JP2015032500A - Anisotropic conductor film, manufacturing method thereof, device, electron emission element, field emission lamp, and field emission display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anisotropic conductor film that does not require complicated process control.SOLUTION: An anisotropic conductor film 1 comprises: a pore structure 21 formed from an anodic oxidation metal film including a plurality of through holes 21H; a conductor film 41 formed on one surface 21S of the pore structure 21; and a conductor 22 selectively formed within a part of the plurality of through holes 21H. The anisotropic conductor film 1 further comprises: an inorganic particle layer 31 formed on the one surface 21S of the pore structure 21; a plurality of particulate cavity parts 33 formed within the inorganic particle layer 31 in contact with the one surface 21S of the pore structure 21 and of which the diameter is larger than that of the through hole 21H; and a conductor film 41 which is formed within the cavity parts 33 in contact with the one surface 21S of the pore structure 21 and formed from a material capable of plating the conductor 22 with a metal. The conductor 22 is selectively formed within the through hole 21H in contact with the conductor film 41 among the plurality of through holes 21H.

Description

  The present invention relates to an anisotropic conductor film, a method for manufacturing the same, and a device / electron emitting element / field emission lamp / field emission display using the anisotropic conductor film.

Field emission (FE) devices are expected to provide high brightness with low power consumption. The FE device can be used as a field emission lamp (Field Emission Lump: FEL) or a field emission display (Field Emission Display: FED).
In the FE device, the phosphor layer provided on the anode substrate is excited by the electron beam emitted from the emitter (electron source) provided on the cathode substrate, and light emission is obtained. Conventionally, spindt emitters, carbon nanotube (CNT) emitters, and the like are used as emitters. However, the Spindt-type emitter has a complicated manufacturing process and it is difficult to increase the area. It is difficult to design a structure of a CNT emitter in which CNTs having high crystallinity are regularly arranged with a uniform length.

An anodized metal film having a plurality of needle-like non-through holes and a barrier layer can be obtained by anodizing at least a part of an anodized metal body such as Al. By partially removing the barrier layer side of the anodized metal film, it is possible to obtain a pore structure having a plurality of needle-like through-holes extending in the direction intersecting the plane direction. A conductor film can be formed on one surface of the pore structure, and a needle-like conductor can be formed inside the plurality of through holes by electrolytic plating. A high electric field can be locally generated in the electric field at the tip of the conductor formed inside the through hole.
Non-Patent Document 1 proposes use of the above structure for an FE device. The conductor film formed on one surface of the pore structure can be used as an electrode layer, and the acicular conductor formed inside the through-hole can be used as an emitter.
Patent Document 1 discloses a structure in which a Spindt-type emitter is further formed on a conductor formed inside a plurality of through holes in the structure (FIG. 1).
In the present specification, a plurality of emitter layers arranged in the plane direction on the electrode layer are referred to as “emitter layers”. An element including an electrode layer and an emitter layer is referred to as an “electron emitting element”.
By using the anodized metal film, the electron-emitting device can be formed by a simple process, and its area can be easily increased. Since it is easy to control the growth direction and the like of the acicular conductor functioning as an emitter, the structure design is also easy.

U.S. Pat.No. 6034468 Japanese Patent No. 5158809 (Japanese Patent Laid-Open No. 2010-205458) Japanese Patent No. 4271467 (Japanese Patent Laid-Open No. 2004-285405) JP-A-4-87213 JP 2004-273289 A

Electrochemistry Communications 11 (2009) 660-663. Electrochemistry Communications 13 (2011) 458-461. Nanoscale Research Letters 2012, 7: 406. J. Appl. Phys., Vol. 93, No. 11, (2003) 9237-9242.

In general, in an electron-emitting device, it is known that if the emitter gap becomes too narrow, the electric field applied to the tip of each emitter is shielded, and the electron emission performance approaches that of a planar electrode.
For example, Patent Document 2 discloses a configuration in which a through hole is provided in a CNT emitter layer (FIG. 1). In Patent Document 2, when the diameter (W) of the through hole is fixed to 80 μm, the pattern width (S) of the CNT emitter layer is reduced to relatively increase the space, thereby improving the electron emission performance. (FIG. 7).

  In an anodized metal film manufactured under normal conditions, the diameter of the through holes is, for example, about 20 to 200 nm, and the interval between adjacent through holes is, for example, about 20 to 200 nm. Therefore, in the electron-emitting device using the anodized metal film proposed in Non-Patent Document 1 and Patent Document 1, the emitter gap is very narrow throughout the device, and it is difficult to obtain high electron-emitting performance.

Although the use is different, Patent Document 3 discloses that an anodized metal body is anodized, and a part of a plurality of non-through holes of the obtained anodized metal film is selectively formed as a through hole. A microelectrode array in which a conductor is selectively formed is described (claims 1, 2, and 2).
In this document, anodization is performed after a plurality of depressions are provided on the surface by pressing a SiC mold against an anodized metal body (Al). In the anodized metal film produced by this method, the pore length of the portion where the depression is formed is longer than the pore length of the portion where the depression is not formed. Since the thickness of the barrier layer is different between the part where the dent is formed and the part where it is not, the non-through hole of the part where the dent is not formed is selectively made a through hole, and a needle-like conductor is selectively formed inside it. can do.
However, this method is complicated in process. Moreover, it is necessary to remove the barrier layer where the depression is not formed while leaving the barrier layer where the depression is formed, and it is difficult to control the removal of the barrier layer. Further, when the surface of the metal to be anodized (Al) has fine irregularities and the flatness is low, the depression cannot be provided even if the SiC mold is pressed. In general, in a processing step during the production of a metal body, irregularities of several μm or more, such as rolling streaks, often occur. Therefore, it is difficult to increase the area from the point of flatness of the anodized metal body (Al).

In Patent Document 4, after obtaining an anodized metal film having a plurality of through-holes in a semiconductor chip application, a resist pattern is formed on the surface, and some through-holes are selected using this resist pattern as a mask. The manufacturing method of the anisotropic conductor film which expands in diameter and forms a conductor selectively in the enlarged through-hole is described (FIGS. 3A to 3E).
Since the anodized metal film has hydrophilicity and the resist has lipophilicity, it is not easy to apply the resist directly on the surface of the anodized metal film. In order to carry out the method described in Patent Document 4, at least a hydrophobizing agent is required. Even if a hydrophobizing agent is used, it is difficult to reliably apply a resist so as to seal the opening in the space in the through hole in which no conductor is to be formed.
As described above, Patent Document 4 is difficult to implement in the first place.
In the method described in Patent Document 4, the tip of the conductor formed in the through hole is contaminated or altered by a hydrophobizing agent, a resist, or a solvent used for resist pattern removal, and the performance as an emitter is lowered. There is also a fear.
Further, when the resist remains in the through hole, the entire emitter may be contaminated by heat diffusion due to the heating process, and the performance as the emitter may be deteriorated.

As related technologies of the present invention, there are Patent Document 5 and Non-Patent Documents 2 to 4.
Patent Document 5 discloses a method for manufacturing an electron-emitting device in which a plurality of particles are arranged on a conductive substrate, an electron-emitting material is formed through the obtained particle mask, and the particle mask is removed. (Summary). According to this method, a protruding emitter can be formed in the gap between a plurality of particles (FIG. 3). As the conductive substrate, a single crystal silicon wafer, titanium, or the like is used (Examples 1 to 5). Examples of the particles include silica, alumina, titanium oxide, zirconium oxide, tantalum pentoxide, gadolinium oxide, yttrium oxide, and polystyrene. Examples of the electron emission material include tungsten, silicon, titanium nitride, and amorphous carbon.
Non-Patent Document 2 describes a method of manufacturing a GaAs pillar structure by arranging a plurality of particles on a GaAs substrate and etching the GaAs substrate through the obtained particle mask.
In Non-Patent Document 3, a particle layer including a plurality of inorganic particles having a relatively large diameter and a plurality of resin particles having a relatively small diameter is formed on a silicon substrate, and the plurality of inorganic particles are removed. A method of manufacturing a porous silicon structure by forming a particulate cavity and forming a conductor film in the cavity is described.
In Non-Patent Document 4, after applying a dispersion containing polystyrene (PS) particles and silica particles on a substrate such as a silicon wafer, the polystyrene (PS) particles are removed by heating at about 400 ° C., A method for producing a porous silica structure is described.
The methods described in Patent Document 5 and Non-Patent Documents 2 to 4 do not use an anodized metal film.

  The present invention has been made in view of the above circumstances, and is selectively formed in a pore structure made of an anodized metal film having a plurality of through holes and inside some of the plurality of through holes. It is an object of the present invention to provide an anisotropic conductive film that can be manufactured without using a resist without requiring complicated process control and a method for manufacturing the same.

The anisotropic conductor film of the present invention is
A pore structure composed of an anodized metal film having a plurality of through-holes extending in a direction crossing the plane direction;
An anisotropic conductive film comprising a conductor selectively formed inside some of the plurality of through holes,
further,
An inorganic particle layer formed on one surface of the pore structure;
A plurality of particulate cavities formed in the inorganic particle layer in contact with the one surface of the pore structure, and having a diameter larger than the through-holes;
A conductor film made of a material capable of plating the conductor, formed in contact with the one surface of the pore structure in the cavity,
The conductor is selectively formed in a through hole in contact with the conductor film among the plurality of through holes.

  In the present specification, the “particulate cavity” is a cavity that originally has particles and is formed by removing the particles.

The method for producing an anisotropic conductive film of the present invention comprises:
A pore structure composed of an anodized metal film having a plurality of through-holes extending in a direction crossing the plane direction;
A method of manufacturing an anisotropic conductor film comprising a conductor selectively formed inside some of the plurality of through holes,
Preparing the pore structure (A);
One surface of the pore structure includes a plurality of inorganic particles and a plurality of resin particles having a diameter larger than the through-holes and the inorganic particles, and at least some of the resin particles are the pore structure. Forming a particle layer in contact with the one surface of (B),
Fixing the bottom of the resin particles in contact with the fine pore structure to the fine pore structure and sealing a part of the openings of the through holes (C);
Removing the plurality of resin particles to form a plurality of particulate cavities in the particle layer (D);
Forming a conductor film in contact with the one surface of the pore structure in the cavity (E);
Step (F) of conducting the electroplating on the pore structure by energizing the conductor film in sequence.

  The device of the present invention comprises the above-described anisotropic conductive film of the present invention.

The electron-emitting device of the present invention is
Comprising the above anisotropic conductive film of the present invention,
An electrode layer including the conductor film and an electron source made of the conductor formed in the through hole are provided.

The field emission lamp (FEL) of the present invention is
A first electrode substrate including the electron-emitting device of the present invention,
A second electrode substrate including an electrode layer and a phosphor layer is disposed opposite to the first electrode substrate via a vacuum space.

The field emission display (FED) of the present invention is
A first electrode substrate including the electron-emitting device of the present invention,
A second electrode substrate disposed opposite to the first electrode substrate via a vacuum space and including an electrode layer and a phosphor layer;
Display is performed by modulation of light emitted from the phosphor layer.

  According to the present invention, comprising a pore structure composed of an anodized metal film having a plurality of through holes, and a conductor selectively formed inside some of the plurality of through holes, An anisotropic conductive film that can be manufactured without using a resist without requiring complicated process control and a method for manufacturing the same can be provided.

It is a schematic cross section which shows the structure of the anisotropic conductor film of one Embodiment which concerns on this invention. It is a figure which shows the example of a planar pattern of a through-hole and a conductor. It is process drawing which shows the manufacturing method of the anisotropic conductor film of FIG. 1A. It is process drawing which shows the manufacturing method of the anisotropic conductor film of FIG. 1A. It is process drawing which shows the manufacturing method of the anisotropic conductor film of FIG. 1A. It is process drawing which shows the manufacturing method of the anisotropic conductor film of FIG. 1A. It is process drawing which shows the manufacturing method of the anisotropic conductor film of FIG. 1A. It is process drawing which shows the manufacturing method of the anisotropic conductor film of FIG. 1A. It is process drawing which shows the manufacturing method of the anisotropic conductor film of FIG. 1A. It is process drawing which shows the manufacturing method of the anisotropic conductor film of FIG. 1A. It is a schematic cross section of FEL of one embodiment concerning the present invention. It is a schematic cross section of FED of one Embodiment concerning this invention.

"Anisotropic conductor film"
With reference to the drawings, a configuration of an anisotropic conductive film according to an embodiment of the present invention will be described.
FIG. 1A is a schematic cross-sectional view of the anisotropic conductive film of this embodiment.
FIG. 1B is a diagram illustrating a planar pattern example of the through hole 21H and the conductor 22.
1A and 1B both show pattern examples of the through holes 21H and the conductors 22, these patterns are different.

The anisotropic conductive film 1 of this embodiment can be preferably used for an electron-emitting device used for a field emission (FE) device or the like.
Although the details will be described later, the FE device has a first electrode substrate including an electron-emitting device including an electrode layer and an emitter (electron source), and is opposed to the first electrode substrate through a vacuum space. The device includes a second electrode substrate that is disposed and includes an electrode layer and a phosphor layer.

  As shown in FIG. 1A, the anisotropic conductor film 1 of the present embodiment is a pore structure formed of an anodized metal film having a plurality of needle-like through-holes 21H extending in a direction crossing the plane direction. 21 is provided. In the anisotropic conductor film 1, a conductor 22 is selectively formed inside some of the through holes 21H among the plurality of through holes 21H.

The anisotropic conductor film 1 further includes an inorganic particle layer 31 composed of a plurality of inorganic particles 31P formed on one surface of the pore structure 21 at 21S (the lower surface in the drawing).
In the inorganic particle layer 31, a plurality of particulate cavities 33 that are in contact with one surface 21S of the pore structure 21 and have a diameter larger than that of the through hole 21H are formed.
In the figure, reference numeral 33 </ b> A is an opening of the cavity 33.
The plurality of inorganic particles 31 </ b> P have a diameter smaller than that of the cavity portion 33 and fill a gap between the adjacent cavity portions 33.
A first conductor film 41 in contact with one surface 21S of the pore structure 21 is formed inside each cavity portion 33.
In the present embodiment, a second conductor film 42 is formed on the surface (the lower surface in the drawing) opposite to the pore structure 21 of the inorganic particle layer 31.
In the present embodiment, the first conductor film 41 and the second conductor film 42 are connected to each other to form one electrode layer 40. In the present embodiment, the first conductor film 41 and the second conductor film 42 may be the same material or different materials. These films may be formed by the same process or may be formed by non-identical processes.
In the anisotropic conductor film 1, the conductor 22 is selectively formed in the through hole 21H in contact with the first conductor film 41 among the plurality of through holes 21H.

The conductor 22 formed inside the through hole 21H is made of a material that can be electrolytically plated.
The conductor 22 preferably includes a metal or a metal compound containing at least one metal element selected from the group consisting of Ag, Au, Cd, Co, Cu, Fe, Mo, Ni, Sn, W, and Zn. .
Among these, a metal or a metal compound containing Ni and / or Ag is particularly preferable from the viewpoint of easy production and high conductivity.
Among these, a metal or a metal compound containing Mo and / or W is particularly preferable from the viewpoint of a high melting point.
The metal may be a pure metal or an alloy.
Examples of the metal compound include metal oxides.

At least the first conductor film 41 in the electrode layer 40 is made of a material capable of plating the material of the conductor 22.
The first conductor film 41 preferably contains a metal or metal compound containing at least one metal element selected from the group consisting of Au, Ag, Cu, Fe, Ni, Sn, and Zn.
Among these, a metal or a metal compound containing Au and / or Ag is particularly preferable from the viewpoint of a high standard electrode potential.
The metal may be a pure metal or an alloy.
Examples of the metal compound include metal oxides.

  The anisotropic conductor film 1 of this embodiment can be used as an electron-emitting device used for an FE device or the like. In this case, the first conductor film 41 and the second conductor film 42 can be used as electrode layers, and the conductor 22 formed inside the through hole 21H can be used as an emitter (electron source).

  The preferred size design of the conductor 22 and the through hole 21H in the electron-emitting device is as follows.

Since the electron emission performance is enhanced, the length of the conductor 22 is preferably 1 μm or more, and particularly preferably 5 μm or more.
In view of high electron emission performance, the diameter of the conductor 22 is preferably 500 nm or less, more preferably 100 nm or less, and particularly preferably 50 nm or less.
Considering the ease of formation, the diameter of the conductor 22 is preferably 20 nm or more.
Since the electron emission performance is improved, the length / diameter of the conductor 22 is preferably 100 or more.

In the present embodiment, the conductor 22 is formed inside the through hole 21H.
Considering a preferable size of the conductor 22, the length of the through hole 21H is preferably 1 μm or more, and particularly preferably 5 μm or more.
The diameter of the through hole 21H is preferably 500 nm or less, more preferably 100 nm or less, and particularly preferably 50 nm or less.
The length / diameter of the through hole 21H is preferably 100 or more.

In the drawing, the case where the filling rate of the conductor 22 in the through hole 21H in which the conductor 22 is formed is 100% is illustrated, but the filling rate of the conductor 22 may not be 100%. .
However, since electron emission performance becomes high, the filling rate of the conductor 22 in the through hole 21H in which the conductor 22 is formed is preferably as high as possible, and is preferably 70 to 100%.
In this specification, the filling rate of the conductor 22 inside the through hole 21H is defined by the length of the conductor 22 / the length of the through hole 21H × 100 (%). The inside of each through hole 21H The filling rate of the conductor 22 is preferably 70 to 100%.

  The filling rate of the conductor 22 in the through hole 21H in which the conductor 22 is formed may vary, but in this case, in-plane variation of the electron emission performance occurs. Considering the in-plane uniformity of the electron emission performance, it is preferable that the variation in the filling rate is small.

  The length of the through hole 21H is determined in consideration of a preferable length of the conductor 22 and a filling rate of the conductor 22 inside the through hole 21H.

  The anisotropic conductor film 1 of this embodiment is manufactured by a manufacturing method described later. Although mentioned later for details, in the manufacturing method of anisotropic conductive film 1 of this embodiment, a plurality of inorganic particles and a plurality of resin particles are used. The anisotropic conductor film 1 of this embodiment is a pattern according to the particle shape and particle diameter of the resin particles used, and the conductor 22 is selectively provided inside some of the through holes 21H among the plurality of through holes 21H. Is formed.

As shown in FIG. 1B, a part of the through holes 21H in which the conductors 22 are formed have a plurality of pattern units 22X in which a plurality of through holes 21H are arranged in a substantially circular shape in plan view. Has a pattern.
A part of the through holes 21H in which the conductors 22 are not formed are generally substantially around the pattern unit 22X having a substantially circular shape in a plan view of the part of the through holes 21H in which the conductors 22 are formed. A plurality of donut-shaped pattern units 22Y are arranged in an array.
The diameters of the pattern units 22X and 22Y, the shapes of the pattern units 22X and 22Y, the number of through holes 21H included in the pattern units 22X and 22Y, and the like can be appropriately changed.

In the present embodiment, a plurality of through holes 21H in which conductors 22 functioning as emitters are formed and a plurality of through holes 21H in which conductors 22 functioning as emitters are not formed are formed in the above pattern. Is formed.
When the anisotropic conductive film 1 of this embodiment is used in a device such as an FE device, the emitter gap (in the present embodiment, the pattern unit 22Y serves as the emitter gap) can be controlled over a wide range. As a result, it is possible to suppress the emitter gap from becoming too narrow, blocking the electric field applied to the tip of each emitter and deteriorating the electron emission performance, and exhibiting high electron emission performance.

"Method for manufacturing anisotropic conductive film"
With reference to drawings, the example of the manufacturing method of an anisotropic conductor film is demonstrated.
2A to 2H are process diagrams. 2A and 2B are schematic perspective views, and FIGS. 2C to 2H are schematic cross-sectional views.

(Process (A))
First, a pore structure 21 having a plurality of through holes 21H is prepared.

<Process (AX)>
First, as shown in FIG. 2A, an anodized metal body M is prepared.
The main component of the anodized metal body M is not particularly limited, and examples thereof include Al, Ti, Ta, Hf, Zr, Si, W, Nb, and Zn. The anodized metal body may contain one or more of these.
As the main component of the anodized metal body, Al or the like is particularly preferable.
In this specification, the “main component of the metal to be anodized” is defined as a component of 99% by mass or more.
The shape of the anodized metal body M is not limited, and examples thereof include a plate shape. Further, it may be used in a form with a support such as a layer in which the metal anodized M is formed on the support.

As shown in FIG. 2B, when at least a part of the anodized metal body M is anodized, a pore structure 21X made of a metal oxide film is generated. For example, when the anodized metal body M has Al as a main component, a pore structure 21X having Al ₂ O ₃ as a main component is generated.
When using a plate-like or other anodized metal body M, a part of the anodized metal body M is usually anodized while leaving a part of the anodized metal body M. In the figure, reference numeral 10 denotes the remainder of the anodized metal body M. In this case, the generated pore structure 21X is usually thin with respect to the remaining portion 10 of the anodized metal body M, but in the drawing, the pore structure 21X is greatly illustrated for easy visual recognition. .

Anodizing is, for example, using an anodized metal body M as an anode, carbon or aluminum as a cathode (counter electrode), immersing them in an anodizing electrolyte, and applying a voltage between the anode and the cathode. Can be implemented.
The electrolytic solution is not limited, and an acidic electrolytic solution containing one or more acids such as sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, and amidosulfonic acid is preferably used.

When the anodized metal body M is anodized, as shown in FIG. 2B, an oxidation reaction proceeds from the surface (upper surface in the drawing) in a direction substantially perpendicular to the surface, and a metal oxide film is generated.
The metal oxide film produced by anodic oxidation has a structure in which a plurality of substantially regular hexagonal columnar columns 21C are arranged adjacent to each other without a gap. A needle-like non-through hole 21A extending in the depth direction from the surface is opened at a substantially central portion of each columnar body 21C. A barrier layer 21B is generated between the bottom surface of the non-through hole 21A and the bottom surface of the metal oxide film.
As shown in the figure, the non-through hole 21A is opened in a direction substantially perpendicular to the surface of the anodized metal body M, but may be opened in a slightly oblique direction.

<Process (AY)>
If there is a remaining part 10 of the anodized metal body M after the step (AX), the remaining part 10 and the barrier layer 21B are removed, and if there is no remaining part 10 of the anodized metal body M after the step (AX). The barrier layer 21B is removed, and the non-through hole 21A is formed as a through hole 21H.
The remaining part 10 of the metal body to be anodized M can be removed, for example, by reverse electrolytic peeling in which reverse electrolysis ⇒ reverse voltage is applied in the anodic oxidation method.
The remaining part 10 of the anodized metal body M and the barrier layer 21B can also be removed by immersing in an acidic liquid such as phosphoric acid.
The remaining part 10 and the barrier layer 21B of the anodized metal body M can be physically removed by cutting or the like.
As described above, the pore structure 21 having the plurality of through holes 21H shown in FIG. 2C is obtained.
In the pore structure 21, either the one surface 21S or the other surface 21T may be the side on which the barrier layer 21B is provided.

(Process (B))
Next, as shown in FIG. 2D, one surface 21S of the pore structure 21 includes a plurality of inorganic particles 31P and a plurality of resin particles 32P having a diameter larger than that of the through holes 21H and the inorganic particles 31P. Part of the resin particles 32 </ b> P forms the particle layer 30 in contact with the one surface 21 </ b> S of the pore structure 21.
The particle layer 30 includes an inorganic particle layer 31 composed of a plurality of inorganic particles 31P and a resin particle layer 32 composed of a plurality of resin particles 32P. The plurality of inorganic particles 31P have a smaller diameter than the resin particles 32P and fill the gaps between the resin particles 32P adjacent to each other.

  Preferably, a dispersion of inorganic particles 31P and resin particles 32P is applied onto the pore structure 21 to form the particle layer 30. As the dispersion, an aqueous dispersion or the like is preferable.

In this step, a plurality of types of inorganic particles 31P having different particle diameters or compositions may be used.
Since the in-plane uniformity of the pattern of the through-hole 21H in which the conductor 22 is formed is increased, it is preferable to use substantially spherical inorganic particles as the inorganic particles 31P. The plurality of inorganic particles 31P preferably have a substantially uniform particle diameter.
Since spherical particles having a uniform particle diameter can be easily obtained, the plurality of inorganic particles 31P is at least one selected from the group consisting of SiO ₂ particles, Al ₂ O ₃ particles, TiO ₂ particles, and ZnO particles. It is preferred to use seed particles.

Similarly, a plurality of types of resin particles having different particle diameters or compositions may be used.
Since the in-plane uniformity of the pattern of the through-hole 21H in which the conductor 22 is formed is increased, it is preferable to use substantially spherical resin particles 32P as the resin particles 32P. The plurality of resin particles 32P preferably have a substantially uniform particle diameter.
Since the spherical particles having a uniform particle diameter can be easily obtained, the plurality of resin particles 32P is at least one selected from the group consisting of polystyrene (PS) particles, poly (meth) acrylic particles, and polylactic acid particles. It is preferred to use seed particles.

  When the dispersion liquid of the inorganic particles 31P and the resin particles 32P is applied, it is preferable to slowly dry the dispersion medium such as water at a temperature lower than the glass transition point of the resin particles 32P before the subsequent step (C). The regularity of the particle arrangement is increased by slowly drying the dispersion.

(Process (C))
Next, as shown in FIG. 2E, the bottoms of the resin particles 32P in contact with the pore structure 21 are fixed to the pore structure 21, and the openings 21D of some of the through holes 21H are sealed.
The pore structure 21 in which the particle layer 30 is formed is heated at a temperature higher than the glass transition point and lower than the melting point to soften the plurality of resin particles 32P, and then cooled or allowed to cool, whereby the pore structure 21 is obtained. The bottoms of the plurality of resin particles 32P in contact with the pore structure 21 can be fixed.
For example, when using substantially spherical resin particles 32 </ b> P, the bottoms of the plurality of resin particles 32 </ b> P in contact with the pore structure 21 are flattened and fixed to the pore structure 21.
In the figure, reference numeral 32A denotes a fixing portion (flattened bottom portion) of the resin particles 32P.
In FIG. 2E, one through hole 21H is sealed by one resin particle 32P. However, depending on the diameter and pitch of the through holes 21H and the diameter of the resin particle 32P, one resin particle 32P is used. The number of through holes 21H to be sealed is appropriately changed.
The diameter of the pattern unit 22X in FIG. 1B corresponds to the diameter of the fixing portion 32A.
When the resin particles 32P are polystyrene (PS particles) or the like, the heating temperature is preferably about 110 ° C., for example.

  In this step, the inorganic particles 31P aggregate during the heating and adhere to the pore structure 21. However, the inorganic particles 31P are not deformed in particle shape like the resin particles 32P.

  In the particle layer 30 after the step (C), the resin particle layer 32 may be a multi-layer, but is preferably a single layer. In the case of a multilayer, after the subsequent step (D), etching may be performed by ion milling or the like so that the thickness of the inorganic particle layer 31 is equal to or less than the height of the particle-shaped cavity portion 33.

(Process (D))
Next, as shown in FIG. 2F, the plurality of resin particles 32P are removed. Examples of the method for removing the resin particles 32P include a method for thermally decomposing the resin particles 32P, a method for dissolving and removing the resin particles 32P using a solvent, and the like.
When the resin particles 32P are polystyrene (PS) particles or the like, the heat decomposition temperature is preferably about 400 ° C., for example.
When the resin particles 32P are polystyrene (PS) particles or the like, toluene or the like can be used as a solvent used for dissolution and removal.
After this step, the particle layer 30 becomes an inorganic particle layer 31 having a plurality of particulate cavities 33. The hollow portion 33 is a portion from which the resin particles 32P are removed.

(Process (E))
Next, as shown in FIG. 2G, a first conductor film 41 in contact with one surface 21S of the pore structure 21 is formed in the cavity 33, and opposite to the pore structure 21 of the inorganic particle layer 31. A second conductor film 42 is formed on the side surface (upper surface in the drawing). In this step, the first conductor film 41 in the cavity 33 and the second conductor film 42 on the inorganic particle layer 31 form one electrode layer 40 connected to each other.
The inorganic particle layer 31 has a gap between the plurality of inorganic particles 31P. In order to prevent the conductor material from entering the gaps between the inorganic particles 31P, the vapor deposition method such as the vapor deposition method is preferable as the film formation method of the first conductor film 41 and the second conductor film 42. .
The surface of the inorganic particle layer 31 has irregularities due to the plurality of inorganic particles 31P. If the thickness of the second conductor film 42 is sufficient, the surface of the inorganic particle layer 31 is covered with the second conductor film 42. Can be covered well.
The thickness of the second conductor film 42 is preferably 100 nm or more.
In order to easily connect the first conductor film 41 in the cavity 33 and the second conductor film 42 on the inorganic particle layer 31 to each other, the inorganic conductor having the cavity 33 is formed before these films are formed. The height of the inorganic particle layer 31 having the cavity 33 may be lowered by etching the particle layer 31 or the like.
After forming the first conductor film 41 and the second conductor film 42, the cavity 33 may be filled with a conductor material.
As long as the first conductor film 41 in the cavity 33 and the second conductor film 42 on the inorganic particle layer 31 are connected to each other, there may be gaps between the plurality of cavities 33.

  In the particle layer 30 after the step (C), when the diameter of the resin particle 32P is equal to or larger than the thickness of the inorganic particle layer 31, the opening 33A of the cavity 33 is widely secured, and the first conductor is formed in the cavity 33. The film 41 is easy to form.

  The first conductor film 41 and the second conductor film 42 are preferably formed by the same process, but they may be formed by different processes.

(Process (D))
Next, as shown in FIG. 2H, the electrode layer 40 is energized, and electrolytic plating is performed on the pore structure 21. Since the first conductor film 41 is in contact with only some of the through holes 21H among the plurality of through holes 21H, the conductor 22 is selectively placed in the through holes 21H in contact with the first conductor film 41. It is formed.
As shown in FIG. 1B, in this embodiment, the conductors 22 are selectively formed inside some of the through holes 21H among the plurality of through holes 21H in a pattern corresponding to the arrangement pattern of the resin particles 32P. The
In the present embodiment, the planar pattern of the conductor 22 can be easily controlled by changing the particle shape or particle diameter of the resin particles 32P to be used.
As described above, the anisotropic conductive film 1 is manufactured.

  The electron emission performance is more effectively exhibited as the extending direction of the conductor 22 is closer to the voltage application direction. According to the anodic oxidation method, the pore structure 21 in which a plurality of through-holes 21H extending in a direction parallel to or close to the voltage application direction is regularly arrayed can be formed by a simple process. According to the anodic oxidation method, the size (length and diameter) and number density of the through holes 21H can be easily controlled, and the area can be easily increased. The anodizing method is a low cost method.

According to the method of the present embodiment, the conductor 22 can be selectively formed inside some of the plurality of through holes 21H without requiring complicated process control, and functions as an emitter. The planar pattern of the conductor 22 can be easily controlled.
Since the anisotropic conductor films 1 and 2 can be manufactured without using a resist, the tip of the conductor 22 formed inside the through hole 21H is a hydrophobic agent, a resist or a solvent used for resist or resist pattern removal. There is no possibility that the performance as an emitter is deteriorated due to contamination or alteration.

  As described above, according to the present embodiment, the pore structure 21 made of an anodized metal film having a plurality of through-holes 21H and a part of the through-holes 21H among the plurality of through-holes 21H are selected. An anisotropic conductor film 1 that can be manufactured without using a resist without requiring complicated process control and a manufacturing method thereof can be provided.

"FE device"
With reference to the drawings, a structure of a field emission lamp (Field Emission Lump: FEL, illumination device) according to an embodiment of the present invention will be described.
FIG. 3A is a schematic cross-sectional view.
The FEL 3 of the present embodiment is a white planar light source.

FEL3 is
A cathode substrate (first electrode substrate) 100 having a substrate body 110 and a cathode layer (electrode layer 40 composed of the first conductor film 41 and the second conductor film 42);
An anode substrate (second electrode substrate) 200 having a substrate body 210 and an anode layer 220 is provided.
A voltage is applied between the cathode layer (the electrode layer 40 including the first conductor film 41 and the second conductor film 42) and the anode layer 220.

In the present embodiment, the cathode substrate 100 is provided with the anisotropic conductive film 1 shown in FIGS. 1A and 1B on the inner surface of the substrate body 110.
As the substrate body 110, a metal plate or a glass substrate with a translucent conductor film such as ITO (indium tin oxide) is used.
The cathode substrate 100 can be obtained by soldering the substrate body 110 or adhering to the anisotropic conductive film 1 of the above embodiment using a conductive double-sided tape.
In the cathode substrate 100, the electrode layer 40 composed of the first conductor film 41 and the second conductor film 42 in the anisotropic conductor film 1 is a cathode layer, and a part of the through holes of the pore structure 21. A conductor 22 selectively formed inside 21H is an emitter (electron source).
In FIG. 3A, although the structure of the anisotropic conductive film 1 is illustrated in a simplified manner, the structure is the same as that shown in FIGS. 1A and 1B. Note that the number of through holes 21H in which the conductor 22 is formed in one pattern unit 22X is appropriately different from that in FIGS. 1A and 1B.

The anode layer 220 is a light-transmitting conductive film such as ITO (Indium Tin Oxide) formed on almost the entire inner surface of the substrate body 210.
A glass substrate or the like is used as the substrate body 210.

A phosphor layer 230 is formed on the inner surface of the anode layer 220.
A known material can be used as the material of the phosphor layer 230.
No particular limitation is imposed on the material of the phosphor layer _{230, ZnS: Ag, Cl,} ZnS: Ag, Al, ZnGa 2 O 4, ZnO: Zn, ZnS: Cu, Al, Y 2 SiO 5: Ce, Y 2 SiO ₅ : Tb, Y ₃ (Al, Ga) ₅ O ₁₂ : Tb, Y ₂ O ₃ : Eu, Y ₂ O ₂ S: Eu, and the like.
The emission color of the phosphor layer 230 is arbitrary.
In the case of a white light source, white light can be obtained by arbitrarily combining a plurality of known materials having different emission colors, such as a blue material, a green material, and a red material, as the material of the phosphor layer 230.

  A spacer 300 is provided between the cathode substrate 100 and the anode substrate 200, and the space between the cathode substrate 100 and the anode substrate 200 is in a high vacuum.

  The phosphor layer 230 is excited by the electron beam emitted from the conductor 22 (emitter) of the cathode substrate 100, and the emitted light is emitted.

  In the FEL 3 of this embodiment, an emitter gap is provided in the emitter layer including the plurality of conductors 22, and the emitter gap can be controlled over a wide range. As a result, it is possible to suppress the emitter gap from becoming too narrow, blocking the electric field applied to the tip of each emitter and deteriorating the electron emission performance, and exhibiting high electron emission performance.

In the present embodiment, the FEL has been described as an example. However, as illustrated in FIG. 3B, as the phosphor layer 230, a red (R) phosphor layer 230R, a green (G) phosphor layer 230G, and a blue (B) If the phosphor layer 230B is patterned and light modulation is performed for each dot, the phosphor layer 230B can be applied to a field emission display (FED, display device).
In FIG. 3B, reference numeral 4 denotes an FED.
In FIG. 3B, the cathode layer (the electrode layer 40 formed of the first conductor film 41 and the second conductor film 42) and the anode layer 220 are not shown.

  Examples The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these.

Example 1
An anisotropic conductor film as shown in FIGS. 1A and 1B was manufactured according to the method described in FIGS. 2A to 2H.

An anodizing process was performed on a 100 × 100 mm aluminum plate having a thickness of 3 mm under the following conditions to form an alumina film having a plurality of needle-like non-through holes and a barrier layer.
-Counter electrode (cathode): Aluminum-Electrolyte: 0.3 M sulfuric acid-Bath temperature: 15-19 ° C
・ Voltage: DC voltage 40V
・ Time: 8 hours

About the obtained alumina film | membrane, the surface and the cross section were observed using the scanning electron microscope (SEM, Hitachi Ltd. "S-4800"). In the surface SEM image (80,000 times), the average pore diameter was determined from the pore area of 100 pores. Further, the pore density was determined from the number of pores in the same surface SEM image. In the cross-sectional SEM image (10,000 times), the average pore length was determined from the pore length of 100 pores.
The obtained alumina membrane had a plurality of needle-like non-through holes opened almost regularly, and had an average pore diameter of 0.02 μm, an average pore length of 50 μm, and an average pore density of 300 / μm ² .

Next, with the alumina film connected to the cathode and the Pt—Ti electrode connected to the anode, a direct current of 5 V was applied to peel the alumina film from the Al substrate.
Next, the alumina film was immersed in phosphoric acid to dissolve the barrier layer at the bottom of the alumina film, and all the plurality of non-through holes of the alumina film were made through holes.
As described above, a 50 μm-thick pore structure having a plurality of through holes was obtained.

Next, a particle layer was formed on one surface of the pore structure as follows.
An aqueous dispersion of 20 nm diameter spherical SiO ₂ particles and 5 μm diameter spherical polystyrene (PS) particles (SiO ₂ particle concentration: 1 mass%, PS particle concentration: 1 mass%) was applied. The aqueous dispersion was dried at 25 ° C. for 20 hours, and spherical SiO ₂ particles and spherical polystyrene (PS) particles were arranged on the alumina film.
The resin particles were arranged without gaps, and the inorganic particle layer was formed so that the plurality of inorganic particles filled the gaps between the plurality of resin particles. The resin particles were arranged in a single layer, and the diameter of the resin particles was larger than the thickness of the inorganic particle layer.
The polystyrene (PS) particles were fixed to the pore structure by heating at 110 ° C. for 120 minutes. The resin particles collapsed at the bottom to become flat fixed portions. From the evaluation of SEM observation described later, it was found that the diameter of the fixed portion was 2.8 μm.
In this example, openings of a plurality of through holes were sealed with one polystyrene (PS) particle.
In this step, the inorganic particles aggregated and adhered to the pore structure.

Next, the pore structure on which the particle layer was formed was heat-treated at 400 ° C. for 5 minutes to burn and remove polystyrene (PS) particles.
After this step, an inorganic particle layer having a plurality of particulate cavities was formed. The thickness of the inorganic particle layer was 3.5 μm.

Next, gold was vapor-deposited on the inorganic particle layer having a particulate cavity. The vapor deposition conditions were as follows.
Degree of vacuum: 5 × 10 ⁻⁴ Pa or less Substrate temperature: 25 ° C.
Deposition rate: 20 nm / min.
Deposition time: 6 min.
A gold film (first conductor film) was formed along the inner surface of each cavity. Also, a gold film (second conductor film) was formed on the surface of the inorganic particle layer opposite to the pore structure. The inside of the cavity and the gold film on the inorganic particle layer were connected to each other to form one electrode layer. The thickness of the gold film was 120 nm.

Finally, the gold film was energized, and Ni was electrolytically deposited on the pore structure. The plating conditions were as follows.
Electrolytic bath: 1.2M nickel sulfate hexahydrate, mixed solution of 0.2M nickel chloride and 0.7M boric acid Bath temperature: 32-37 ° C
-PH: 4.0-5.0
-Voltage: -0.9V vs. Ag / AgCl
Treatment time: 120 minutes An anisotropic conductive film was obtained as described above.

The SEM surface observation of the obtained anisotropic conductor film was implemented.
Sealing portions in which Ni was formed inside the through holes were seen in a pattern in which a plurality of pattern units in which a plurality of through holes were arranged in a substantially circular shape in a plan view were arranged in an array.
Unsealed portions where Ni was not formed in the through-holes were seen in a pattern in which a plurality of doughnut-shaped pattern units in a plan view were arranged in an array.
The diameter of the sealing part was 2.8 μm. This diameter corresponds to the diameter of the particle fixing portion 32A shown in FIG. 2E. The pitch of the sealing portion corresponds to the diameter of the polystyrene (PS) particles used and was 5 μm.
As shown in FIGS. 1A and 1B, it was confirmed that Ni was selectively formed inside some of the plurality of through holes of the pore structure.

(Example 2)
An anisotropic conductive film was obtained in the same manner as in Example 1 except that an aqueous dispersion of spherical polystyrene (PS) particles having a diameter of 8 μm was used instead of spherical polystyrene (PS) particles having a diameter of 5 μm.
The SEM surface observation of the obtained anisotropic conductor film was implemented.
As in Example 1, the sealed portion in which Ni was formed inside the through hole was seen as a pattern in which a plurality of pattern units in which a plurality of through holes were arranged in a substantially circular shape in plan view were arranged in an array.
Similar to Example 1, unsealed portions where Ni was not formed inside the through-holes were seen in a pattern in which a plurality of substantially donut-shaped pattern units in a plan view were arranged in an array.
The diameter of the sealing part was 4.5 μm. This diameter corresponds to the diameter of the particle fixing portion 32A shown in FIG. 2E. The pitch of the sealing portions was 8 μm, corresponding to the diameter of the polystyrene (PS) particles used.

Example 3
An anisotropic conductor film was obtained in the same manner as in Example 1 except that Ag was electrolytically plated on the pore structure instead of Ni.
The Ag plating conditions were as follows.
Electrolytic bath: Mixed solution of 0.4M silver methanesulfonate, 0.5M methanesulfonic acid, and 1.5M potassium hydroxide Bath temperature: 22-27 ° C
-PH: 7.5-8.5
Current density: 0.5 mA / cm ²
-Processing time: 120 minutes SEM surface observation of the obtained anisotropic conductor film was implemented.
As in Example 1, the sealing part in which Ag was formed inside the through hole was seen in a pattern in which a plurality of pattern units in which a plurality of through holes were arranged in a substantially circular shape in plan view were arranged in an array.
Similar to Example 1, unsealed holes in which Ag was not formed in the through holes were seen as a pattern in which a plurality of substantially donut-shaped pattern units in a plan view were arranged in an array.
The diameter of the sealing part was 2.8 μm. This diameter corresponds to the diameter of the particle fixing portion 32A shown in FIG. 2E. The pitch of the sealing portion corresponds to the diameter of the polystyrene (PS) particles used and was 5 μm.

Example 4
An anisotropic conductive film was obtained in the same manner as in Example 1 except that an aqueous dispersion of spherical Al ₂ O ₃ particles having a diameter of 20 nm was used instead of the spherical SiO ₂ particles having a diameter of 20 nm.
The SEM surface observation of the obtained anisotropic conductor film was implemented.
As in Example 1, the sealed portion in which Ni was formed inside the through hole was seen as a pattern in which a plurality of pattern units in which a plurality of through holes were arranged in a substantially circular shape in plan view were arranged in an array.
Similar to Example 1, unsealed portions where Ni was not formed inside the through-holes were seen in a pattern in which a plurality of substantially donut-shaped pattern units in a plan view were arranged in an array.
The diameter of the sealing part was 2.8 μm. This diameter corresponds to the diameter of the particle fixing portion 32A shown in FIG. 2E. The pitch of the sealing portion corresponds to the diameter of the polystyrene (PS) particles used and was 5 μm.

(Comparative Example 1)
After obtaining a pore structure having a plurality of through holes, an anisotropic conductor film was produced in the same manner as in Example 1 except that a gold film was formed on one surface and electrolytic plating was performed.
When SEM observation of the pore structure after electrolytic plating was performed, it was confirmed that Ni was formed inside all the through holes of the pore structure.

(Comparative Example 2)
An anisotropic conductor film was obtained in the same manner as in Comparative Example 1 except that Ag was electrolytically plated on the pore structure instead of Ni.
When SEM observation of the pore structure after electrolytic plating was performed, it was confirmed that Ag was formed inside all the through holes of the pore structure.

(Measurement of IV characteristics and electric field concentration factor β in vacuum)
With respect to the anisotropic conductive films obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the IV characteristics and the electric field concentration factor β in vacuum were measured.
The obtained anisotropic conductor film was bonded to the glass substrate with the ITO film by soldering using indium to obtain a cathode substrate.
A glass substrate with an ITO film was prepared as an anode substrate.
An alumina plate was disposed as a spacer between the cathode substrate and the anode substrate.
The distance between the anisotropic conductive film and the anode substrate was 0.5 mm.
The obtained sample was installed in a vacuum chamber, and the degree of vacuum was 1 × 10 ⁻⁴ Pa or less. A voltage was applied between the cathode electrode and the anode electrode using a DC power source (“HJPM-5N1.2-SP” manufactured by Matsusada Precision Co., Ltd.).
The current density discharged into the vacuum is expressed by the following Fowler-Nordheim equation.
I = sAF ² / φexp (−B ^3/2 / F),
F = βV
In the above formula, I is a field emission current, s is a field emission area, A is a constant, F is an electric field strength, φ is a work function, B is a constant, β is an electric field concentration factor, and V is an applied voltage.
The electric field concentration coefficient β is a coefficient for converting the applied voltage V into electric field strength F (V / cm) according to the shape of the tip portion or the geometric shape of the element.
About each anisotropic conductor film, the IV characteristic in a vacuum was analyzed with the said Fowler-Nordheim (Fowler-Nordheim) type | formula, and the electric field concentration factor (beta) was measured.
Table 1 shows the main production conditions and evaluation results for each example.
In Examples 1 to 4, higher characteristics than those of Comparative Examples 1 and 2 were obtained.

(Manufacture of FEL)
FEL was manufactured using the anisotropic conductor film obtained in Example 1.
The obtained anisotropic conductor film was bonded to the glass substrate with the ITO film by soldering using indium to obtain a cathode substrate.
A glass substrate with an ITO film coated with a ZnO: Zn phosphor layer was prepared as an anode substrate.
An alumina plate was disposed as a spacer between the cathode substrate and the anode substrate.
The distance between the anisotropic conductive film and the anode substrate was 0.5 mm.
The obtained device was installed in a vacuum chamber, and the degree of vacuum was 1 × 10 ⁻⁴ Pa or less. A voltage was applied between the cathode electrode and the anode electrode using a DC power source (“HJPM-5N1.2-SP” manufactured by Matsusada Precision Co., Ltd.).
Visual observation confirmed blue-green light emission.
It was 5000 cd / m < ² > when the light-emitting luminance of the obtained device was measured using the luminance meter ("BM-9" by Topcon).

  The anisotropic conductive film and the manufacturing method thereof of the present invention can be preferably applied to an electron-emitting device used for FE devices such as FEL and FED.

DESCRIPTION OF SYMBOLS 1 Anisotropic conductor film 21 Pore structure 21S One surface 21T The other surface 21A Non-through-hole 21B Barrier layer 21H Through-hole 21D Opening 22 Conductor (emitter, electron source)
22X, 22Y Pattern unit 30 Particle layer 31 Inorganic particle layer 31P Inorganic particle 32 Resin particle layer 32P Resin particle 32A Adhering portion 33 Cavity portion 33 Opening portion 40 Electrode layer (cathode layer)
41 1st conductor film 42 2nd conductor film 3 FEL
4 FED
100 Cathode substrate 200 Anode substrate 220 Anode layer 230, 230R, 230G, 230B Phosphor layer M Metal object to be anodized

Claims (12)

A pore structure composed of an anodized metal film having a plurality of through-holes extending in a direction crossing the plane direction;
An anisotropic conductive film comprising a conductor selectively formed inside some of the plurality of through holes,
further,
An inorganic particle layer formed on one surface of the pore structure;
A plurality of particulate cavities formed in the inorganic particle layer in contact with the one surface of the pore structure, and having a diameter larger than the through-holes;
A conductor film made of a material capable of plating the conductor, formed in contact with the one surface of the pore structure in the cavity,
An anisotropic conductor film, wherein the conductor is selectively formed in a through hole in contact with the conductor film among the plurality of through holes. The part of the through-hole in which the conductor is formed is
The anisotropic conductor film according to claim 1, wherein the anisotropic conductive film has a pattern in which a plurality of pattern units in which a plurality of the through holes are arranged in a substantially circular shape in plan view are arranged in an array. The conductor includes a metal or a metal compound including at least one metal element selected from the group consisting of Ag, Au, Cd, Co, Cu, Fe, Mo, Ni, Sn, W, and Zn.
The anisotropic conductor film according to claim 1. A pore structure composed of an anodized metal film having a plurality of through-holes extending in a direction crossing the plane direction;
A method of manufacturing an anisotropic conductor film comprising a conductor selectively formed inside some of the plurality of through holes,
Preparing the pore structure (A);
One surface of the pore structure includes a plurality of inorganic particles and a plurality of resin particles having a diameter larger than the through-holes and the inorganic particles, and at least some of the resin particles are the pore structure. Forming a particle layer in contact with the one surface of (B),
Fixing the bottom of the resin particles in contact with the fine pore structure to the fine pore structure and sealing a part of the openings of the through holes (C);
Removing the plurality of resin particles to form a plurality of particulate cavities in the particle layer (D);
Forming a conductor film in contact with the one surface of the pore structure in the cavity (E);
A method for producing an anisotropic conductor film, comprising sequentially supplying a current to the conductor film and performing electrolytic plating on the pore structure. Step (A)
A step (AX) of obtaining an anodized metal film having a plurality of non-through holes and a barrier layer by anodizing at least a part of the anodized metal body;
When there is a remainder of the metal to be anodized after the step (AX), the remainder and the barrier layer are removed. When there is no remainder of the metal to be anodized after the step (AX), the barrier layer is removed. The manufacturing method of the anisotropic conductor film of Claim 4 including the process (AY) which removes and makes the said non-through-hole into the said through-hole.   The method for producing an anisotropic conductor film according to claim 4 or 5, wherein, in the step (B), substantially spherical inorganic particles are used as the inorganic particles, and substantially spherical resin particles are used as the resin particles. In the step (B), at least one kind of particles selected from the group consisting of SiO ₂ particles, Al ₂ O ₃ particles, TiO ₂ particles, and ZnO particles is used as the plurality of inorganic particles. The manufacturing method of the anisotropic electrically conductive film in any one of.   In the step (B), at least one kind of particle selected from the group consisting of polystyrene particles, poly (meth) acrylic particles, and polylactic acid particles is used as the plurality of resin particles. The manufacturing method of the anisotropic electrically conductive film as described in any one of.   A device comprising the anisotropic conductive film according to claim 1. It comprises the anisotropic conductor film according to any one of claims 1 to 3,
An electron-emitting device comprising: an electrode layer including the conductor film; and an electron source made of the conductor formed in the through hole. A first electrode substrate comprising the electron-emitting device according to claim 10;
A field emission lamp comprising a second electrode substrate disposed opposite to the first electrode substrate via a vacuum space and including an electrode layer and a phosphor layer. A first electrode substrate comprising the electron-emitting device according to claim 10;
A second electrode substrate disposed opposite to the first electrode substrate via a vacuum space and including an electrode layer and a phosphor layer;
A field emission display that performs display by modulating light emitted from the phosphor layer.

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