that can be meshed with the concavo-convex shape of the surface of the electrode substrate obtained in the step (b), and produced in the step (a). The oriented carbon nanotube film is bonded to the surface of the oriented carbon nanotube film, and then the base substrate is peeled off, leaving the oriented carbon nanotube film adhered to the convex part of the surface of the flexible substrate. Transferring to the side,
(D) attaching a conductive binder to the surface of the oriented carbon nanotube film transferred to the flexible substrate;
(E) After bonding the surface of the conductive binder adhering to the surface of the oriented carbon nanotube film and the concave portion of the surface of the electrode substrate, the flexible substrate is peeled off leaving the conductive binder and the oriented carbon nanotube film. And a step of transferring the oriented carbon nanotube film to the electrode substrate side.
(4) A method for producing a field emission cold cathode, wherein an oriented carbon nanotube film is formed in a pattern on the electrode substrate surface,
(A) producing an oriented carbon nanotube film on the base substrate surface;
(B) After bonding the surface of the oriented carbon nanotube film produced in the step (a) to the surface of the first flexible substrate having a reversible adhesive surface, A step of transferring the oriented carbon nanotube film to the first flexible substrate side by peeling the base substrate leaving the adhered oriented carbon nanotube film; and
(C) a step of sequentially laminating an insulating layer and a gate layer on the electrode substrate surface;
(D) A convex portion on the surface of the second flexible substrate having a reversible adhesive surface that can be meshed with the irregular shape on the surface of the electrode substrate obtained in the step (c), and the first flexible After bonding the surface of the oriented carbon nanotube film transferred to the permeable substrate, the first flexible substrate is peeled off leaving the oriented carbon nanotube film bonded to the convex portion of the surface of the second flexible substrate. A step of transferring the oriented carbon nanotube film to the second flexible substrate side;
(E) attaching a conductive binder to the surface of the oriented carbon nanotube film transferred to the second flexible substrate;
(F) After bonding the surface of the conductive binder attached to the surface of the oriented carbon nanotube film and the recess on the surface of the electrode substrate, the second flexible substrate leaving the conductive binder and the oriented carbon nanotube film And a step of transferring the oriented carbon nanotube film to the electrode substrate side by peeling the film.
(5) A flexible substrate having a reversible adhesive surface that can be meshed with the concavo-convex shape of the surface of the electrode substrate, the surface of the electrode substrate in which an insulating layer and a gate layer are sequentially laminated, and the flexibility The field emission according to any one of (1) to (4), which is obtained by contacting with the surface of the substrate, reversing and storing the uneven shape on the surface of the electrode substrate, and then peeling off the surface. Type cold cathode manufacturing method.
(6) The method for producing a field emission cold cathode according to (5), wherein light irradiation or heating is used in the process of inverting and storing the irregular shape on the surface of the electrode substrate.
(7) The material of the surface of the flexible substrate having a reversible adhesive surface is made of polyepoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy resin, fluororesin, polyamide, phenol resin, and polyvinyl chloride. The method for producing a field emission cold cathode according to any one of (1) to (4), which is a single resin or a plurality of resins selected from the group.
(8) Screen printing method, baking method, CVD method, laser irradiation method, photolithography method, sand blasting method, nozzle printing method, and etching method in the step of sequentially laminating the insulating layer and the gate layer on the electrode substrate surface. The manufacturing method of the field emission type cold cathode in any one of (1)-(4) using the single method or multiple methods chosen from the group which consists of.
(9) In the step of producing an oriented carbon nanotube film on the surface of the base substrate, in the presence of the base substrate formed by supporting a catalyst containing a transition metal or a transition metal compound on a support substrate coated with aluminum, The method for producing a field emission cold cathode according to any one of (1) to (4), wherein a carbon nanotube film oriented in a direction perpendicular to the basic substrate is grown on the surface of the basic substrate by decomposing a carbon compound. .
(10) The method for producing a field emission cold cathode according to (9), wherein the method of coating the support substrate with aluminum is a vacuum deposition method, an electrodeposition method, a sputtering method, or a sol-gel method.
(11) The method for producing a field emission cold cathode according to (9), wherein the method of supporting a catalyst containing a transition metal or a transition metal compound on a support substrate coated with aluminum is an impregnation method, an immersion method, or a sol-gel method. .
(12) The carbon compound is one or a mixture of two or more selected from the group consisting of a saturated hydrocarbon compound, an unsaturated hydrocarbon compound, an aromatic hydrocarbon compound, and an oxygen-containing hydrocarbon compound. A method for producing a field emission cold cathode.
(13) The method for producing a field emission cold cathode according to any one of (1) to (4), wherein the outer diameter of the carbon nanotube is in the range of 1 nm to 10 nm.
(14) A method for adhering a surface of an oriented carbon nanotube film and a surface of a flexible substrate having a reversible adhesive surface includes: a surface of the oriented carbon nanotube film and a reversible adhesive surface of the flexible substrate; The method for producing a field emission cold cathode according to any one of (1) to (4), which is subjected to drying, pressure bonding, heating or thermocompression bonding.
(15) The method for producing a field emission cold cathode according to any one of (1) to (4), wherein the electrode substrate is a plate in which a conductive circuit is previously formed on the surface of an insulating plate.
(16) A method in which the surface of the oriented carbon nanotube film and the surface of the conductive binder are bonded to each other by bringing the surface of the oriented carbon nanotube film and the surface of the conductive binder into contact with each other, followed by drying, pressure bonding, heating, or thermocompression bonding. The method for producing a field emission cold cathode according to any one of (1) to (4), wherein:
(17) The method for producing a field emission cold cathode according to any one of (1) to (4), wherein the conductive binder is a conductive paste.
(18) The field emission cold cathode according to any one of (1) to (4), wherein the conductive binder is a conductive silver paste, a conductive gold paste, a conductive carbon paste, or a conductive copper paste. Method.
(19) The method for producing a field emission cold cathode according to any one of (1) to (4), wherein the conductive binder is indium, tin, lead, zinc, copper, or an alloy containing one or more of these metals. .
(20) The method for producing a field emission cold cathode according to any one of (1) to (4), wherein the flexible substrate having a reversible adhesive surface is a resin sheet having a pressure-sensitive adhesive applied to the surface.
(21) A field emission cold cathode obtained by any one of the methods (1) to (20).

  According to the method of manufacturing a field emission cold cathode of the present invention, a two-layer structure of an insulating layer and a gate layer in which a hole with a small area is first formed is formed, and a vertical alignment property is formed on the electrode surface which is a recess of the hole. Thus, a field emission cold cathode having an assembly of oriented CNTs having uniform height and density can be easily manufactured in a large area. By using the cathode manufactured by the method of the present invention, it is possible to obtain a surface-emitting display device that operates at a low voltage and has uniform luminance.

There are the following four methods (A, B, C, or D methods) for producing the field emission cold cathode in the present embodiment.
As shown in FIG. 1, method A includes (a) a step of producing an oriented CNT film on the surface of the base substrate, (b) a step of sequentially laminating an insulating layer and a gate layer on the electrode substrate surface, (C) Protrusions on the surface of a flexible substrate having a reversible adhesive surface that can be meshed with the concavo-convex shape of the surface of the electrode substrate obtained in the step (b), and produced in the step (a). After adhering the surface of the oriented CNT film, the oriented CNT film is transferred to the flexible substrate side by peeling the base substrate leaving the oriented CNT film adhered to the convex portion of the surface of the flexible substrate. (D) a step of patterning a conductive binder in the concave portion of the surface of the electrode substrate obtained in the step (b), and (e) a surface of the oriented CNT film transferred to the flexible substrate. After bonding the surface of the patterned conductive binder to the conductive binder By peeling off the flexible substrate to leave the orientation CNT film adhered with over, the method comprising the step of transferring the oriented CNT film on the electrode substrate.

  The oriented CNT film produced in step (a) of method A is preferably constant in height and density because it is used as a field emission electron source. Each CNT preferably has the smallest possible tube diameter. However, since single-walled CNT has a problem in strength, a multilayered CNT having two or more layers is desirable. Furthermore, the orientation CNT film on the base substrate surface is preferably one having weak adhesion between the base substrate and the CNTs on the base substrate surface in order to perform an operation of peeling from the base substrate in step (c).

Examples of the oriented CNT film satisfying the above conditions include oriented CNT films disclosed by the present inventors in JP-A Nos. 2002-338221 and 2004-002182. As described in Japanese Patent Application Laid-Open No. 2002-338221, the CNT film is prepared by forming a base substrate for CNT growth on a support substrate on which aluminum is vapor-deposited by supporting a CNT generation catalyst. It can be produced by decomposing the compound. In addition, as described in JP-A-2004-002182, the CNT film has a CNT-forming catalyst supported on a support substrate on which a sol-gel porous carrier having 0.1 to 50 nm pores is prepared. It can be produced by preparing a basic substrate for CNT growth and decomposing a carbon compound on the substrate.

The CNT generation catalyst used here may be any catalyst that forms CNTs, and a catalyst containing a transition metal or a transition metal compound is used. For example, a catalyst containing iron, cobalt, nickel, molybdenum or a compound thereof is used. These catalysts can be used alone or as a mixture.

Any catalyst loading method may be used as long as the catalyst is supported on a carrier, and examples thereof include an impregnation method, an immersion method, and a sol-gel method. In some cases, the CNT growth substrate is heated after supporting the catalyst.

By decomposing the carbon compound using the CNT growth substrate, an oriented CNT film is formed on the substrate. Any carbon compound may be used as long as it generates CNTs in the presence of a suitable catalyst, for example, saturated hydrocarbon compounds such as methane, ethane, and propane, and unsaturated hydrocarbon compounds such as ethylene, propylene, and acetylene. , Aromatic hydrocarbon compounds such as benzene and toluene, and oxygen-containing hydrocarbon compounds such as methanol, ethanol, and acetone, preferably methane, ethylene, propylene, acetylene, methanol, ethanol, and propanol.

As a form of introducing the carbon compound, it may be introduced in a gaseous state, mixed with an inert gas such as argon, or introduced as a saturated vapor in the inert gas. Also good. Further, a hetero element-containing nanotube can be obtained by mixing a compound containing a hetero element such as boron or nitrogen incorporated into the nanotube.

As the decomposition reaction of the carbon compound, thermal decomposition is the most common, and a preferable reaction temperature is 400 to 1100 ° C, more preferably 500 to 900 ° C. A preferable reaction pressure is 1 kPa to 1 MPa, more preferably 0.01 to 0.12 MPa.

In the present embodiment, the catalyst particles are often included in the tip portion of each CNT, that is, the tip side of the oriented CNT film, after the CNTs are generated. According to the manufacturing method of the present invention, an oriented CNT film having a height of 1 to 100 μm can be uniformly formed on a basic substrate. At this time, the outer diameter of each CNT can be manufactured in the range of 1 nm to 10 nm. Further, the basic substrate and the CNT film on the basic substrate are only in physical contact, and the adhesion between the basic substrate and the CNT film on the substrate is weak.

In the step (b) in the method A, that is, in the step of sequentially laminating the insulating layer and the gate layer on the surface of the electrode substrate, a normal pattern laminating method, that is, screen printing method, firing method, CVD method, laser An irradiation method, a photolithography method, a sand blast method, a nozzle printing method, an etching method, or a combination of these methods is used.

As a material for forming the insulating layer, an insulating material that does not generate gas in a vacuum is preferable, and a material that can maintain its shape even at a temperature during vacuum sealing (about 500 ° C.) is preferable. In general, it is advantageous in terms of cost to perform a method of screen-printing a paste composed of a glassy sol containing silicon as a main component and a solvent in a pattern and solidifying the organic component such as the solvent by baking. In addition, a photosensitive organic silicate film developed in recent years also has a function as an insulating layer and can be used.

  As a material for forming the gate layer, a material made of a conductive material that does not generate gas in a vacuum is preferable, and a material that can maintain its shape even at a temperature during vacuum sealing (about 500 ° C.) is preferable. In general, it is advantageous in terms of cost to perform a screen printing process in which a paste composed of fine metal particles and a solvent is overcoated on an insulating layer pattern, and then solidified by removing organic components such as a solvent by baking.

The pattern formed in this step refers to a state in which a two-layer structure including an insulating layer and a gate layer has holes partially opened on the electrode surface. The shape of the hole varies depending on the use of the cold cathode finally obtained, but is often circular or strip-shaped. In the case of a circular shape, the diameter is often 5 to 100 μm. In the case of a strip shape, the shorter side is often 5 to 100 μm, and the longer side is not particularly determined.

The flexible substrate having a reversible adhesive surface used in the adhesion and transfer step of step (c) in method A is a flexible substrate capable of adhering or peeling an object to the surface, and the surface portion Means a substrate having a shape that can be meshed with the uneven shape of the surface of the electrode substrate. Regarding the structure, there are a case where the adhesive component is applied to the entire surface of the supporting substrate or a partial pattern according to a pattern, and a case where the substrate itself is a material having adhesiveness. Regarding the function, a substrate that does not have an adhesive function under a normal environment or a substrate that exhibits a function under a special environment such as a humid atmosphere or high temperature can be used. Conversely, even a substrate that has a function under a normal environment can use a substrate that loses its function by a special operation such as light irradiation or heating. Moreover, the reversible expression of such a function can also be controlled stepwise.

  The flexible substrate surface can be meshed with the uneven shape of the electrode substrate surface when the flexible substrate and the electrode substrate are brought close to each other from the vertical direction so that the convex portions of each other can be brought close to each other without being in contact with each other. A shape that can be used. As the most clear shape, as shown in FIG. In addition, in the subsequent step (e), the alignment CNT film to be transferred may be in contact with the conductive binder on the surface of the electrode substrate. Therefore, as shown in FIG. It may be lower than the convex portion on the surface. Further, as a method of attaching the oriented CNT film to a part of the concave portion on the surface of the electrode substrate in the subsequent step (e), the convex portion on the surface of the flexible substrate is a concave portion on the surface of the electrode substrate as shown in FIG. It is also possible to use a narrower one having a convex portion on the surface of the flexible substrate as shown in FIG.

  As shown in FIG. 2, the surface shape can be memorized as a method for producing a flexible substrate having a shape in which the uneven shape on the surface of the electrode substrate is reversed as easily as possible even with a large area. There is a method using a flexible substrate having a reversible adhesive surface. “Surface shape can be memorized” means that the convex portion of the opposite surface shape that is in close contact becomes concave, the concave portion becomes convex, and the shape is inverted and stored. In the process of this memory, light irradiation or heating may be required.

  In particular, the material of the surface of the flexible substrate used here is a photocurable resin exemplified by polyepoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, or the like, or epoxy resin, fluororesin, polyamide, phenol resin Thermosetting resins exemplified by polyvinyl chloride and the like are preferable. When the support substrate is used, the material is not particularly limited, such as a soft resin sheet or a slightly bendable glass plate.

  Here, when the shape of the electrode substrate surface obtained in the step (b) is memorized using a flexible substrate having a reversible adhesive surface capable of memorizing the surface shape, as shown in FIG. The surface of the flexible substrate is brought into contact with the surface of the electrode substrate, the shape of the surface of the electrode substrate is memorized on the surface of the flexible substrate, and then peeled off. In general, it is pressed to some extent so that the flexible substrate surface portion penetrates well into a hole formed on the electrode substrate surface by a two-layer structure including an insulating layer and a gate layer. In the process of storing the shape, light irradiation or heating operation may be performed depending on the material of the flexible substrate surface. By this series of operations, the surface of the electrode with the holes formed thereon becomes convex on the surface of the flexible substrate, the surface of the gate layer becomes concave, and the uneven shape of the electrode surface is inverted and stored.

  In the step (c) in the method A, the oriented CNT film produced in the step (a) is attached to the convex portion on the surface of the flexible substrate. As a method of attaching, the film surface of the oriented CNT film and the convex part of the surface of the flexible substrate are brought into contact, and the contact surface is adhered by drying, pressure bonding, heating or thermocompression bonding, and then the oriented CNT This is done by removing the film. Since the oriented CNT film is only physically on the base substrate, the portion where the film surface is bonded to the convex portion on the surface of the flexible substrate can be easily peeled off. On the other hand, since the portion where the film surface did not adhere to the convex portion on the surface of the flexible substrate remains without being peeled off, the oriented CNT film can be attached only to the convex portion of the surface of the flexible substrate. .

  In the step (d) in the method A, that is, in the step of patterning a conductive binder in the concave portion on the surface of the electrode substrate, the conductive surface is formed on the electrode surface of the hole formed by the two-layer structure composed of the insulating layer and the gate layer. Adhesive binder is adhered. The conductive binder pattern may be attached to the electrode surface of the hole, may be a pattern that follows the shape of the hole, or may be a pattern in which the outer peripheral portion or the central portion of the hole is removed.

  As the conductive binder, a conductive paste or a low melting point metal is often used. When the conductive binder is a conductive paste, a conductive silver paste, a conductive gold paste, a conductive carbon paste, a conductive copper paste, or the like is preferable. As a pattern forming method of these conductive pastes, a nozzle printing method such as an ink jet method is generally used. When the conductive binder is a low melting point metal, it is preferable to use indium, tin, lead, zinc, copper, or an alloy containing one or more of these metals.

Here, when the field emission type cold cathode manufactured in the present invention is used as an electron source of an image display device such as an FED, a conductive circuit is previously formed on the surface of an insulating plate as an electrode substrate. It is preferable to use a flat plate. As the insulating plate, glass which is inexpensive even in a large area is preferable. On the other hand, a method of forming a conductive circuit on an electrode substrate after forming an oriented CNT film on the electrode substrate is very complicated.

  In the last step (e) in the method A, the surface of the orientation CNT film transferred to the convex portion of the flexible substrate surface in the adhesion and transfer step in the step (c), and the surface of the electrode substrate in the step (d) The surface of the conductive binder patterned in the recess is adhered, and the flexible substrate is peeled off. Specifically, the surface of the oriented CNT film and the surface of the conductive binder are brought into contact with each other, dried, pressure-bonded, heated or heat-bonded to bond the contact surface, and then the convex portion on the surface of the flexible substrate. The orientation CNT film is peeled off from the substrate.

  In the peeling operation, the adhesive force between the oriented CNT film and the conductive binder only needs to exceed the adhesive force between the oriented CNT film and the convex portion on the surface of the flexible substrate. Usually, it is possible to easily exceed the first half of the bonding operation in the step (e), but the transfer can be completed more reliably by adding the above-described operation for reducing the adhesive force of the flexible substrate surface.

The electron emission surface of the oriented CNT film transferred to the field emission cold cathode obtained by the method A is the film surface side of the oriented CNT film obtained in the step (a). However, depending on the operation of the step (a), the electron emission performance may differ between the film surface side of the obtained oriented CNT film and the base substrate side. Although the manufacturing method is the same as the above-mentioned method A, when it is more advantageous to use the base substrate side as the electron emission surface, the following method B in which two types of flexible substrates are introduced is used.

Of the method for manufacturing a field emission cold cathode according to the present embodiment, as shown in FIG. 7, method B includes (a) a step of forming an oriented CNT film on the surface of the base substrate, and (b) the step (a After the surface of the oriented CNT film prepared in step 1) is adhered to the surface of the first flexible substrate having a reversible adhesive surface, the oriented CNT film adhered to the surface of the first flexible substrate is left. A step of transferring the oriented CNT film to the first flexible substrate side by peeling the base substrate, and (c) a step of sequentially laminating an insulating layer and a gate layer on the surface of the electrode substrate, d) Convex part of the surface of the second flexible substrate having a reversible adhesive surface that can mesh with the uneven shape of the surface of the electrode substrate obtained in the step (c), and the surface of the oriented CNT film After bonding, the base substrate leaving the oriented CNT film bonded to the convex part of the flexible substrate surface A step of transferring the oriented CNT film to the second flexible substrate side by peeling, and (e) pattern-forming a conductive binder in the concave portion of the surface of the electrode substrate obtained in the step (c). And (f) after bonding the surface of the oriented CNT film transferred to the second flexible substrate and the surface of the conductive binder, leaving the oriented CNT film adhered to the conductive binder, And a step of transferring the oriented CNT film to the electrode substrate side by peeling off the flexible substrate.

  Step (a) in Method B is the same as Step (a) in Method A. The first flexible substrate having a reversible adhesive surface used in the transfer step of step (b) in Method B is the same substrate as the flexible substrate having a reversible adhesive surface used in Method A. However, it is different in that it does not require an uneven surface. However, it is preferable to use the material constituting the flexible substrate described in the method A as the material constituting the first flexible substrate.

Step (c) in Method B is the same as Step (b) in Method A.

The flexible substrate having the second reversible adhesive surface used in step (d) in the method B is the same as the flexible substrate having the reversible adhesive surface used in the method A. Omitted.

Hereinafter, steps (e) and (f) in Method B are the same as steps (d) and (e) in Method A, respectively.

  Of the method for manufacturing a field emission cold cathode according to the present embodiment, as shown in FIG. 8, method C includes (a) a step of producing an oriented CNT film on the base substrate surface, and (b) a surface of the electrode substrate. A step of laminating an insulating layer and a gate layer in a sequential pattern; and (c) a flexible substrate having a reversible adhesive surface that can be meshed with the irregular shape of the surface of the electrode substrate obtained in the step (b). After aligning the convex part of the surface of the substrate and the surface of the oriented CNT film, the oriented CNT film can be made by peeling off the base substrate leaving the oriented CNT film adhered to the convex part of the surface of the flexible substrate. A step of transferring to the flexible substrate side, (d) a step of attaching a conductive binder to the surface of the oriented CNT film transferred to the flexible substrate, and (e) a conductive material attached to the surface of the oriented CNT film. After bonding the surface of the conductive binder and the recesses on the surface of the electrode substrate, By peeling off the flexible substrate to leave the sex binder and orientation CNT film, the method comprising the step of transferring the oriented CNT film on the electrode substrate.

  Steps (a) to (c) in the method C are the same as steps (a) to (c) in the method A, respectively, so description thereof is omitted here.

  The conductive binder used in step (d) in method C is the same as the conductive binder used in step (d) in method A. The attachment method is not particularly limited, but a thin film of a conductive binder is separately formed on the substrate, and the oriented CNT film on the convex portion of the surface of the flexible substrate obtained in step (c) is brought into contact therewith. Generally, the contact surface is adhered by drying, pressure bonding, heating, or heat pressure bonding. That is, after the step (d), an oriented CNT film and a conductive binder are laminated in this order on the convex portion on the surface of the flexible substrate.

  In the step (e) in the method C, there is no particular limitation on the adhesion in the first half, but in general, both are brought into contact with each other and subjected to drying, pressure bonding, heating or thermocompression bonding. In the latter half of the transfer, the adhesive force between the electrode substrate and the conductive binder only needs to exceed the adhesive force between the oriented CNT film and the convex portion on the surface of the flexible substrate. Usually, it is possible to easily exceed the first half by the bonding operation, but the transfer can be completed more reliably by adding the above-described operation for lowering the adhesive force of the flexible substrate surface.

The electron emission surface of the oriented CNT film transferred to the field emission cold cathode obtained by the C method is the film surface side of the oriented CNT film obtained in the step (a). However, depending on the operation of the step (a), the electron emission performance may differ between the film surface side of the obtained oriented CNT film and the base substrate side. Although the manufacturing method is the same as the above-mentioned method C, when it is more advantageous to use the base substrate side as the electron emission surface, the following method D in which two types of flexible substrates are introduced is used.

  Among the methods for manufacturing a field emission cold cathode according to the present embodiment, as shown in FIG. 9, the method D includes (a) a step of producing an oriented CNT film on the base substrate surface, and (b) the step ( After the surface of the oriented CNT film produced in a) is adhered to the surface of the first flexible substrate having a reversible adhesive surface, the oriented CNT film adhered to the surface of the first flexible substrate is A step of transferring the oriented CNT film to the first flexible substrate side by peeling off the base substrate, and (c) a step of sequentially laminating an insulating layer and a gate layer in a pattern on the electrode substrate surface; (D) a convex portion on the surface of the second flexible substrate having a reversible adhesive surface that can mesh with the irregular shape on the surface of the electrode substrate obtained in the step (c); After bonding the surface of the oriented CNT film transferred to the flexible substrate, the convex portion on the surface of the second flexible substrate A step of transferring the oriented CNT film to the second flexible substrate side by peeling off the first flexible substrate while leaving the attached oriented CNT film; and (e) a second flexibility. A step of attaching a conductive binder to the surface of the oriented CNT film transferred to the substrate; (f) after bonding the surface of the conductive binder attached to the surface of the oriented CNT film and the concave portion of the surface of the electrode substrate; And transferring the oriented CNT film by peeling the second flexible substrate while leaving the conductive binder and the oriented CNT film.

  Steps (a) to (d) in Method D are the same as Steps (a) to (d) in Method B. Steps (e) and (f) in Method D are steps (d) in Method C. And (e) are the same as each other, and the description is omitted here.

  As described above, according to the method of manufacturing a field emission cold cathode of the present invention, a two-layer structure including an insulating layer and a gate layer, in which a hole with a very small area is opened, is formed on an electrode substrate, and a recess is formed in the hole. A field emission cold cathode in which an assembly of oriented CNTs having a vertical orientation and a uniform height and density is installed on a certain electrode surface can be provided. By using the cathode manufactured by the method of the present invention, a surface-emitting display device that operates at a low voltage and has a large area and uniform luminance can be obtained.

Example 1 (Method B)
(A) Step of producing an oriented CNT film on the base substrate surface:
A square silica alumina plate having a composition of 25% silica and 75% alumina and a thickness of 2 mm and a side of 30 mm was selected as a support substrate, and was coated by vacuum evaporation of aluminum. At this time, the thickness of the aluminum thin film was 0.5 μm. Subsequently, it was immersed in a cobalt nitrate aqueous solution having a concentration of 0.2 mol / l for 2 hours. After raising the substrate, the substrate was baked in air at 400 ° C. for 3 hours to obtain a basic substrate. After firing, the base substrate was placed in a quartz tube furnace with the aluminum deposition side facing up horizontally. The tube furnace was heated to 700 ° C. while blowing argon at 1000 cm ³ / min in the horizontal direction. Then, while holding 700 ° C., and blown into a tubular furnace of propylene to argon 1000 cm ³ / min was mixed with 300 cm ³ / min. After flowing a propylene / argon mixed gas for 3 minutes, while switching to only argon again, the heating of the tubular furnace was stopped and the mixture was allowed to cool to room temperature. After completion of the reaction, the surface of the basic substrate was observed with a scanning electron microscope (SEM). As a result, it was confirmed that an oriented CNT film having a thickness of 15 μm was formed on the upper side of the basic substrate.
The film was made of CNTs oriented in the vertical direction, and had a constant thickness and a smooth surface. When this alignment film was observed with a transmission electron microscope (TEM), the CNT constituting the alignment film was a multilayer CNT having an outer diameter of 5 to 8 nm and about 5 to 7 layers.

(B) After bonding the surface of the oriented CNT film to the surface of the first flexible substrate, the base substrate is peeled off while leaving the oriented CNT film adhered to the surface of the first flexible substrate. Transferring the conductive CNT film to the first flexible substrate side:
The surface of the adhesive sheet made of acrylic resin / polyolefin and the surface of the oriented CNT film obtained in (a) were brought into contact with each other and pressed with a press machine at 2 kg / cm ² . After the pressure bonding, the adhesive sheet was pulled to leave the oriented CNT film, and the base substrate was peeled off to transfer the oriented CNT film onto the adhesive sheet.

(C) Step of sequentially laminating an insulating layer and a gate layer in a pattern on the electrode substrate surface:
A square ITO substrate having a side of 30 mm was selected as an electrode substrate, and a glass paste was screen-printed in a stripe shape having a line width of 50 μm and a line interval of 70 μm, followed by air baking at 500 ° C. By repeating the same printing and baking twice, an insulating layer having a height of 50 μm was formed. A conductive silver paste was screen-printed on the surface of this insulating layer and air-baked at 500 ° C. to form a gate layer having a thickness of 1 μm on the insulating layer.

(D) A convex portion on the surface of the second flexible substrate having a reversible adhesive surface that can be meshed with the irregular shape on the surface of the electrode substrate, and an oriented CNT film transferred to the first flexible substrate. After adhering to the surface of the second flexible substrate, the first flexible substrate is peeled off, leaving the oriented CNT film adhered to the convex portion of the surface of the second flexible substrate. The process of transferring to the flexible substrate side:
A UV curable adhesive sheet mainly composed of polyepoxy acrylate was laminated on the surface of the electrode substrate obtained in the step (c). Next, 250 mJ / cm ² of UV was irradiated for 15 minutes from the UV curable adhesive sheet side in the laminated state. After the irradiation, the UV curable adhesive sheet was peeled off from the electrode substrate. As a result, stripe-shaped convex portions having a line width of 70 μm and a line interval of 50 μm were formed on the surface. The convex part of this UV curable adhesive sheet and the surface of the oriented CNT film on the adhesive sheet obtained in the step (b) were brought into contact with each other and pressure-bonded with a press at 2 kg / cm ² . After pressure bonding, the UV curable adhesive sheet is pulled to leave the orientation CNT film, and the adhesive sheet is peeled off to form a stripe shape having a height of 15 μm and a line width of 70 μm on the convex portion of the UV curable adhesive sheet. The oriented CNT film was transferred.

(E) A step of patterning the conductive binder in the recesses on the surface of the electrode substrate:
A conductive silver paste is applied to the recesses on the surface of the electrode substrate obtained in step (c) by a nozzle printing method, and a conductive silver paste thin film is formed in a stripe shape having a thickness of 5 μm and a line width of 70 μm on the recesses on the surface of the electrode substrate. did.

(F) After bonding the surface of the oriented CNT film transferred to the second flexible substrate and the surface of the conductive binder, the second flexible film is left with the oriented CNT film adhered to the conductive binder. Step of transferring the oriented CNT film by peeling off the substrate:
The surface of the oriented CNT film obtained in the step (d) and the surface of the conductive silver paste thin film formed in the step (e) were brought into contact with each other and pressure-bonded with a press machine at 4 kg / cm ² . Furthermore, 250 mJ / cm ² of UV was irradiated for 15 minutes from the side of the UV curable adhesive sheet to which the oriented CNT film was adhered. After irradiation, the UV curable adhesive sheet was peeled from the electrode substrate to obtain a field emission cold cathode in which the oriented CNT film was transferred to the concave surface.

Example 2 (Method D)
Steps (a) to (d):
Same as steps (a) to (d) of Method B in Example 1.

(E) A step of attaching a conductive binder to the surface of the oriented CNT film transferred to the second flexible substrate:
A conductive silver paste was screen-printed on a glass plate to form a conductive silver paste thin film having a thickness of 5 μm. The surface of the oriented CNT film obtained in the step (d) and the surface of the conductive silver paste thin film on the glass plate were brought into contact with each other and pressed with a press at 2 kg / cm ² . The glass plate was peeled off, and a conductive silver paste having a thickness of 5 μm was deposited on the oriented CNT film.

(F) After bonding the surface of the conductive binder attached to the surface of the oriented CNT film and the recess on the surface of the electrode substrate, the second flexible substrate is peeled off leaving the conductive binder and the oriented CNT film. The step of transferring the oriented CNT film by:
The concave portion on the surface of the electrode substrate obtained in the step (c) and the surface of the conductive silver paste thin film adhered in the step (e) were brought into contact with each other and pressure-bonded at 4 kg / cm ² with a press. Furthermore, 250 mJ / cm ² of UV was irradiated for 15 minutes from the side of the UV curable adhesive sheet to which the oriented CNT film was adhered. After irradiation, the UV curable adhesive sheet was peeled from the electrode substrate to obtain a field emission cold cathode in which the oriented CNT film was transferred to the concave surface.

Manufacturing method of field emission cold cathode (Method A) An example of a flexible substrate having a reversible adhesive surface that can mesh with the irregular shape of the surface of the electrode substrate An example of a flexible substrate having a reversible adhesive surface that can mesh with the irregular shape of the surface of the electrode substrate An example of a flexible substrate having a reversible adhesive surface that can mesh with the irregular shape of the surface of the electrode substrate An example of a flexible substrate having a reversible adhesive surface that can mesh with the irregular shape of the surface of the electrode substrate Method for manufacturing flexible substrate storing uneven shape Manufacturing method of field emission cold cathode (Method B) Manufacturing method of field emission cold cathode (Method C) Manufacturing method of field emission cold cathode (Method D)

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base substrate 2 Oriented carbon nanotube film 3 Electrode substrate 4 Insulating layer 5 Gate layer 6 A flexible substrate having a reversible adhesive surface that can be meshed with the irregular shape on the surface of the electrode substrate 7 Conductive binder 8 Shape memory Flexible substrate 9 having a reversible adhesive surface capable First first flexible substrate 10 having a reversible adhesive surface Second having a reversible adhesive surface that can mesh with the irregular shape of the surface of the electrode substrate Flexible substrate

Claims (21)

A method of manufacturing a field emission cold cathode in which an oriented carbon nanotube film is formed in a pattern on an electrode substrate surface,
(A) producing an oriented carbon nanotube film on the base substrate surface;
(B) a step of sequentially laminating an insulating layer and a gate layer in a pattern on the electrode substrate surface;
(C) Protrusions on the surface of a flexible substrate having a reversible adhesive surface that can be meshed with the concavo-convex shape of the surface of the electrode substrate obtained in the step (b), and produced in the step (a). The oriented carbon nanotube film is bonded to the surface of the oriented carbon nanotube film, and then the base substrate is peeled off, leaving the oriented carbon nanotube film adhered to the convex part of the surface of the flexible substrate. Transferring to the side,
(D) a step of patterning a conductive binder in the recesses on the surface of the electrode substrate obtained in the step (b);
(E) After bonding the surface of the oriented carbon nanotube film transferred to the flexible substrate and the surface of the patterned conductive binder, the flexibility is left leaving the oriented carbon nanotube film adhered to the conductive binder. And a step of transferring the oriented carbon nanotube film to the electrode substrate side by peeling off the substrate. A method of manufacturing a field emission cold cathode in which an oriented carbon nanotube film is formed in a pattern on an electrode substrate surface,
(A) producing an oriented carbon nanotube film on the base substrate surface;
(B) After bonding the surface of the oriented carbon nanotube film produced in the step (a) to the surface of the first flexible substrate having a reversible adhesive surface, A step of transferring the oriented carbon nanotube film to the first flexible substrate side by peeling the base substrate leaving the adhered oriented carbon nanotube film; and
(C) a step of sequentially laminating an insulating layer and a gate layer on the electrode substrate surface;
(D) A convex portion on the surface of the second flexible substrate having a reversible adhesive surface that can be meshed with the irregular shape on the surface of the electrode substrate obtained in the step (c), and the first flexible After bonding the surface of the oriented carbon nanotube film transferred to the permeable substrate, the first flexible substrate is peeled off leaving the oriented carbon nanotube film bonded to the convex portion of the surface of the second flexible substrate. A step of transferring the oriented carbon nanotube film to the second flexible substrate side;
(E) a step of patterning a conductive binder in the recesses on the surface of the electrode substrate obtained in the step (c);
(F) After the surface of the oriented carbon nanotube film transferred to the second flexible substrate and the surface of the conductive binder are bonded, the second carbon nanotube film bonded with the conductive binder is left and the second possible carbon nanotube film is left. And a step of transferring the oriented carbon nanotube film to the electrode substrate side by peeling the flexible substrate. A method of manufacturing a field emission cold cathode in which an oriented carbon nanotube film is formed in a pattern on an electrode substrate surface,
(A) producing an oriented carbon nanotube film on the base substrate surface;
(B) a step of sequentially laminating an insulating layer and a gate layer in a pattern on the electrode substrate surface;
(C) Protrusions on the surface of a flexible substrate having a reversible adhesive surface that can be meshed with the concavo-convex shape of the surface of the electrode substrate obtained in the step (b), and produced in the step (a). The oriented carbon nanotube film is bonded to the surface of the oriented carbon nanotube film, and then the base substrate is peeled off, leaving the oriented carbon nanotube film adhered to the convex part of the surface of the flexible substrate. Transferring to the side,
(D) attaching a conductive binder to the surface of the oriented carbon nanotube film transferred to the flexible substrate;
(E) After bonding the surface of the conductive binder adhering to the surface of the oriented carbon nanotube film and the concave portion of the surface of the electrode substrate, the flexible substrate is peeled off leaving the conductive binder and the oriented carbon nanotube film. And a step of transferring the oriented carbon nanotube film to the electrode substrate side. A method of manufacturing a field emission cold cathode in which an oriented carbon nanotube film is formed in a pattern on an electrode substrate surface,
(A) producing an oriented carbon nanotube film on the base substrate surface;
(B) After bonding the surface of the oriented carbon nanotube film produced in the step (a) to the surface of the first flexible substrate having a reversible adhesive surface, A step of transferring the oriented carbon nanotube film to the first flexible substrate side by peeling the base substrate leaving the adhered oriented carbon nanotube film; and
(C) a step of sequentially laminating an insulating layer and a gate layer on the electrode substrate surface;
(D) A convex portion on the surface of the second flexible substrate having a reversible adhesive surface that can be meshed with the irregular shape on the surface of the electrode substrate obtained in the step (c), and the first flexible After bonding the surface of the oriented carbon nanotube film transferred to the permeable substrate, the first flexible substrate is peeled off leaving the oriented carbon nanotube film bonded to the convex portion of the surface of the second flexible substrate. A step of transferring the oriented carbon nanotube film to the second flexible substrate side;
(E) attaching a conductive binder to the surface of the oriented carbon nanotube film transferred to the second flexible substrate;
(F) After bonding the surface of the conductive binder attached to the surface of the oriented carbon nanotube film and the recess on the surface of the electrode substrate, the second flexible substrate leaving the conductive binder and the oriented carbon nanotube film And a step of transferring the oriented carbon nanotube film to the electrode substrate side by peeling the film.   A flexible substrate having a reversible adhesive surface that can be meshed with the concavo-convex shape of the surface of the electrode substrate, the surface of the electrode substrate in which an insulating layer and a gate layer are sequentially laminated, and the surface of the flexible substrate The field emission cold cathode according to any one of claims 1 to 4, which is obtained by bringing the electrode substrate into contact with each other, reversing and storing the irregular shape of the surface of the electrode substrate, and then peeling off. Method.   6. The method of manufacturing a field emission cold cathode according to claim 5, wherein light irradiation or heating is used in the process of inverting and storing the irregular shape on the surface of the electrode substrate.   The material of the surface of the flexible substrate having a reversible adhesive surface is selected from the group consisting of polyepoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy resin, fluororesin, polyamide, phenol resin and polyvinyl chloride The method for producing a field emission cold cathode according to any one of claims 1 to 4, wherein the field emission cold cathode is a single resin or a plurality of resins.   A group consisting of a screen printing method, a baking method, a CVD method, a laser irradiation method, a photolithography method, a sand blasting method, a nozzle printing method, and an etching method in the step of sequentially laminating an insulating layer and a gate layer on the surface of the electrode substrate. The manufacturing method of the field emission type cold cathode in any one of Claims 1-4 using the method chosen more than one or more.   In the step of producing an oriented carbon nanotube film on the surface of the base substrate, a gaseous carbon compound is formed in the presence of the base substrate in which a support substrate coated with aluminum is loaded with a catalyst containing a transition metal or a transition metal compound. The method of manufacturing a field emission cold cathode according to any one of claims 1 to 4, wherein a carbon nanotube film oriented in a direction perpendicular to the base substrate is grown on the surface of the base substrate by decomposition.   The method for producing a field emission cold cathode according to claim 9, wherein the method of coating the support substrate with aluminum is a vacuum deposition method, an electrodeposition method, a sputtering method or a sol-gel method.   The method for producing a field emission cold cathode according to claim 9, wherein the method of supporting a catalyst containing a transition metal or a transition metal compound on a support substrate coated with aluminum is an impregnation method, an immersion method or a sol-gel method.   The field emission according to claim 9, wherein the carbon compound is one or a mixture of two or more selected from the group consisting of a saturated hydrocarbon compound, an unsaturated hydrocarbon compound, an aromatic hydrocarbon compound, and an oxygen-containing hydrocarbon compound. Type cold cathode manufacturing method.   The manufacturing method of the field emission type cold cathode in any one of Claims 1-4 whose outer diameter of a carbon nanotube is the range of 1 nm-10 nm.   A method for adhering the surface of an oriented carbon nanotube film and the surface of a flexible substrate having a reversible adhesive surface brings the surface of the oriented carbon nanotube film into contact with the reversible adhesive surface of the flexible substrate. The method for producing a field emission cold cathode according to any one of claims 1 to 4, wherein drying, pressure bonding, heating or thermocompression bonding is performed.   The method of manufacturing a field emission cold cathode according to any one of claims 1 to 4, wherein the electrode substrate is a plate in which a conductive circuit is previously formed on the surface of an insulating plate.   The method of adhering the surface of the oriented carbon nanotube film and the surface of the conductive binder is such that the surface of the oriented carbon nanotube film and the surface of the conductive binder are brought into contact with each other and dried, pressure-bonded, heated or thermo-compressed. The manufacturing method of the field emission type cold cathode in any one of Claims 1-4 which are these.   The method for producing a field emission cold cathode according to any one of claims 1 to 4, wherein the conductive binder is a conductive paste.   The manufacturing method of the field emission type cold cathode in any one of Claims 1-4 whose conductive binder is a conductive silver paste, a conductive gold paste, a conductive carbon paste, or a conductive copper paste.   The method for producing a field emission cold cathode according to any one of claims 1 to 4, wherein the conductive binder is indium, tin, lead, zinc, copper, or an alloy containing one or more of these metals.   The manufacturing method of the field emission type cold cathode in any one of Claims 1-4 whose flexible substrate which has a reversible adhesive surface is a resin sheet which apply | coated the adhesive to the surface.   A field emission cold cathode obtained by the method according to claim 1.

Images