WO2015079706A1

WO2015079706A1 - Anisotropic conductive film, method for producing same, device, electron emission element, field emission lamp, and field emission display

Info

Publication number: WO2015079706A1
Application number: PCT/JP2014/005965
Authority: WO
Inventors: 能久乾; 祥平小林; 聖也木町
Original assignee: 株式会社クラレ
Priority date: 2013-11-29
Filing date: 2014-11-28
Publication date: 2015-06-04
Also published as: TW201528309A

Abstract

The objective of the present invention is to provide an anisotropic conductive film that can have improved durability when used in an FE device or the like. The anisotropic conductive film (1) is provided with: a fine pore structure (21) comprising a positive electrode metal oxide film having a plurality of through holes (21H) extending in a direction intersecting the plane direction; and a conductor (22) that is selectively formed within a subset of the plurality of through holes (21H). In the anisotropic conductive film (1), at least a subset of the non-sealed areas (NSAs) at which the conductor (22) has not been formed within the through holes (21H) has been eliminated.

Description

Anisotropic conductor film and manufacturing method thereof, device, electron-emitting device, field emission lamp, and field emission display

The present invention relates to an anisotropic conductor film, a manufacturing method thereof, 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 after 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 Japanese Patent Application No. 2013-162364 (unpublished at the time of filing this application) Japanese Patent No. 4681939

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 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 (alumina) manufactured 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 portion where the depression is formed and the portion where the depression is not formed, the non-through hole of the portion where the depression is not formed is selectively used as a through hole, and a needle-like conductor is selectively formed in the inside. be able to.
In this document, after forming the acicular conductor, the anodized metal film (alumina) is removed in a sodium hydroxide solution, and the portion from which the anodized metal film (alumina) has been removed is again formed using a polymer resin. The microelectrode array is manufactured by filling.

However, the method described in Patent Document 3 has a complicated 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 this method, unlike the anisotropic conductive film of the present invention, the anodized metal film (alumina) is completely removed. Therefore, no through hole and no anodized portion around it are left.

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. A method of manufacturing an anisotropic conductive film is described in which the diameter of the conductive film is increased and the conductive material is selectively formed in the expanded through hole (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.

In the patent document 5 (unpublished at the time of the present application) which is the previous application, the present inventors,
A pore structure composed of an anodized metal film having a plurality of through-holes extending in a direction intersecting with the surface direction, and a conductive material selectively formed inside some of the plurality of through-holes With body,
further,
One surface of the pore structure covers the opening of the through-hole in which the conductor is formed, and can be plated with the material of the conductor; An anisotropy comprising a second conductor film that covers the opening of the through hole where no body is formed, is connected to the first conductor film, and is difficult to plate the material of the conductor A conductor film is disclosed (claim 1).
This anisotropic conductor film can be manufactured without using a resist without requiring complicated process control.
When this anisotropic conductive film is used in a device such as an FE device, 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 anisotropic conductor film disclosed in Patent Document 5, the openings of the through-holes of the unsealed portion are closed by foreign matter such as polishing dust or adsorbed water generated in the manufacturing process, and FE It has been found that when a device or the like is configured, the inside of the through hole in the unsealed portion may not be decompressed well.
If an FE device or the like is operated while the inside of the through hole in the unsealed part is not properly decompressed, the gas remaining in the through hole in the unsealed part is brought into the vacuum space due to heat generated during electron emission or ion collision. Released. The gas released into the vacuum space is ionized, and the generated ions may give a plasma impact to the anisotropic conductive film, and the anisotropic conductive film may be damaged by abnormal discharge. This leads to a decrease in durability of the FE device or the like.

Further, in the FE device, it is preferable that the surface emission unevenness is small. For this purpose, it is preferable that the length uniformity of the plurality of emitters constituting the FE device is high.
In the conventional DC plating method, variation in the growth rate of needle-shaped conductors formed in a plurality of through-holes due to uneven diffusion rates of metal ions results in variation in the length of the needle-shaped conductors in the plurality of through-holes. Occurs.
For example, Non-Patent Document 2 includes a SEM cross-sectional photograph of an anisotropic conductive film in which Ni is formed in a plurality of through holes of an anodized alumina film by a direct current plating method (FIG. 6).
In the SEM cross-sectional photograph of Non-Patent Document 2, there is a variation in the length of the needle-like conductor formed in the plurality of through holes.
Therefore, conventionally, a process for making the lengths of the needle-shaped conductors formed in the plurality of through holes uniform by electrolytic polishing after electrolytic plating is generally performed (claim 2 of Patent Document 6). Considering the production efficiency and the production cost, it is preferable that a needle-like conductor having a uniform length can be formed in the plurality of through holes without performing a process such as surface polishing.
In the FE device, it is also preferable that the durability of the emitter is high. For this purpose, the emitter preferably has good crystallinity, high chemical stability, and a high melting point.

The above problems are the same when a conductor is formed by electrolytic plating in a plurality of through-holes of a pore structure made of an anodized film regardless of the application.

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 conductor film that can improve durability when used in an FE device or the like, and a method for manufacturing the same.

The present invention also provides
A pore structure composed of an anodized metal film having a plurality of through holes, and a conductor formed inside at least some of the plurality of through holes,
The conductors in the plurality of through holes have good crystallinity, high chemical stability, high melting point, and uniform length.
An object of the present invention is to provide an anisotropic conductive film that can be manufactured with fewer manufacturing steps than before and a manufacturing method thereof.

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 conductor film comprising a conductor selectively formed inside some of the plurality of through holes,
At least a part of the unsealed hole portion where the conductor is not formed inside the through hole is removed.

In the anisotropic conductor film of the present invention, it is preferable that the conductor formed inside the through hole contains an induced eutectoid alloy.

The method for producing an anisotropic conductive film of the present invention comprises:
A method for producing the anisotropic conductive film of the present invention as described above,
Preparing the pore structure (A);
A step (B) of forming the conductor in a part of the through holes among the plurality of through holes;
And a step (C) of removing at least a part of the unsealed portion.

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

The electron-emitting device of the present invention is
Comprising the above anisotropic conductive film of the present invention,
An electron source made of the conductor formed in the through hole;
And an electrode layer formed on one surface of the pore structure and conducted to the electron source.

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 conductor film capable of improving durability when used in an FE device or the like and a method for producing the same can be provided.

In the anisotropic conductor film of the present invention, the conductor formed inside the through hole preferably contains an induced eutectoid alloy.
According to this aspect,
A pore structure composed of an anodized metal film having a plurality of through holes, and a conductor formed inside at least some of the plurality of through holes,
The conductors in the plurality of through holes have good crystallinity, high chemical stability, high melting point, and uniform length.
An anisotropic conductor film that can be manufactured with fewer manufacturing steps than before 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. 1B is a schematic plan view of the anisotropic conductive film of FIG. 1A. FIG. 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 which shows the example of a design change of the anisotropic conductor film of FIG. 1A. It is a schematic cross section which shows the example of a design change 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. In Example 1, it is the SEM surface photograph before the melt | dissolution process of the unsealed hole part of an anisotropic conductor film. In Example 1, it is the SEM perspective photograph and SEM cross-sectional photograph after the melt | dissolution process of the unsealed part of an anisotropic conductor film. In Example 2, it is the SEM perspective photograph and SEM cross-sectional photograph after the melt | dissolution process of the unsealed part of an anisotropic conductor film. In Example 6, it is a SEM surface photograph before the melt | dissolution process of the unsealed hole part of an anisotropic conductor film. In Example 7, it is a SEM surface photograph before the melt | dissolution process of the unsealed hole part of an anisotropic conductor film. 2 is a light emission photograph of FEL using the anisotropic conductive film obtained in Example 1. It is explanatory drawing explaining the electroplating method in a manufacturing method in case a conductor contains a eutectoid type alloy. It is explanatory drawing explaining the conventionally well-known electrolytic plating method. 4 is a SEM cross-sectional photograph in the middle of electrolytic plating in Reference Example 1. 6 is a SEM surface photograph of an anisotropic conductive film obtained in Example 8. 3 is an XRD pattern of an anisotropic conductive film obtained in Reference Example 1. FIG. 3 is an XRD pattern of an anisotropic conductive film obtained in Comparative Example 1. FIG.

"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 schematic plan view of the anisotropic conductive film of the present embodiment, and is a view showing a planar pattern of the through holes 21H and the conductors 22.

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 emitter (electron source) and an electrode layer, 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.

In the figure, reference numeral 21S denotes one surface (the lower surface in the drawing) of the pore structure 21, and reference numeral 21D denotes an opening of the through hole 21H in the surface 21S.

In the anisotropic conductor film 1, a portion where the conductor 22 is formed inside the through hole 21H is referred to as a “sealing portion SA”. Further, a portion where the conductor 22 is not formed inside the through hole 21H is referred to as an “unsealed hole portion NSA”.

The number of through holes 21H included in one sealing part SA may be singular or plural.
In the present embodiment, one sealing portion SA includes a plurality of adjacent through holes 21H, an anodized portion around each through hole 21H, and a conductor 22 formed inside each through hole 21H. Is included.
The anisotropic conductor film 1 of this embodiment has at least one sealing part SA.
In the illustrated example, the anisotropic conductive film 1 has a plurality of sealing portions SA, and one sealing portion SA includes a through hole 21H in which conductors 22 are formed inside 2 × 2. ing.
One sealing portion SA corresponds to a pattern unit 31P of the first conductor film 31 to be described later shown in FIG. 1B.

In the anisotropic conductor film 1 of the present embodiment, at least a part of the unsealed portion NSA where the conductor 22 is not formed in the through hole 21H is removed.
The unsealed hole portion NSA is at least partially removed in the thickness direction from the opening side of the through hole 21H.
In the present embodiment, a part of the unsealed hole NSA is removed in the thickness direction from the opening side of the through hole 21H, and at least one conductor 22 is not formed in the unsealed hole NSA. An unsealed through hole 21H and an anodized portion around each through hole 21H are included.
Like the anisotropic conductive film 2 shown in FIG. 2H, all of the unsealed portion NSA in which the conductor 22 is not formed inside the through hole 21H may be removed.

When removing at least a part of the unsealed portion NSA, as shown in FIGS. 1 and 2H, the anodized portion of the sealed portion SA is partially removed, and the top of the conductor 22 is thinned. It may protrude from the hole structure 21. Further, the protruding top portions of the plurality of conductors 22 constituting one sealing portion SA may be in close contact with each other (see the SEM photograph of Example 2 in FIG. 7).

A conductor film 30 composed of a first conductor film 31 and a second conductor film 32 is formed on one surface 21 S of the pore structure 21.
On the surface 21S of the pore structure 21, a first conductor film 31 that covers the opening 21D of the through hole 21H in which the conductor 22 is formed and can be plated with the material of the conductor 22, and the inside A second conductor film 32 is formed which covers the opening 21D of the through hole 21H where the conductor 22 is not formed, is connected to the first conductor film 31, and is difficult to plate the material of the conductor 22. Has been.

In the present embodiment, the first conductor film 31 covers the opening 21D of the through hole 21H in which the conductor 22 is formed, and the opening 21D of the through hole 21H in which the conductor 22 is not formed. In a pattern that does not cover the film, it is divided into a plurality of regions. The second conductor film 32 covers the opening 21D of the through hole 21H in which the conductor 22 is not formed, and is a pattern unit of the first conductor film 31 formed in a plurality of regions. It is formed to connect each other. In the present embodiment, the second conductor film 32 is a solid film having no pattern.

In the present embodiment, the first conductor film 31 and the second conductor film 32 are formed so as to be connected to each other in order to integrally form the electrode layer. As a result, a plurality of pattern units of the first conductor film 31 that are spaced apart from each other can be conducted through the second conductor film 32.

In the example shown in FIGS. 1A and 1B, the pattern unit 31 P of the first conductor film 31 has a substantially rectangular pattern including 2 × 2 through holes 21 H in which conductors 22 are formed. It is. Between the pattern units 31P of the first conductor films 31 adjacent to each other in plan view, there are 2 × 2 through holes 21H in which the conductor 22 is not formed. As described above, the second conductor film 32 is formed immediately below the through hole 21H in which the conductor 22 is not formed.
Note that the pattern design is merely an example, and it is possible to freely design which of the plurality of through holes 21H the conductor 22 is formed in. In the present embodiment, by changing the pattern of the first conductor film 31, the through hole 21H in which the conductor 22 is formed can be freely selected.

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 single metal or an alloy.
Examples of the metal compound include metal oxides.

The conductor 22 formed inside the through hole 21H is made of a material that can be electroplated and preferably contains an induced eutectoid alloy.
Induced eutectoid alloy is
At least one first metal element that can be plated in the through-hole 21H alone;
Although it has a melting point higher than that of the first metal element and cannot be plated in the through hole 21H alone, it contains the first metal element and at least one second metal element capable of inducing eutectoid.
The first metal element is at least one selected from the group consisting of Fe, Ni, and Co, and the second metal element is at least one selected from the group consisting of Mo, W, and B Preferably there is.

The first conductor film 31 is made of a material capable of plating the material of the conductor 22.
The first conductor film 31 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 single metal or an alloy.
Examples of the metal compound include metal oxides.

The second conductor film 32 is made of a material that is difficult to plate the material of the conductor 22 (a difficult plating material). Examples of the difficult plating material include a metal or a metal compound in which a highly insulating oxide film is easily generated on the surface.
The second conductor film 32 preferably contains a metal or metal compound containing at least one metal element selected from the group consisting of Al, Mg, Si, Ti, Mo, and W, or stainless steel.
Among these, a metal or a metal compound containing Al is particularly preferable from the viewpoint of easy production and low cost.
The metal may be a single metal or an alloy.
Examples of the metal compound include metal oxides.
Examples of stainless steel include Fe—Ni—Cr alloy.

The anisotropic conductive films 1 and 2 of the present embodiment can be used as electron-emitting devices used in FE devices and the like. In this case, the conductor 22 formed inside the through hole 21H is an emitter (electron source), and the conductor film 30 composed of the first conductor film 31 and the second conductor film 32 is an electrode layer. Each can be used.

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. However, the filling rate of the conductor 22 is not 100%. Also good.
However, since the electron emission performance is enhanced, 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 filling rate of the conductor 22 in each through hole 21H 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.

In the present embodiment, the conductor 22 formed inside the plurality of through holes 21H formed immediately above one pattern unit 31P of the first conductor film 31 constitutes one sealing part SA. ing. In plan view, the plurality of sealing portions SA are separated from each other via a plurality of through holes 21H (unsealed portions NSA) in which the conductor 22 is not formed.
In the present embodiment, the plurality of sealing portions SA are separated from each other, and the control of the intervals is easy.
When the anisotropic conductive film 1 of this embodiment is used for an FE device or the like, the emitter gap can be controlled over a wide range. For example, the emitter gap (in this embodiment, the gap between the sealing portions SA adjacent to each other) can be controlled in the range of about 100 nm to several tens of μm. 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 an FE device or the like, heat is generated in the conductor 22 which is an emitter that emits electrons.
In the present embodiment, the individual conductors 22 are surrounded and protected by the anodized portion, so that it is considered that damage due to heat due to electron emission is suppressed.
In the present embodiment, one sealing portion SA includes a plurality of through holes 21H adjacent to each other, an anodized portion around each through hole 21H, and a conductor 22 formed inside each through hole 21H. It is included.
When attention is paid to the plurality of conductors 22 constituting one sealing part SA, it is considered that electrons are emitted from a part of the conductors 22 constituting one sealing part SA at a certain timing. . Heat is generated in the conductor 22 that emits electrons at a certain timing, but the adjacent conductors 22 are connected via the anodized portion, so that the generated heat is generated by the anodized portion and the same sealing hole. It is considered that the portion SA is formed and diffuses to other conductors 22 that do not emit electrons at that timing.
That is, in the anisotropic conductor films 1 and 2 of this embodiment, even if heat is generated by electron emission, the generated heat is easily diffused, and damage to the conductor 22 that has emitted electrons is suppressed. it is conceivable that.

As described in the section “Problems to be Solved by the Invention”, in an anisotropic conductive film having a sealed portion and an unsealed portion, an opening portion of a through hole in the unsealed portion is manufactured. When the FE device or the like is closed by foreign matter such as polishing dust or adsorbed water generated in the process, the inside of the through hole of the unsealed part may not be decompressed well. If the FE device or the like is operated without the pressure inside the through hole in the unsealed part being reduced well, the gas remaining in the through hole in the unsealed part is brought into the vacuum space due to heat generated during electron emission, ion collision, etc. Released. The gas released into the vacuum space is ionized, and the generated ions may give a plasma impact to the anisotropic conductive film, and the anisotropic conductive film may be damaged by abnormal discharge.
In the anisotropic conductor films 1 and 2 of this embodiment, since at least a part of the unsealed portion NSA is removed, the foreign matter that closes the opening of the through hole 21H of the unsealed portion NSA in the manufacturing process. Even if this occurs, the foreign matter is completely removed. Therefore, when the FE device or the like is constituted by the anisotropic conductor films 1 and 2, damage to the anisotropic conductor films 1 and 2 due to abnormal discharge is suppressed.
When completely removing the unsealed part NSA, the pressure reduction in the through hole 21H of the unsealed part NSA becomes unnecessary in the FE device or the like. Even when the unsealed part NSA is partially left, the length of the through hole 21H of the unsealed part NSA is shortened, so that the inside of the through hole 21H of the unsealed part NSA is easily decompressed in the FE device or the like. .
Combined with the above effects, in the anisotropic conductor films 1 and 2 of the present embodiment, the removal process of the unsealed portion NSA (in this specification, unless otherwise specified, As compared with a case where partial removal processing is not performed), durability when an FE device or the like is configured can be improved.

When the conductor 22 includes an induced eutectoid alloy, as described in detail in the manufacturing method described later, the conductive material in the plurality of through holes 21H can be formed without performing surface polishing or the like after the formation of the conductor 22. The length (filling rate) of the body 22 can be made uniform.
Since the lengths (filling ratios) of the conductors 22 in the plurality of through holes 21H are uniform, when the anisotropic conductor films 1 and 2 of this embodiment are used in an FE device, surface emission unevenness is suppressed. can do.
The conductor 22 using the induced eutectoid alloy has a crystallinity equivalent to that of Ni or the like generally used for conventional electrolytic plating. The conductor 22 using the induced eutectoid alloy also contains a second metal element having a high chemical stability and a high melting point as compared with Ni or the like generally used for conventional electrolytic plating. Since the conductor 22 including an induced eutectoid alloy has good crystallinity, high chemical stability, and a high melting point, when the anisotropic conductor films 1 and 2 of this embodiment are used for an FE device, The material stability of the emitter (electron source) is high and the durability is excellent.

`` Design change example ''
FIG. 3 is a schematic cross-sectional view showing a design change example of the anisotropic conductive film. The same components as those of the anisotropic conductive films 1 and 2 of the above embodiment are denoted by the same reference numerals.
In the anisotropic conductor film 3 shown in FIG. 3, the second conductor film 32 covers the opening 21D of the through hole 21H in which the conductor 22 is not formed, and the conductor 22 is formed inside. The opening 21 D of the through-hole 21 H is formed in a pattern that does not cover the plurality of regions. The first conductor film 31 covers the opening portion 21D of the through hole 21H in which the conductor 22 is formed, and the pattern units of the second conductor film 32 formed separately in a plurality of regions. It is formed to connect. In this example, the first conductor film 31 is a solid film having no pattern.

Also in this design modification example, the first conductor film 31 and the second conductor film 32 are formed so as to be connected to each other in order to integrally form the electrode layer. Thereby, a plurality of pattern units of the second conductor film 32 formed to be separated from each other can be conducted through the first conductor film 31.

Also in the design change example shown in FIG. 3, it is possible to freely design which of the plurality of through holes 21H the conductor 22 is formed in. In this design change example, by changing the pattern of the second conductor film 32, the through hole 21H in which the conductor 22 is formed can be freely selected.
In the anisotropic conductor film 3, the conductor 22 formed inside the plurality of through holes 21H formed immediately above one pattern unit of the second conductor film 32 is one sealed portion. Configure the SA. Also in the anisotropic conductor film 3, the plurality of sealing portions SA are separated from each other through a plurality of through holes 21H (unsealed portions NSA) in which the conductor 22 is not formed.
Also in this design change example, the plurality of sealing portions SA are separated from each other, and the interval can be easily controlled.
Also in the anisotropic conductor film 3, at least a part of the unsealed portion NSA is removed.
Also in the anisotropic conductor film 3, the same effect as the anisotropic conductor films 1 and 2 is acquired.

"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))
A pore structure 21 having a plurality of through holes 21H is prepared as follows.

<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 21 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 M to be anodized can be removed, for example, by reverse electrolytic stripping in which a voltage is applied in the reverse direction 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, a pore structure 21 having a plurality of through holes 21H shown in FIG. 2C is obtained.

(Process (B))
In the following manner, the conductor 22 is formed inside some of the through holes 21H among the plurality of through holes 21H, and the sealing portion SA is formed.

<Process (BX)>
A conductor film 30 composed of a first conductor film 31 and a second conductor film 32 is formed on one surface (lower surface in the drawing) 21S of the pore structure 21 obtained in the step (A).
In this step, the surface 21S of the pore structure 21 covers the opening 21D of the through hole 21H in which the conductor 22 is formed, and the first conductor film 31 capable of plating the material of the conductor 22 The second conductor film 32 that covers the opening 21D of the through hole 21H that does not form the conductor 22 therein, is connected to the first conductor film 31, and is difficult to plate the material of the conductor 22. Can be formed.
In the pore structure 21, the surface on which the conductor film 30 is formed may be the side where the non-through hole 21A is provided or the side where the barrier layer 21B is provided.

As shown in FIGS. 2D and 2E, the second conductor film 32 can be formed after the first conductor film 31 is formed. In this case, the first conductor film 31 covers the opening 21D of the through hole 21H in which the conductor 22 is formed, and does not cover the opening 21D of the through hole 21H in which the conductor 22 is not formed. Thus, it can be divided into a plurality of regions. For example, the first conductor film 31 can be patterned by metal deposition using a mask such as a metal mesh. The second conductor film 32 covers the opening 21D of the through-hole 21H in which the conductor 22 is not formed, and the pattern units of the first conductor film 31 formed in a plurality of regions are separated from each other. It can be formed to connect. In the illustrated example, the second conductor film 32 is a solid film having no pattern.

Contrary to the above process, the first conductor film 31 may be formed after the second conductor film 32 is formed. In this case, as shown in FIG. 3, the second conductor film 32 covers the opening 21 D of the through hole 21 H in which the conductor 22 is not formed, and the through hole 21 H that forms the conductor 22 in the inside. A pattern that does not cover the opening 21 D can be formed in a plurality of regions. The first conductor film 31 covers the opening 21D of the through hole 21H in which the conductor 22 is formed, and the pattern units of the second conductor film 32 formed separately in a plurality of regions Can be formed to connect.

<Process (BY)>
Next, as shown in FIG. 2F, electrolytic plating is performed on the pore structure 21 using the conductive film 30 formed of the first conductive film 31 and the second conductive film 32 as an electrode layer. Thereby, the conductor 22 can be selectively formed inside the through hole 21H in which the first conductor film 31 is formed immediately below, and the sealing portion SA can be formed.

In the step (BY), plating containing a metal or 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 Electrolytic plating can be performed using a liquid by a conventionally known electrolytic plating method.

In the step (BY), at least one first metal element that can be plated in the through-hole 21H alone and a melting point higher than that of the first metal element, and cannot be plated in the through-hole 21H by itself. However, it is preferable to perform electrolytic plating by a direct current plating method using a plating solution containing the first metal element and at least one second metal element capable of inducing eutectoid.
Hereinafter, this method is referred to as “induced eutectoid alloy plating method”.
In this method, the conductor 22 containing an induced eutectoid alloy is formed.

The difference between the induced eutectoid alloy plating method and the conventionally known DC plating method will be described with reference to FIGS. 11A and 11B.
The left figure of FIG. 11A is a schematic cross-sectional view showing a state in which electroplating is being performed by the induced eutectoid alloy plating method.
FIG. 11B is a schematic cross-sectional view showing a state in which electrolytic plating is being performed by a conventionally known DC plating method.

Conventionally, for electrolytic plating on a plurality of through-holes of a pore structure, a plating solution containing an inexpensive metal such as Ni is generally used.
FIG. 11B illustrates the case where Ni is used as an example.
The plating efficiency of Ni is as high as about 80%. Here, “plating efficiency” is a parameter determined from the amount of precipitation (mole) relative to the amount of electricity.
In the DC plating method, the plating rate into the through hole is influenced by the diffusion rate of metal ions.
As shown in FIG. 11B, in the conventional DC plating method, variation in the growth rate of the conductor 22 formed in the plurality of through holes 21H occurs due to uneven diffusion rate of metal ions, and the conductivity in the plurality of through holes 21H. In general, the length of the body 22 varies.
Therefore, in the conventional manufacturing method, generally, the lengths of the conductors 22 in the plurality of through holes 21H are made uniform by surface polishing or the like after electrolytic plating.

In the induced eutectoid alloy plating method, as described above, at least one first metal element that can be plated in the through-hole 21H alone and a melting point higher than that of the first metal element, the through-hole by itself. Electrolytic plating is carried out by a direct current plating method using a plating solution containing at least one second metal element that is incapable of plating within 21H but can be induced and co-deposited.
It is considered that a metal complex ion in which a ligand containing the second metal element is bonded around the ion of the first metal element is formed in the plating solution.
In FIG. 11A, the case where the first metal element is Ni and the second metal element is Mo is illustrated as an example. In this case, for example, as shown in the right diagram of FIG. 11A, complex ions in which a plurality of MoO ₆ ions (polymolybdate ions) are coordinated around Ni ions are formed.
Since complex ions require energy to solve their structure, a high overvoltage is required to deposit metal ions. In plating under high overvoltage, the hydrogen generation reaction preferentially proceeds, so the plating efficiency is low.
For example, in the case of Mo—Ni eutectoid, the plating efficiency is about 6%.
In the conventional electrolytic plating method, higher plating efficiency is preferred.
In the induced eutectoid alloy plating method, electrolytic plating is performed with a system having low plating efficiency. As a result, as shown in FIG. 11A, the consumption rate of metal ions (metal complex ions) can be reduced as a whole, and metal ions (metal complex ions) can be sufficiently supplied into the plurality of through holes 21H. As a result, the plating reaction in the plurality of through holes 21H proceeds at an electron supply rate-determining rate, and the growth rate of the conductor 22 in the plurality of through holes 21H can be made uniform.
Inductive eutectoid alloy plating requires a higher energy for electrolytic plating than when using a material with high plating efficiency such as Ni, but by increasing the applied voltage or increasing the plating time, A conductor 22 having a desired length can be grown.
In the electrolytic plating in the induced eutectoid alloy plating method, the conductor 22 grows in a specific direction (the direction in which the through hole 21H extends), so that the conductor 22 having good crystallinity can be grown.
The electroplating of Mo—Ni alloy on a flat plate is described in Non-Patent Documents 3 and 4 listed in the “Background Art” section, but for application to a pore structure composed of an anodized metal film. It is not known so far.

Any method other than the above may be adopted as long as the conductor 22 can be selectively formed inside the through holes 21H of the plurality of through holes 21H and the sealing portion SA can be formed. .

(Process (C))
Next, as shown in FIG. 2G or FIG. 2H, at least a part of the unsealed portion NSA is removed.
As a method for removing the non-sealed portion NSA, dissolution removal using a solution in which the anodized portion dissolves (hereinafter referred to as a solution) is preferable.
Examples of the solution include a sodium hydroxide aqueous solution or a mixed aqueous solution of phosphoric acid and chromic acid.
For example, at least a part of the unsealed hole portion NSA can be removed by immersing the structure obtained after step (B) in the solution.
In this step, the solution enters the through hole 21H of the unsealed portion NSA in which the conductor 22 is not formed, and the dissolution removal of the anodized portion of the unsealed portion NSA is performed in the depth direction from the opening side. Proceed to. For the same solution, the longer the immersion time, the deeper the unsealed part is removed.
Since the conductor 22 is formed in the through-hole 21H of the sealing portion SA and the solution does not enter, the anodized portion of the sealing portion SA can be used if the immersion time in the solution is relatively short. Is not dissolved or removed, but the amount is small even if dissolved and removed. If the immersion time in the solution is relatively long, the anodized portion of the sealing portion SA is partially removed, and the top of the conductor 22 of the sealing portion SA protrudes from the pore structure 21 There is. Further, the protruding top portions of the conductor 22 constituting one sealing portion SA may be in close contact with each other (see the SEM photograph of Example 2 in FIG. 7).
As described above, the anisotropic conductor films 1 to 3 are manufactured.

The electron emission performance is more effective as the direction in which the conductor 22 extends 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 to 3 can be manufactured without using a resist, the tip of the conductor 22 formed inside the through hole 21H is a hydrophobizing agent, a resist or a solvent used for resist pattern removal. There is no possibility that the performance as an emitter is deteriorated due to contamination or alteration.

According to the method of the present embodiment, since at least a part of the unsealed portion NSA is removed, even if a foreign matter that closes the opening of the through hole 21H of the unsealed portion NSA is generated in the manufacturing process, This foreign matter can be completely removed. Therefore, damage to the anisotropic conductor films 1 to 3 due to abnormal discharge in the FE device or the like is suppressed.
When the unsealed portion NSA is completely removed, it is not necessary to reduce the pressure in the through hole 21H of the unsealed portion NSA in an FE device or the like. Even when the unsealed part NSA is partially left, the length of the through hole 21H of the unsealed part NSA is shortened, so that the inside of the through hole 21H of the unsealed part NSA is easily decompressed in the FE device or the like. .
Combined with the above effects, according to the method of the present embodiment, the durability when an FE device or the like is configured as compared with the case where the removal process (partial removal process) of the unsealed portion NSA is not performed. Anisotropic conductor films 1 to 3 with improved resistance can be produced.

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. It is possible to provide anisotropic conductive films 1 to 3 and a method for manufacturing the same which can improve durability when used in an FE device or the like.

"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. 4A is a schematic cross-sectional view.

FEL4 is
A cathode substrate (first electrode substrate) 100 having a substrate body 110 and a cathode layer (conductor film 30);
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 (conductor film 30) 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 conductor film 30 composed of the first conductor film 31 and the second conductor film 32 in the anisotropic conductor film 1 is a cathode layer, and a part of the pore structure 21. The conductor 22 selectively formed inside the through hole 21H is an emitter (electron source).
In FIG. 4A, the structure of the anisotropic conductive film 1 is illustrated in a simplified manner, but the structure is the same as that shown in FIGS. 1A and 1B.
It should be noted that the number of through-holes 21H that are formed immediately above one pattern unit 31P of the first conductor film 31 and in which the conductor 22 is formed is larger than 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, RbVO ₃ , CsVO _{3 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 an electron beam emitted from the conductor 22 (emitter) of the cathode substrate 100, and emitted light is emitted.

In the FEL 4 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 FEL 4 of this embodiment, since at least a part of the unsealed portion NSA of the anisotropic conductor film 1 is removed, abnormal discharge in the anisotropic conductor film 1 is suppressed, and the durability is excellent. Yes.

In the present embodiment, the FEL has been described as an example. However, as illustrated in FIG. 4B, 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. 4B, reference numeral 5 denotes an FED.
In FIG. 4B, illustration of the cathode layer (conductor film 30) and the anode layer 220 is omitted.

Hereinafter, examples, reference examples, and comparative examples according to the present invention will be described.

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

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 25V
・ Time: 8 hours

The surface and cross section of the obtained alumina film were observed using a scanning electron microscope (SEM, “S-4800” manufactured by Hitachi, Ltd.). 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 resulting 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 40 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 pore structure having a plurality of through holes and having a thickness of 40 μm was obtained.

Next, with respect to one surface of the pore structure (the surface on the side where the barrier layer was present), a vacuum deposition apparatus ("VE -2030 "), a 60 nm thick gold film (Au film, first conductor film) was formed. The vapor deposition conditions were as follows.
・ Vapor deposition source: 99.9% gold wire (manufactured by Niraco)
・ Degree of vacuum: 1 × 10 ⁻⁴ Pa or less ・ Substrate temperature: 25 ° C.
-Deposition rate: 5 nm / min.

Next, an aluminum film having a thickness of 150 nm was formed on almost the entire surface of the pore structure on which gold deposition was performed using a vacuum deposition apparatus (“VE-2030” manufactured by Vacuum Device Inc.) (Al Film, second conductor film). The vapor deposition conditions were as follows.
・ Vapor deposition source: 99.99% aluminum wire (manufactured by Niraco)
・ Degree of vacuum: 1 × 10 ⁻⁴ Pa or less ・ Substrate temperature: 25 ° C.
-Deposition rate: 10 nm / min.

Next, Ni was electrolytically deposited on the pore structure using a conductor film composed of a gold film and an aluminum film as an electrode layer. The plating conditions were as follows.
Electrolysis 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 to 5.0
・ Voltage: -0.9V vs. Ag / AgCl
・ Processing time: 120 minutes

SEM surface observation and SEM cross-section observation of the pore structure after electrolytic plating were performed.
The obtained SEM surface photograph is shown in FIG.
In FIG. 5, the upper left figure is a SEM surface photograph at a magnification of 3000 times. Corresponding to the pattern of the opening part of the metal mesh used for gold vapor deposition, a pattern in which a plurality of substantially rectangular pattern units of 8 μm × 8 μm were formed in a matrix with a space of 8 μm was observed.
In FIG. 5, the right figure is a SEM photograph at a magnification of 20000 times. This photograph is an enlarged view of the portion of the substantially rectangular pattern unit. This portion is a portion where a gold film (first conductor film) is formed immediately below the through hole. It was observed that Ni was formed inside the through hole (sealed portion). In SEM cross-sectional observation, the filling rate of Ni in the through hole of the sealed portion was 70 to 100%. In addition, since the SEM surface photograph in the upper right figure is a photograph of the surface, a through hole with a Ni filling rate of less than 100% looks like a hole, but Ni is actually formed inside. .
In FIG. 5, the lower figure is a SEM surface photograph at a magnification of 20000 times. This photograph is an enlarged view of a portion of the lattice pattern excluding the plurality of substantially rectangular pattern units. This portion is a portion where an aluminum film (second conductor film) is formed immediately below the through hole. All the through holes remained as holes, and Ni formation was not observed in the through holes (unsealed portion).
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.

The obtained structure was immersed in a 0.4% by mass (0.1 mol / L) sodium hydroxide aqueous solution for 10 minutes to remove a part of the unsealed portion.
FIG. 6 shows an SEM perspective photograph and an SEM sectional photograph after the unsealed hole portion is dissolved. It was observed that the unsealed portion was removed from the opening side to a depth of about 10 μm with respect to the through-hole length of 40 μm.

(Example 2)
An anisotropic conductor film was formed in the same manner as in Example 1 except that the dissolution treatment conditions for the unsealed pores were changed to immersion in an aqueous solution of 0.4% by mass (0.1 mol / L) sodium hydroxide for 30 minutes. Obtained.
FIG. 7 shows an SEM perspective photograph and an SEM sectional photograph after the unsealed portion is dissolved.
It was observed that the unsealed hole portion was removed from the opening side to a depth of about 30 μm with respect to the through-hole length of 40 μm.
In the dissolution treatment conditions for the unsealed portion in this example, the anodized alumina in the sealed portion is partially removed, and the top of the conductor formed in the plurality of through-holes constituting one sealed portion is It protruded from the anodized alumina and was in close contact with each other, and the tip of the sealed portion became substantially conical.

Example 3
An anisotropic conductor film was obtained in the same manner as in Example 2 except that a titanium film was formed instead of the aluminum film as the second conductor film.
SEM surface observation of the pore structure after electrolytic plating was performed.
Similar to Example 1, a pattern in which a plurality of substantially rectangular pattern units were formed in a matrix corresponding to the openings of the metal mesh used for gold deposition was observed.
As in the first embodiment, the portion of the substantially rectangular pattern unit is a portion in which a gold film (first conductor film) is formed immediately below the through hole, and Ni is formed in the through hole. Was observed (sealed portion). In SEM cross-sectional observation, the filling rate of Ni in the through hole of the sealed portion was 70 to 100%.
The portion of the lattice pattern excluding the plurality of substantially rectangular pattern units is a portion where a titanium film (second conductor film) is formed immediately below the through hole, and the through hole remains a hole. Ni formation was not observed in the through hole (unsealed portion).
Similar to Example 1, it was confirmed that Ni was selectively formed inside some of the plurality of through holes of the pore structure.
When SEM observation was performed after the unsealed portion was dissolved, as in Example 2, it was observed that the unsealed portion was removed to a depth of about 30 μm from the opening side with respect to the through-hole length of 40 μm. It was done. Further, as in Example 2, the anodized alumina in the sealing part is partially removed, and the conductors formed in the plurality of through holes constituting one sealing part protrude from the anodized alumina and adhere to each other. And the mode that the front-end | tip part of a sealing part is substantially cone shape was observed.

Example 4
An anisotropic conductor film was obtained in the same manner as in Example 2 except that a conductor film composed of a gold film and an aluminum film was used as an electrode layer, and Ag was electroplated on the pore structure instead of Ni. It was. 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 to 8.5
Current density: 0.5 mA / cm ²
Treatment time: 120 minutes SEM surface observation of the pore structure after electrolytic plating was performed.
Similar to Example 1, a pattern in which a plurality of substantially rectangular pattern units were formed in a matrix corresponding to the openings of the metal mesh used for gold deposition was observed.
As in Example 1, the portion of the substantially rectangular pattern unit is a portion where a gold film (first conductor film) is formed immediately below the through hole, and Ag is formed in the through hole. Was observed (sealed portion). In SEM cross-sectional observation, the filling rate of Ag in the through hole of the sealed part was 70 to 100%.
The portion of the lattice pattern excluding the plurality of substantially rectangular pattern units is a portion in which an aluminum film (second conductor film) is formed immediately below the through hole, and the through hole remains a hole. Ni formation was not observed in the through hole (unsealed portion).
As in Example 1, it was confirmed that Ag was selectively formed inside some of the plurality of through holes of the pore structure.
When SEM observation was performed after the unsealed portion was dissolved, as in Example 2, it was observed that the unsealed portion was removed to a depth of about 30 μm from the opening side with respect to the through-hole length of 40 μm. It was done. Further, as in Example 2, the anodized alumina in the sealing part is partially removed, and the conductors formed in the plurality of through holes constituting one sealing part protrude from the anodized alumina and adhere to each other. And the mode that the front-end | tip part of a sealing part is substantially cone shape was observed.

(Example 5)
Except that a conductive film composed of a gold film and an aluminum film is used as an electrode layer, and Mo—Ni alloy (Mo: Ni (mass ratio) = 20: 80) is electrolytically plated instead of Ni on the pore structure. In the same manner as in Example 2, an anisotropic conductive film was obtained. The plating conditions for the Mo—Ni alloy were as follows.
Electrolytic bath: 0.1M sodium molybdate, 0.3M sodium gluconate, 0.2M nickel sulfate, 1.0M ammonium chloride Bath temperature: 22-27 ° C
・ PH: 8.0 to 11.0
Current density: 5.0 mA / cm ²
Treatment time: 120 minutes SEM surface observation of the pore structure after electrolytic plating was performed.
Similar to Example 1, a pattern in which a plurality of substantially rectangular pattern units were formed in a matrix corresponding to the openings of the metal mesh used for gold deposition was observed.
As in Example 1, the portion of the substantially rectangular pattern unit is a portion in which a gold film (first conductor film) is formed immediately below the through hole, and a Mo—Ni alloy is formed in the through hole. (Sealed part). In SEM cross-sectional observation, the filling rate of Mo—Ni in all the through holes in the sealed portion was 100%, and no variation in the filling rate was observed. The SEM surface photograph was the same as the SEM photograph (upper right figure of FIG. 13) of the sealing part of Example 8 described later, and it was observed that Mo—Ni reached the surface in all the through holes.
The portion of the lattice pattern excluding the plurality of substantially rectangular pattern units is a portion in which an aluminum film (second conductor film) is formed immediately below the through hole, and the through hole remains a hole. No Mo—Ni alloy was formed in the through hole (unsealed portion).
As in Example 1, it was confirmed that Mo—Ni alloy was selectively formed inside some of the plurality of through holes of the pore structure.
When SEM observation was performed after the unsealed portion was dissolved, as in Example 2, it was observed that the unsealed portion was removed to a depth of about 30 μm from the opening side with respect to the through-hole length of 40 μm. It was done. Further, as in Example 2, the anodized alumina in the sealing part is partially removed, and the conductors formed in the plurality of through holes constituting one sealing part protrude from the anodized alumina and adhere to each other. And the mode that the front-end | tip part of a sealing part is substantially cone shape was observed.

(Example 6)
An anisotropic conductor in the same manner as in Example 2 except that a metal mesh having a mesh size of 16 μm and a wire diameter of 16 μm was used as a mask used when forming a gold film (first conductor film) by vapor deposition. A membrane was obtained.

SEM surface observation of the pore structure after electrolytic plating was performed.
The obtained SEM surface photograph is shown in FIG.
Similar to Example 1, a pattern was formed in which a plurality of 16 μm × 16 μm substantially rectangular pattern units were formed in a matrix with a space of 16 μm corresponding to the openings of the metal mesh used for gold deposition.
As in the first embodiment, the portion of the substantially rectangular pattern unit is a portion in which a gold film (first conductor film) is formed immediately below the through hole, and Ni is formed in the through hole. Was observed (sealed portion). In SEM cross-sectional observation, the filling rate of Ni in the through hole of the sealed portion was 70 to 100%.
The portion of the lattice pattern excluding the plurality of substantially rectangular pattern units is a portion in which an aluminum film (second conductor film) is formed immediately below the through hole, and the through hole remains a hole. Ni formation was not observed in the through hole (unsealed portion).
Similar to Example 1, it was confirmed that Ni was selectively formed inside some of the plurality of through holes of the pore structure.
When SEM observation was performed after the unsealed portion was dissolved, as in Example 2, it was observed that the unsealed portion was removed to a depth of about 30 μm from the opening side with respect to the through-hole length of 40 μm. It was done. Further, as in Example 2, the anodized alumina in the sealing part is partially removed, and the conductors formed in the plurality of through holes constituting one sealing part protrude from the anodized alumina and adhere to each other. And the mode that the front-end | tip part of a sealing part is substantially cone shape was observed.

(Example 7)
An anisotropic conductor film as shown in FIG. 3 was produced in the same manner as in Example 2 except that the formation order of the gold film and the aluminum film was reversed.
In the same manner as in Example 1, a pore structure having a plurality of through holes was obtained.
With respect to one surface (surface on which the barrier layer was present) of the obtained pore structure, a 60 nm thick aluminum film (Al Film, second conductor film). The vapor deposition conditions were as follows.
・ Vapor deposition source: 99.99% aluminum wire (manufactured by Niraco)
・ Degree of vacuum: 1 × 10 ⁻⁴ Pa or less ・ Substrate temperature: 25 ° C.
-Deposition rate: 10 nm / min.
Next, a gold film having a thickness of 150 nm was formed on almost the entire surface of the pore structure on which aluminum was deposited using a vacuum deposition apparatus (“VE-2030” manufactured by Vacuum Device Inc.) (Au Film, first conductor film). The vapor deposition conditions were as follows.
・ Vapor deposition source: 99.99% gold wire (Niraco)
・ Degree of vacuum: 1 × 10 ⁻⁴ Pa or less ・ Substrate temperature: 25 ° C.
-Deposition rate: 5 nm / min.
Next, Ni was electrolytically deposited on the pore structure under the same conditions as in Example 1 using a conductor film composed of an aluminum film and a gold film as an electrode layer.

SEM surface observation of the pore structure after electrolytic plating was performed.
The obtained SEM surface photograph is shown in FIG.
The reverse pattern of Example 1 was seen. The portion of the substantially rectangular pattern unit (8 μm × 8 μm) is a portion in which an aluminum film (second conductor film) is formed immediately below the through hole, and the through hole remains a hole, No Ni formation was observed (unsealed portion).
The portion of the lattice pattern excluding the substantially rectangular pattern unit is a portion in which a gold film (first conductor film) is formed immediately below the through hole, and Ni is formed in the through hole. It was seen (sealed part). In SEM cross-sectional observation, the filling rate of Ni in the through hole of the sealed portion was 70 to 100%.
As shown in FIG. 3, it was confirmed that Ni was selectively formed inside some of the plurality of through holes of the pore structure.
When SEM observation was performed after the unsealed portion was dissolved, as in Example 2, it was observed that the unsealed portion was removed to a depth of about 30 μm from the opening side with respect to the through-hole length of 40 μm. It was done. Further, as in Example 2, the anodized alumina in the sealing part is partially removed, and the conductors formed in the plurality of through holes constituting one sealing part protrude from the anodized alumina and adhere to each other. And the mode that the front-end | tip part of a sealing part is substantially cone shape was observed.

(Comparative Example 1)
Forming a gold film (solid film) on the substantially entire surface without using a mask as the first conductor film on one surface (the surface on which the barrier layer was present) of the pore structure, An anisotropic conductor film was produced in the same manner as in Example 1 except that the second conductor film was not formed and the unsealed hole was not dissolved.
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 (no unsealed portion).

(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.

(Measurement of IV characteristics and electric field concentration factor β in vacuum)
With respect to the anisotropic conductive films obtained in Examples 1 to 7 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 placed in a vacuum chamber so that 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 = βE = βV / d
In the above formula, I is a field emission current, s is a field emission area, A is a constant, F is a field intensity at the tip of a conductor, φ is a work function, B is a constant, β is an electric field concentration factor, and E is a flat plate. Electric field strength, V is an applied voltage, and d is a distance between the cathode substrate and the anode substrate.
The electric field concentration coefficient β (dimensionless) is a coefficient indicating how much the electric field concentration coefficient β is increased as compared with the electric field strength of the flat plate according to the shape of the tip portion or the geometric shape of the element.
For each anisotropic conductive film, the IV characteristics in vacuum were analyzed by the Fowler-Nordheim equation, and the electric field concentration factor β was measured.
In each example, the ratio of the current value after 1 hour to the initial current value (100 μA) when the voltage application was continued for 1 hour was evaluated.
Tables 1 and 2 show the main production conditions and evaluation results for each example.
In the initial state, in Examples 1 to 7, higher characteristics were obtained than in Comparative Examples 1 and 2.
In Comparative Examples 1 and 2, the current value after voltage application for 1 hour was 10% or less of the initial value, and the durability was insufficient, whereas in Examples 1 to 7, the voltage value was applied after 1 hour voltage application. The current value was maintained at the same level as the initial stage, and the durability was significantly improved.

(Manufacture of FEL)
FELs were manufactured using the anisotropic conductor films obtained in Examples 1 to 7 and Comparative Examples 1 and 2.
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 placed in a vacuum chamber so that 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.).
In any of the FELs obtained using the anisotropic conductive films of Examples 1 to 7 and Comparative Examples 1 and 2, blue-green light emission was confirmed visually.
FIG. 10 shows a light emission photograph of the device obtained using the anisotropic conductive film of Example 1 using an optical microscope.
When the luminance of the devices obtained using the anisotropic conductive films of Examples 1 to 7 and Comparative Examples 1 and 2 was measured using a luminance meter ("BM-9" manufactured by Topcon Corporation), both of them were measured. It was 8000 cd / m ² . Here, the initial light emission luminance in each example is aligned.
The ratio of the luminance with respect to the initial value when the FEL obtained using the anisotropic conductive film of each example was allowed to emit light continuously for 1 hour was evaluated. The evaluation results are shown in Table 2.
In Comparative Examples 1 and 2, the luminance after continuous light emission for 1 hour was 10% or less of the initial value, and the durability was insufficient, whereas in Examples 1 to 7, even after continuous light emission for 1 hour. The brightness was maintained at the same level as the initial stage, and the durability was greatly improved.

(Reference Example 1)
In the same manner as in Example 1, a 50 μm-thick pore structure (anodized alumina) having a plurality of through holes was obtained.
Next, a vacuum deposition apparatus (“VE-2030” manufactured by Vacuum Device Inc.) was used on almost the entire surface with respect to one surface of the pore structure (the surface on which the barrier layer was present), and a mask was used. In addition, a 60 nm thick gold film (Au film, conductor film) was formed. The vapor deposition conditions were as follows.
・ Vapor deposition source: 99.9% gold wire (manufactured by Niraco)
・ Degree of vacuum: 1 × 10 ⁻⁴ Pa or less ・ Substrate temperature: 25 ° C.
-Deposition rate: 5 nm / min.

Next, using a gold film as an electrode layer, a Mo—Ni alloy (Mo: Ni (mass ratio) = 36: 64) was electrolytically deposited on the pore structure by a direct current method. The plating conditions were as follows.
Electrolytic bath: 0.2M nickel sulfate hexahydrate, mixed solution of 0.1M sodium molybdate and 0.3M sodium gluconate Counter electrode: Pt electrode Bath temperature: 25 ° C
-PH: adjusted to 10 using aqueous ammonia-Voltage: -1.8 V vs. Ag / AgCl
・ Processing time: 450 minutes

SEM observation of the pore structure in the middle stage of electrolytic plating was performed.
The obtained SEM cross-sectional photograph is shown in FIG.
In the figure, AAO represents a pore structure (anodized alumina), and AAO_Mo36-Ni64 (%) represents a Mo—Ni alloy (Mo: Ni) in a plurality of through holes of the pore structure (anodized alumina) AAO. (Mass ratio) = 36: 64) is shown. In the figure, solder is an alloy film containing Sn as a main component.
This SEM photograph is a photograph of a sample in which the obtained anisotropic conductive film is adhered to a glass substrate with an ITO film using an alloy solder containing Sn as a main component.
It was observed that the Mo—Ni alloy grew to a height of 6.5 μm in the through-hole of the pore structure. Although it was an intermediate stage of electrolytic plating, the length of the Mo—Ni alloy grown in the through hole of the pore structure was very uniform with no variation.

SEM observation of the pore structure after electrolytic plating was performed.
In SEM cross-sectional observation, the filling rate of Mo—Ni in all the through holes was 100%, and there was no variation in the filling rate.
The SEM surface photograph was the same as the SEM photograph (upper right figure of FIG. 13) of the sealing part of Example 8 described later, and it was observed that Mo—Ni reached the surface in all the through holes.

(Example 8)
In the same manner as in Example 1, a 50 μm-thick pore structure (anodized alumina) having a plurality of through holes was obtained.
Next, with respect to one surface of the pore structure (the surface on the side where the barrier layer was present), a vacuum deposition apparatus ("VE -2030 "), a 60 nm thick gold film (Au film, first conductor film) was formed. The vapor deposition conditions were as follows.
・ Vapor deposition source: 99.9% gold wire (manufactured by Niraco)
・ Degree of vacuum: 1 × 10 ⁻⁴ Pa or less ・ Substrate temperature: 25 ° C.
-Deposition rate: 5 nm / min.

Next, using a conductor film made of a gold film and an aluminum film as an electrode layer, Mo—Ni alloy (Mo: Ni (mass ratio) = 36: 64) was electrolytically deposited on the pore structure. The plating conditions were as follows.
Electrolytic bath: 0.2M nickel sulfate hexahydrate, mixed solution of 0.1M sodium molybdate and 0.3M sodium gluconate Counter electrode: Pt electrode Bath temperature: 25 ° C
-PH: adjusted to 10 using aqueous ammonia-Voltage: -1.8 V vs. Ag / AgCl
・ Processing time: 450 minutes

SEM observation of the pore structure after electrolytic plating was performed.
The obtained SEM surface photograph is shown in FIG.
In FIG. 13, the upper left figure is a SEM surface photograph at a magnification of 1000 times. Corresponding to the pattern of the opening part of the metal mesh used for gold vapor deposition, a pattern in which a plurality of substantially rectangular pattern units of 8 μm × 8 μm were formed in a matrix with a space of 8 μm was observed.
In FIG. 13, the right figure is an SEM photograph at a magnification of 60000 times. This photograph is an enlarged view of the portion of the substantially rectangular pattern unit. This portion is a portion where a gold film (first conductor film) is formed immediately below the through hole. It was observed that Mo—Ni was formed inside the through hole (sealed portion). When SEM cross-sectional observation was performed, the filling rate of Mo—Ni in all the through-holes of the sealed portion was 100%, and there was no variation in the filling rate.
In FIG. 13, the lower figure is a SEM surface photograph at a magnification of 150,000 times. This photograph is an enlarged view of a portion of the lattice pattern excluding the plurality of substantially rectangular pattern units. This portion is a portion where an aluminum film (second conductor film) is formed immediately below the through hole. All the through holes remained as vacancies, and no Mo—Ni formation was observed in the through holes (unsealed portions).
It was confirmed that Mo—Ni was selectively formed inside some of the plurality of through holes of the pore structure.

Also in Example 8, in the same manner as in Examples 1 to 7, the obtained structure was immersed in a 0.4% by mass (0.1 mol / L) aqueous sodium hydroxide solution for 10 to 30 minutes to obtain unsealed pores. At least a part of the part can be removed.

(Comparative Example 3)
In Example 1, the structure before dissolution treatment of the unsealed hole portion was used as Comparative Example 3 for evaluation. The SEM photograph of Comparative Example 3 is as shown in FIG.

(XRD analysis)
The anisotropic conductive film obtained in Reference Example 1 and Comparative Example 1 was subjected to XRD (X-ray diffraction) analysis. The obtained XRD patterns are shown in FIGS. 14A and 14B.
In the Mo—Ni alloy in Reference Example 1, a diffraction peak was observed at the same position as Ni in Comparative Example 1. This peak is a peak derived from the Ni (220) crystal.
The Mo—Ni alloy in Reference Example 1 had good crystallinity like Ni. Note that Mo in the Mo—Ni alloy in Reference Example 1 seems to exist in an amorphous state in the Ni (220) crystal.

(Measurement of IV characteristics and electric field concentration factor β in vacuum)
For each anisotropic conductive film obtained in Reference Example 1, Example 8, and Comparative Examples 1 and 3, the IV characteristics in vacuum and the electric field concentration coefficient β were obtained in the same manner as in Examples 1 to 7. Was measured.
Tables 3 and 4 show main production conditions and evaluation results in each example.
In the initial state, the reference example 1 obtained higher characteristics than the comparative example 1, and the example 8 obtained higher characteristics than the comparative example 3.
In Comparative Example 1, the half time of the initial current density of 3 μA / cm ² was about 5 hours, whereas in Reference Example 1 and Example 8, the same half time was extended to 10 hours or more, A significant improvement in the durability of the conductor (emitter) was observed.

(Manufacture of FEL)
Using the anisotropic conductive film obtained in Example 8, FEL was produced in the same manner as in Examples 1-7.
As in Examples 1 to 7, light emission of blue-green color was visually confirmed. The light emission luminance of the obtained device was measured using a luminance meter (“BM-9” manufactured by Topcon Corporation), and it was 6000 cd / m ² .

This application has priority based on Japanese Patent Application No. 2013-247354 filed on November 29, 2013 and Japanese Patent Application No. 2013-259330 filed on December 26, 2013. Claims and incorporates all of its disclosure here.

The present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention.

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

1-3 Anisotropic Conductor Film 21 Pore Structure

21A Non-Through Hole

21B Barrier Layer 21H Through Hole 21D Opening 21S Surface 22 Conductor (Emitter, Electron Source)
30 Conductor film (cathode layer)
31 1st conductor film 31P Pattern unit 32 2nd conductor film 4 FEL
5 FED
DESCRIPTION OF SYMBOLS 100 Cathode substrate 200 Anode substrate 220

Anode layer

230, 230R, 230G, 230B Phosphor layer SA Sealing part NSA Unsealed part M Metal object to be anodized

Claims

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 conductor film comprising a conductor selectively formed inside some of the plurality of through holes,
At least part of the unsealed hole where no conductor is formed inside the through hole is removed,
Anisotropic conductor film.
The top of the conductor protruded from the pore structure,
The anisotropic conductor film according to claim 1.
The conductor formed inside the through hole contains at least one metal element selected from the group consisting of Ag, Au, Cd, Co, Cu, Fe, Mo, Ni, Sn, W, and Zn. Including metals or metal compounds,
The anisotropic conductor film according to claim 1.
The conductor formed inside the through hole includes an induced eutectoid alloy.
The anisotropic conductive film according to any one of claims 1 to 3.
The induced eutectoid alloy is
At least one first metal element capable of being plated alone in the through hole;
Although it has a melting point higher than that of the first metal element and cannot be plated in the through hole by itself, it contains at least one second metal element that can be induced eutectoid with the first metal element. ,
The anisotropic conductor film according to claim 4.
One surface of the pore structure covers the opening of the through-hole in which the conductor is formed, and can be plated with the material of the conductor; A second conductor film that covers the opening of the through-hole where no body is formed, is connected to the first conductor film, and is difficult to plate the material of the conductor;
The anisotropic conductive film according to any one of claims 1 to 5.
The first conductor film has a pattern that covers the opening of the through-hole in which the conductor is formed and does not cover the opening of the through-hole in which the conductor is not formed. It is divided into areas of
The second conductor film covers the opening of the through-hole in which the conductor is not formed, and is divided into the plurality of regions and is a pattern unit of the first conductor film. Formed to connect each other,
The anisotropic conductor film according to claim 6.
The second conductor film has a pattern that covers the opening of the through hole in which the conductor is not formed and does not cover the opening of the through hole in which the conductor is formed. It is divided into areas of
The first conductor film covers the opening of the through-hole in which the conductor is formed, and the pattern units of the second conductor film formed separately in the plurality of regions. Formed to connect,
The anisotropic conductor film according to claim 6.
The first conductor film includes a metal or a metal compound containing at least one metal element selected from the group consisting of Au, Ag, Cu, Fe, Ni, Sn, and Zn,
The second conductor film includes a metal or metal compound containing at least one metal element selected from the group consisting of Al, Mg, Si, Ti, Mo, and W, or stainless steel.
The anisotropic conductive film according to any one of claims 6 to 8.
A method for producing an anisotropic conductor film according to any one of claims 1 to 9,
Preparing the pore structure (A);
A step (B) of forming the conductor in a part of the through holes among the plurality of through holes;
And sequentially removing at least a part of the unsealed portion (C),
A method for producing an anisotropic conductor film.
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. And removing the non-through hole as the through hole (AY),
The manufacturing method of the anisotropic conductor film of Claim 10.
Step (B)
One surface of the pore structure covers the opening of the through-hole in which the conductor is formed, and can be plated with the material of the conductor; A step (BX) of forming a second conductor film that covers the opening of the through hole in which a body is not formed and is connected to the first conductor film and is difficult to plate the material of the conductor; ,
A step (BY) of performing electrolytic plating on the pore structure using the first conductor film and the second conductor film as electrode layers,
The manufacturing method of the anisotropic conductor film of Claim 10 or 11.
In step (B),
At least one first metal element that can be plated in the through-hole alone and a melting point higher than that of the first metal element, and cannot be plated in the through-hole alone. Using a plating solution containing the metal element and at least one second metal element capable of inducing eutectoid, electrolytic plating is performed inside some of the plurality of through holes.
The method for producing an anisotropic conductive film according to any one of claims 10 to 12.
In the step (C), at least a part of the unsealed hole portion is dissolved and removed.
The method for producing an anisotropic conductive film according to any one of claims 10 to 13.
A device comprising the anisotropic conductive film according to any one of claims 1 to 9.
Comprising the anisotropic conductive film according to any one of claims 1 to 5,
An electron-emitting device, comprising: an electron source made of the conductor formed in the through hole; and an electrode layer formed on one surface of the pore structure and connected to the electron source.
Comprising the anisotropic conductive film according to any one of claims 6 to 9,
An electron-emitting device, comprising: an electron source made of the conductor formed in the through hole; and an electrode layer including the first conductor film and the second conductor film.
A first electrode substrate comprising the electron-emitting device according to claim 16 or 17,
A second electrode substrate disposed opposite to the first electrode substrate via a vacuum space and including an electrode layer and a phosphor layer;
Field emission lamp.
A first electrode substrate comprising the electron-emitting device according to claim 16 or 17,
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 by modulation of light emitted from the phosphor layer;
Field emission display.