TW201528309A - Anisotropic conductor film and its manufacturing method, device, electron emission component, field emission lamp, and field emission display - Google Patents

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, manufacturing method therefor, electronic emitting component, field emission lamp, and field emission display

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

Field Emission (FE, electric field electron emission) devices are expected to achieve high luminance with low power consumption. The FE device can be utilized as a Field Emission Lump (FEL) or a 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 can be obtained. Heretofore, a Sprite-type emitter (Spindt emmiter) and a carbon nanotube (CNT) emitter have been used as the emitter. However, the Speight-type emitter is difficult to make a large area due to the complicated manufacturing process. On the other hand, in the CNT emitter, it is difficult to make the structural length of the CNTs having high crystallinity uniform and regularly arranged.

At least a part of the anodized metal body is anodized by Al or the like, and a plurality of needle-shaped non-through holes and barriers can be obtained. An anodized metal film of the layer. 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-shaped through holes which extend in the cross direction with respect to the plane direction. . A conductor film is formed on one surface of the pore structure, and a needle-shaped conductor can be formed by plating inside the plurality of through holes. The tip end of the conductor formed inside the through hole can locally generate a high electric field in the electric field.

Non-Patent Document 1 proposes the use of the above-described structure in the FE device. A conductor film formed on one surface of the pore structure can be used as an electrode layer, and a needle-shaped conductor formed inside the through hole can be used as an emitter.

Patent Document 1 discloses a structure in which a Speight-type emitter is further formed on a conductor formed inside a plurality of through holes in the above-described structure (Fig. 1).

In the present specification, a layer in which a plurality of emitters arranged in the plane direction on the electrode layer is referred to as an "emitter layer". Further, an element including an electrode layer and an emitter layer is referred to as an "electron emitting element".

By using an anodized metal film, an electron emission element can be formed by a simple procedure, and it is easy to increase the area. The structural design is also easy because it is easy to control the growth direction of the needle-shaped conductor functioning as an emitter.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 6034468

[Patent Document 2] Japanese Patent No. 5158809 (JP-A-2010-205458)

[Patent Document 3] Japanese Patent No. 4271467 (JP-A-2004-285405)

[Patent Document 4] Japanese Patent Laid-Open No. 4-87213

[Patent Document 5] Japanese Patent No. 2013-162364 (not disclosed in the case of this case)

[Patent Document 6] Japanese Patent No. 4681939

[Non-patent literature]

[Non-Patent Document 1] Electrochemistry Communications 11 (2009) 660-663.

[Non-Patent Document 2] M.P. Proenca et. al., Electrochimica Acta 72 (2012) 215-221.

[Non-Patent Document 3] "Mo-compound structure in aqueous solution and Mo alloy plating mechanism", Surface Technology 49 (1998) 87-93.

[Non-Patent Document 4] "Preparation and Corrosion Resistance of Electrodeposited Ni-Mo Alloy from Glucose Bath", Surface Technology 55 (2004) 56-60.

Generally speaking, in the case of an electron emitting element, it is known that if the emitter gap becomes too narrow, the electric field applied to the front end of each emitter is shielded, and the electron emission performance is close to that of the plane electrode.

For example, Patent Document 2 discloses a configuration in which a through hole is provided in a CNT emitter layer (FIG. 1). Patent Document 2 shows that the diameter of the through hole will be (W) When fixed at 80 μm, the pattern width (S) of the CNT emitter layer is reduced and the space is relatively increased, and the electron emission performance is improved (Fig. 7).

In the anodized metal film produced under normal conditions, the diameter of the through hole is, for example, about 20 to 200 nm, and the interval between the adjacent through holes is, for example, about 20 to 200 nm. Therefore, in the electron emission element using the anodized metal film proposed in Non-Patent Document 1 and Patent Document 1, the emitter gap of the entire element is extremely narrow, and it is difficult to obtain high electron emission performance.

Although the use is different, Patent Document 3 discloses a microelectrode array in which an anodized metal body is anodized to selectively pass a part of a plurality of non-through holes of the obtained anodized metal film. The hole, which selectively forms an electric conductor inside thereof (request 1, 2, and 2).

In this document, an anodic oxidation is carried out by pressing a SiC film with a pair of anodized metal bodies (Al) to form a plurality of depressions on the surface. In the case of the anodized metal film (alumina) produced by this method, the pore length of the portion where the depression is formed becomes longer than the pore length of the portion where the depression is not formed. Since the portion where the recess is formed and the portion where the recess is not formed, the thickness of the barrier layer is different, and the non-through hole in which the recessed portion is not formed can be selectively formed as the through hole, and the needle-shaped conductor can be selectively formed inside.

In this document, after the needle-shaped conductor is formed, the anodized metal film (alumina) is removed in a sodium hydroxide solution, and the portion of the anodized metal film (alumina) is refilled with a polymer resin to produce micro Electrode array.

However, in the method described in Patent Document 3, the program is complicated. Further, the barrier layer forming the depressed portion is left, and the barrier layer in which the depressed portion is not formed needs to be surely removed, and the control of the barrier layer removal is difficult. Further, when there is fine unevenness on the surface of the anodized metal body (Al) and the flatness is low, the SiC film can not be provided with a depression even if it is pressed. In general, in the processing step in the production of a metal body, irregularities of several μm or more, such as rolling stripe, often occur. Therefore, from the viewpoint of the flatness of the anodized metal body (Al), it is difficult to increase the area.

Further, in this method, unlike the anisotropic conductor film of the present invention, the anodized metal film (alumina) is completely removed. Therefore, the through-hole and the anodized portion around it are not left at all.

Patent Document 4 discloses that, in the use of a semiconductor wafer, an anodized metal film having a plurality of through holes is obtained, and a photoresist pattern is formed on the surface thereof, and the photoresist pattern is selectively used as a mask. A method for producing an anisotropic conductor film in which a through hole is formed in a portion of a diameter and selectively forms a conductive body in the through hole having a diameter (Fig. 3(a) to (e)).

The anodized metal film is hydrophilic, and relatively, the photoresist has lipophilicity, and it is not easy to directly apply a photoresist to 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 the photoresist system so as to encapsulate the opening portion of the through hole in the inside of the through hole where the conductor is not formed.

As described above, Patent Document 4 is difficult to implement.

Further, in the method described in Patent Document 4, the tip end of the conductor formed in the through hole is contaminated or deteriorated by removing the solvent used for the hydrophobizing agent, the photoresist or the photoresist pattern, and The performance of the emitter is reduced.

Further, when the photoresist remains in the through hole, heat is diffused by the heating process, and the entire emitter is contaminated, and the performance of the emitter is lowered.

The inventors of the present invention disclose an anisotropic conductor film having a pore structure and an electric conductor in Patent Document 5 of the prior application (not disclosed in the present application), the pore structure system being An anodic metal oxide film having a plurality of through holes extending in a direction intersecting in a plane direction, the conductive system being selectively formed inside a through hole of a part of the plurality of through holes; and further, the pores One of the structures includes a first conductor film and a second conductor film, and the first conductor film covers an opening in which the through hole of the conductor is formed, and the material of the conductor can be In the plating, the second conductor film covers the opening in which the through hole of the conductor is not formed, and is formed by connecting the first conductor film, and it is difficult to plate the material of the conductor (request) Item 1).

The anisotropic conductor film can be manufactured without using a photoresist without complicated program control.

When the anisotropic conductor film is used in a state of a device such as an FE device, the emitter gap can be controlled to a wide range. As a result, the emitter gap becomes too narrow, and the electric field applied to the front end of each emitter is received by the screen. It can suppress the degradation of electron emission performance and can exhibit high electron emission performance.

In the anisotropic conductor film disclosed in Patent Document 5, the inventors have found that the opening of the through hole in the unsealed portion is closed by foreign matter such as polishing dust or water adsorbed in the manufacturing process. When the FE device or the like is formed, there is a case where the through hole of the unsealed portion is not well decompressed.

If the FE device or the like is operated without being decompressed well in the through hole of the unsealed portion, it may remain in the through hole of the unsealed portion due to heat or ion collision or the like generated during electron emission. The gas is released into the vacuum space. The gas that is released into the vacuum space is ionized, and the generated ions impart plasma damage to the anisotropic conductor film, and the anisotropic conductor film is damaged due to abnormal discharge. This causes a decrease in durability of the FE device or the like.

Further, in the case of the FE device, it is preferable that the unevenness of the surface is less. For this reason, the uniformity of the plurality of emitter lengths constituting the FE device is preferably high.

In the direct current plating method of the prior art, the growth rate of the acicular conductor formed in the plurality of through holes is uneven due to the uneven diffusion speed of the metal ions, and the acicular conduction in the plurality of through holes The length of the body is uneven.

For example, Non-Patent Document 2 discloses an SEM cross-sectional photograph of an anisotropic conductor film in which Ni is formed in a plurality of through holes of an anodized aluminum oxide film by a DC plating method (Fig. 6).

In the SEM cross-sectional photograph of Non-Patent Document 2, it is formed in a plurality of The length of the needle-like conductor in the through hole can be seen to be uneven.

For this reason, the length of the needle-shaped conductor formed in the plurality of through holes is generally uniformized by surface polishing or the like after the plating (request 2 of Patent Document 6, etc.). In consideration of manufacturing efficiency and manufacturing cost, it is preferable to form a needle-shaped conductor of uniform length in a plurality of through holes without performing processing such as surface polishing.

In the case of the FE device, the durability of the emitter is preferably high. For this reason, the emitter is preferably excellent in crystallinity, high in chemical stability, and high in melting point.

The above-described problem is the same in the case where a conductor is formed in a plurality of through holes of a pore structure composed of an anodized film by plating.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an anisotropic conductor film having a pore structure and a conductor, and which can be used for FE The durability of the device is such that the pore structure is composed of an anodized metal film having a plurality of through holes, and the conductive system is selectively formed inside a through hole of a part of the plurality of through holes.

The present invention further provides an anisotropic conductor film having a pore structure and an electric conductor, and a method for producing the same, wherein the pore structure is anodized by a plurality of through holes The metal film is formed, and the conductive system is formed inside the through hole of at least a part of the plurality of through holes; the conductive system in the plurality of through holes has good crystallinity, high chemical stability, high melting point, and uniform length; Manufactured in less than the manufacturing steps to date.

An anisotropic conductor film of the present invention comprising an anisotropic conductor film having a pore structure and a conductor, wherein the pore structure system has a plurality of through holes extending in a direction intersecting the surface direction The anodized metal film is formed by selectively forming a conductive hole in a part of the through hole of the plurality of through holes, and at least a part of the unsealed portion in which the conductor is not formed inside the through hole is removed.

In the anisotropic conductor film of the present invention, the conductor formed inside the through hole preferably contains an induction eutectoid type alloy.

The method for producing an anisotropic conductor film according to the present invention is the method for producing an anisotropic conductor film of the present invention, which comprises the steps of: preparing the pore structure (A); a step (B) of forming a part of the through holes in the plurality of through holes to form the conductor; and a step (C) of removing at least a part of the unsealed portion.

The device of the present invention comprises the above anisotropic conductor film of the present invention.

An electron emission device according to the present invention includes the anisotropic conductor film of the present invention, and includes an electron source and an electrode layer formed on the foregoing The conductive body is formed in the through hole, and the electrode layer is formed on one surface of the pore structure and is electrically connected to the electron source.

The field emission lamp (FEL) of the present invention includes a first electrode substrate and a second electrode substrate, wherein the first electrode substrate includes the electron emission device of the present invention, and the second electrode substrate is the first electrode substrate It is disposed opposite to each other across the vacuum space, and includes an electrode layer and a phosphor layer.

A field emission display (FED) according to the present invention includes a first electrode substrate and a second electrode substrate, and is displayed by modulating light emitted from the phosphor layer, wherein the first electrode substrate includes In the above-described electronic discharge device of the present invention, the second electrode substrate is disposed to face the first electrode substrate with a vacuum space interposed therebetween, and includes an electrode layer and a phosphor layer.

According to the present invention, it is possible to provide an anisotropic conductor film having a pore structure and a conductor, and which can improve durability when used in an FE device or the like, and a method for producing the same The pore structure system is composed of an anodized metal film having a plurality of through holes, and the conductive system is selectively formed inside a through hole of a part of the plurality of through holes.

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, an anisotropic conductor film and a method of manufacturing the same can be provided. The anisotropic conductor film system includes a pore structure and a conductor. The pore structure system is composed of an anodized metal film having a plurality of through holes formed in at least a part of the plurality of through holes. The inside of the hole; the conductive system in the plurality of through holes has good crystallinity, high chemical stability, high melting point, and uniform length; and can be manufactured in less than the manufacturing steps to date.

1~3‧‧‧ anisotropic conductor film

21‧‧‧Pore structure

21A‧‧‧non-through holes

21B‧‧‧Barrier

21H‧‧‧through hole

21D‧‧‧ openings

21S‧‧‧ face

22‧‧‧Electrical conductor (emitter, electron source)

30‧‧‧Electrical film (cathode layer)

31‧‧‧1st conductor film

31P‧‧‧ pattern unit

32‧‧‧2nd conductor film

4‧‧‧FEL

5‧‧‧FED

100‧‧‧Cathode substrate

200‧‧‧Anode substrate

220‧‧‧anode layer

230, 230R, 230G, 230B‧‧‧ fluorescent layer

SA‧‧‧Blocking Department

NSA‧‧‧Unsealed

M‧‧‧ anodized metal body

Fig. 1A is a schematic cross-sectional view showing the configuration of an anisotropic conductor film according to an embodiment of the present invention.

Fig. 1B is a schematic plan view of the anisotropic conductor film of Fig. 1A.

Fig. 2A is a view showing a step of a method of manufacturing the anisotropic conductor film of Fig. 1A.

Fig. 2B is a step diagram showing a method of manufacturing the anisotropic conductor film of Fig. 1A.

Fig. 2C is a view showing the steps of a method of manufacturing the anisotropic conductor film of Fig. 1A.

Fig. 2D is a step diagram showing a method of manufacturing the anisotropic conductor film of Fig. 1A.

Fig. 2E is a step diagram showing a method of manufacturing the anisotropic conductor film of Fig. 1A.

Fig. 2F is a step view showing a method of manufacturing the anisotropic conductor film of Fig. 1A.

Fig. 2G is a step diagram showing a method of manufacturing the anisotropic conductor film of Fig. 1A.

Fig. 2H is a schematic cross-sectional view showing a modification of the design of the anisotropic conductor film of Fig. 1A.

Fig. 3 is a schematic cross-sectional view showing a modification of the design of the anisotropic conductor film of Fig. 1A.

Fig. 4A is a schematic cross-sectional view showing an FEL according to an embodiment of the present invention.

Fig. 4B is a schematic cross-sectional view showing an FED according to an embodiment of the present invention.

Fig. 5 is a SEM surface photograph of the unsealed portion of the anisotropic conductor film before the dissolution treatment in Example 1.

Fig. 6 is a SEM oblique photograph and a SEM cross-sectional photograph of the anisotropic conductor film after the unsealed portion was dissolved in the first embodiment.

Fig. 7 is a SEM oblique photograph and a SEM cross-sectional photograph of the anisotropic conductor film after the unsealed portion was dissolved and treated in Example 2.

Fig. 8 is a SEM surface photograph of the anisotropic conductor film before the dissolution treatment of the unsealed portion in Example 6.

Fig. 9 is a SEM surface photograph of the anisotropic conductor film before the dissolution treatment of the unsealed portion in Example 7.

Fig. 10 is a luminescent photograph of the FEL using the anisotropic conductor film obtained in Example 1.

Fig. 11A is an explanatory view for explaining a plating method in a manufacturing method in a case where the conductor contains a state of an eutectoid alloy.

Fig. 11B is an explanatory view showing a plating method hitherto known.

Fig. 12 is a SEM cross-sectional photograph of the intermediate stage of electroplating in Reference Example 1.

Figure 13 is an anisotropic conductor film obtained in Example 8. SEM surface photo.

Fig. 14A is an XRD pattern of the anisotropic conductor film obtained in Reference Example 1.

Fig. 14B is an XRD pattern of the anisotropic conductor film obtained in Comparative Example 1.

[Formation of the Invention]

"Anisotropic Conductor Film"

The configuration of the anisotropic conductor film according to one embodiment of the present invention will be described with reference to the drawings.

Fig. 1A is a schematic cross-sectional view of an anisotropic conductor film of the present embodiment.

Fig. 1B is a schematic plan view showing an anisotropic conductor film of the present embodiment, showing a planar pattern of the through holes 21H and the conductors 22.

The anisotropic conductor film 1 of the present embodiment can be preferably used for an electron emission element used in a field emission (FE) device or the like.

Specifically, the FE device includes a first electrode substrate and a second electrode substrate, and the first electrode substrate includes an electron emission element including an emitter (electron source) and an electrode layer, and the second electrode substrate is provided. The first electrode substrate is disposed to face each other with a vacuum space interposed therebetween, and includes an electrode layer and a phosphor layer.

As shown in FIG. 1A, the anisotropic conductor film 1 of the present embodiment includes a pore structure composed of an anodized metal film having a plurality of needle-shaped through holes 21H extending in the intersecting direction with respect to the plane direction. Body 21. In the anisotropic conductor film 1, selectively in a plurality of through A conductor 22 is formed inside a portion of the through hole 21H of the hole 21H.

In the figure, reference numeral 21S denotes one surface (lower surface in the figure) 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 in which 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 portion NSA".

The number of the through holes 21H included in one of the plugging portions SA may be a single number or a plurality.

In the present embodiment, the one plugging portion SA includes a plurality of through holes 21H adjacent to each other, an anodized portion around each of the through holes 21H, and a conductor 22 formed inside each of the through holes 21H.

The anisotropic conductor film 1 of the present embodiment has at least one plugging portion SA.

In the example of the drawing, the anisotropic conductor film 1 has a plurality of plugging portions SA, and one of the plugging portions SA includes a through hole in which the conductors 22 are formed inside two × 2 holes. 21H.

The one plugging portion SA corresponds to the pattern unit 31P of the first conductor film 31 which will be described later in FIG. 1B.

In the anisotropic conductor film 1 of the present embodiment, at least a part of the unsealed portion NSA in which the conductor 22 is not formed inside the through hole 21H is removed.

The unsealed portion NSA removes at least a portion from the opening side of the through hole 21H in the thickness direction.

In the present embodiment, the unsealed portion NSA is partially removed in the thickness direction from the opening side of the through hole 21H, and the unsealed portion NSA includes at least one unsealed hole in which the conductor 22 is not formed inside. The through hole 21H and the anodized portion around each of the through holes 21H.

As in the anisotropic conductor film 2 shown in FIG. 2H, the unsealed portion NSA in which the conductor 22 is not formed inside the through hole 21H can be completely removed.

When at least a part of the unsealed portion NSA is removed, as shown in FIGS. 1 and 2H, the anodized portion of the plugged portion SA is partially removed, and the top portion of the conductor 22 has a finer pore structure. The condition in which the body 21 is prominent. Moreover, the head tops in which the plurality of conductors 22 constituting the one plugging portion SA protrude are in close contact with each other (see the SEM photograph of Example 2 in Fig. 7).

A conductor film 30 composed of the first conductor film 31 and the second conductor film 32 is formed on one surface 21S of the pore structure 21 .

The first conductor film 31 and the second conductor film 32 are formed on the surface 21S of the pore structure 21, and the first conductor film 31 covers the opening of the through hole 21H in which the conductor 22 is formed. 21D, and the material of the conductor 22 can be plated, and the second conductor film 32 is formed by covering the opening 21D in which the through hole 21H of the conductor 22 is not formed, and the first conductor film 31 is connected thereto. It is also difficult to plate the material of the conductor 22.

In the first embodiment, the first conductor film 31 covers the opening 21D in which the through hole 21H of the conductor 22 is formed, and does not cover the opening 21D in which the through hole 21H of the conductor 22 is not formed. The pattern is formed by dividing into a plurality of regions. The second conductor film 32 is covered with The opening 21D of the through hole 21H of the conductor 22 is not formed inside, and the pattern unit of the first conductor film 31 formed by dividing the plurality of regions is formed to be connected to each other. In the present embodiment, the second conductor film 32 is a solid film that does not have a pattern.

In the present embodiment, the first conductor film 31 and the second conductor film 32 are connected to each other in order to integrally form the electrode layer. Thereby, the plurality of pattern elements of the first conductor film 31 formed to be separated from each other can be electrically connected to each other through the second conductor film 32.

In the example shown in FIG. 1A and FIG. 1B, the pattern unit 31P of the first conductor film 31 includes two substantially two substantially rectangular patterns having through holes 21H in which the conductors 22 are formed. In plan view, between the pattern cells 31P of the first conductor film 31 adjacent to each other, there are two × 2 through holes 21H in which the conductors 22 are not formed. As described above, the second conductor film 32 is formed directly under the through hole 21H in which the conductor 22 is not formed.

Further, the pattern design is merely an example, and it is possible to freely design the conductor 22 to be formed inside one of the plurality of through holes 21H. In the present embodiment, the through hole 21H in which the conductor 22 is to be formed can be freely selected by changing the pattern of the first conductor film 31.

The conductor 22 formed inside the through hole 21H is made of a material that can be plated.

The conductor 22 preferably contains 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 the above, from the viewpoint of easy manufacture and high conductivity, Particularly preferred are metals or metal compounds containing Ni and/or Ag.

Among the above, 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.

The metal compound may, for example, be a metal oxide or the like.

The conductor 22 formed inside the through hole 21H is made of a material that can be plated, and preferably includes an induced eutectoid alloy.

The induced eutectoid alloy includes at least one first metal element and at least one second metal element; the first metal element can be individually plated in the through hole 21H, and the second metal element is the first metal element It also has a high melting point and cannot be plated in the through hole 21H alone, but can induce eutectoid precipitation with the above first metal element.

The first metal element is preferably selected from at least one selected from the group consisting of Fe, Ni, and Co, and the second metal element is preferably selected from at least one of the group consisting of Mo, W, and B.

The first conductor film 31 is made of a material that can plate the conductor 22.

The first conductor film 31 preferably contains 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.

Among the above, from the viewpoint of high standard electrode potential, it is particularly preferable to contain a metal or a metal compound of Au and/or Ag.

The metal may be a single metal or an alloy.

The metal compound may, for example, be a metal oxide or the like.

The second conductor film 32 is made of a material (hard-to-plating material) which is difficult to plate the conductor 22 . The hard-to-plating material is a metal or a metal compound which is likely to generate an oxide film having high insulating properties on the surface.

The second conductor film 32 preferably contains a metal or a 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 the above, from the viewpoint of ease of production and low cost, it is particularly preferable to contain a metal or a metal compound of Al.

The metal may be a single metal or an alloy.

The metal compound may, for example, be a metal oxide or the like.

As the stainless steel, a Fe-Ni-Cr alloy or the like can be mentioned.

The anisotropic conductor films 1 and 2 of the present embodiment can be used as an electron emission element used in an FE device or the like. In this case, the conductor 22 formed inside the through hole 21H can be used as an emitter (electron source), and the conductor film 30 composed of the first conductor film 31 and the second conductor film 32 can be used as an electrode. Floor.

The size design of the conductor 22 and the through hole 21H in the electron emission element is as follows.

The length of the conductor 22 is preferably 1 μm or more, and particularly preferably 5 μm or more, based on the 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, based on the high electron emission performance.

When the ease of formation is considered, the diameter of the conductor 22 is preferably 20 nm or more.

The length/diameter of the conductor 22 is preferably 100 or more based on the high electron emission performance.

In the present embodiment, the conductor 22 is formed inside the through hole 21H.

When the conductor 22 is preferably sized, 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, although the filling rate of the conductor 22 in the through hole 21H in which the conductor 22 is formed inside is 100%, the filling rate of the conductor 22 may not be 100%.

However, since the electron emission performance is high, the filling rate of the conductor 22 in the through hole 21H in which the conductor 22 is formed inside is preferably as high as possible, and is preferably 70 to 100%.

In the present specification, the filling rate of the conductor 22 in the inside of 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 of the through holes 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 be uneven. However, in this case, in-plane unevenness of electron emission performance may occur. When the in-plane uniformity of the electron emission performance is considered, the unevenness of the filling rate is preferably small.

The length of the through hole 21H is considered to be a preferred conductor 22 The length and the filling rate of the conductor 22 in the inside of the through hole 21H are determined.

In the present embodiment, the conductor 22 formed inside the plurality of through holes 21H formed directly above the one pattern unit 31P of the first conductor film 31 constitutes one plug portion SA. In the plan view, the plurality of plugging portions SA are separated from each other by a plurality of through holes 21H (unsealed portions NSA) in which the conductors 22 are not formed.

In the present embodiment, the plurality of plugging portions SA are separated from each other, and the control of the interval is also easy.

When the anisotropic conductor film 1 of the present embodiment is used in a state of an FE device or the like, the emitter gap can be controlled to a wide range. For example, the emitter gap (the gap of the plugging portions SA adjacent to each other in the present embodiment) can be controlled in a range from about 100 nm to several tens of μm. As a result, the emitter gap becomes too narrow, and the electric field applied to the tips of the respective emitters is shielded, and the electron emission performance can be suppressed from being lowered, and high electron emission performance can be exhibited.

In the FE device or the like, heat is generated in the conductor 22 that emits the emitter of the electron.

In the present embodiment, it is considered that each of the conductors 22 is protected by being surrounded by the anodized portion, so that it is possible to suppress damage due to heat due to electron emission.

In the present embodiment, the one plugging portion SA includes a plurality of through holes 21H adjacent to each other, an anodized portion around each of the through holes 21H, and a conductor 22 formed inside each of the through holes 21H.

When focusing on the plurality of electric conductors 22 constituting one plugging portion SA At this time, it is considered that the electrons that emit electrons at a certain timing constitute the conductor 22 of one of the one plugging portions SA. Although heat is generated in the conductor 22 that emits electrons at a certain timing, since the adjacent conductors 22 are connected via the anodized portion, it is considered that the generated heat is diffused to the anodized portion and constitutes the same plugged portion. SA and other electrical conductors 22 that do not emit electrons at this timing.

In other words, in the anisotropic conductor films 1 and 2 of the present embodiment, even if heat is generated by electron emission, it is considered that the generated heat is easily diffused, and damage due to heat of the electron conductor 22 is released. Suppressed.

As described in the "Problems to be Solved by the Invention", in the anisotropic conductor film having the plugged portion and the unsealed portion, the opening of the through hole of the unsealed portion is generated in the manufacturing step. The foreign matter such as the polishing dust or the adsorbed water is closed, and when the FE device or the like is formed, the through hole of the unsealed portion is not decompressed well. If the FE device or the like is operated without being decompressed well in the through hole of the unsealed portion, the through hole may remain in the unsealed portion due to heat or ion collision or the like generated during electron emission. The gas inside is discharged to the vacuum space. The gas that is released into the vacuum space is ionized, and the generated ions cause plasma damage to the anisotropic conductor film, and the anisotropic conductor film is damaged due to abnormal discharge.

In the anisotropic conductor films 1 and 2 of the present embodiment, at least a part of the unsealed portion NSA is removed, so that an opening that closes the through hole 21H of the unsealed portion NSA is generated in the manufacturing process. Foreign matter in the part, the foreign matter can also be completely removed. Therefore, by diversification When the conductive film 1 and 2 constitute an FE device or the like, damage of the anisotropic conductor films 1 and 2 due to abnormal discharge is suppressed.

When the unsealed portion NSA is completely removed, the pressure reduction in the through hole 21H of the unsealed portion NSA in the FE device or the like is not required. Even when the unsealed portion NSA is partially left, the length of the through hole 21H of the unsealed portion NSA is shortened, and the inside of the through hole 21H of the unsealed portion NSA in the FE device or the like is easily reduced. Pressure.

When the above effects are combined with each other, the anisotropic conductor films 1 and 2 of the present embodiment are not subjected to the removal process of the unsealed portion NSA (the removal process is not particularly described in the present specification). The durability of the FE device or the like can be improved as compared with the case where the partial removal processor is included.

When the conductor 22 includes a state in which the eutectoid alloy is induced, the conductors in the plurality of through holes 21H can be formed without performing a surface polishing or the like after the conductor 22 is formed as described in the later-described manufacturing method. The length (filling rate) of 22 is uniform.

Since the length (filling ratio) of the conductors 22 in the plurality of through holes 21H is uniform, when the anisotropic conductor films 1 and 2 of the present embodiment are used in the case of the FE device, it is possible to suppress surface light emission. All.

The conductor 22 using the induced eutectoid alloy has crystallinity equivalent to that of Ni which has hitherto been generally used for electroplating. Further, the conductor 22 for inducing the eutectoid alloy is used, and it is a second metal element having high chemical stability and high melting point as compared with Ni or the like which has been conventionally used for electroplating. The conductor 22 including the induced eutectoid alloy has different crystallinity, high chemical stability, and high melting point. When the conductive films 1 and 2 are used in the case of the FE device, the emitter (electron source) has high material stability and excellent durability.

"Design change example"

Fig. 3 is a schematic cross-sectional view showing a modification of the design of the anisotropic conductor film. The same components as those of the anisotropic conductor films 1 and 2 of the above-described 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 in which the through hole 21H of the conductor 22 is not formed, and the conductive portion is not covered. The pattern of the opening 21D of the through hole 21H of the body 22 is formed into a plurality of regions. The first conductor film 31 is formed by covering the opening 21D in which the through hole 21H of the conductor 22 is formed, and the pattern unit of the second conductor film 32 formed by dividing the plurality of regions is connected to each other. . In this example, the first conductor film 31 is a full-surface film having no pattern.

In this design modification, the first conductor film 31 and the second conductor film 32 are connected to each other in order to integrally form the electrode layer. Thereby, the plurality of pattern elements of the second conductor film 32 formed to be separated from each other can be electrically connected to each other through the first conductor film 31.

In the design modification example shown in FIG. 3, the conductor 22 is formed in any of the plurality of through holes 21H, and can be freely designed. In this design modification, the through hole 21H in which the conductor 22 is to be formed can be freely selected by changing the pattern of the second conductor film 32.

The anisotropic conductor film 3 is formed inside the plurality of through holes 21H formed directly above one pattern unit of the second conductor film 32. The conductor 22 constitutes one plugging portion SA. In the anisotropic conductor film 3, the plurality of plugging portions SA are also separated from each other by a plurality of through holes 21H (unsealed portions NSA) in which the conductors 22 are not formed.

In this design modification, the plurality of plugging portions SA are also separated from each other, and the control of the interval is also easy.

In the anisotropic conductor film 3, at least a part of the unsealed portion NSA is also removed.

In the anisotropic conductor film 3, the same effects as those of the anisotropic conductor films 1 and 2 can be obtained.

"Method for producing anisotropic conductor film"

An example of a method of producing an anisotropic conductor film will be described with reference to the drawings.

2A to 2H are step diagrams. 2A and 2B are schematic perspective views, and Figs. 2C to 2H are schematic cross-sectional views.

(Step (A))

The pore structure 21 having a plurality of through holes 21H is prepared as follows.

<Step (AX)>

First, as shown in Fig. 2A, the metal body M to be anodized 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 system can comprise one or more of these.

The main component of the anodized metal body is particularly preferably Al or the like.

In the present specification, the "main component of the anodized metal body" is defined as a component of 99% by mass or more.

The shape of the anodized metal body M is not limited, and may be a plate shape or the like. In addition, the form in which the anodized metal body M is formed into a layer on the support is used, and the use of the support is not hindered.

As shown in FIG. 2B, if at least a part of the anodized metal body M is anodized, a pore structure 21X composed of a metal oxide film is formed. For example, when the anodized metal body M is mainly composed of Al, a pore structure 21X containing Al ₂ O ₃ as a main component is formed.

When a plate-like state or the like is used to anodize the metal body M, usually, a part of the anodized metal body M is left, and a part of the anodized metal body M is anodized. In the figure, the symbol 10 is the remaining portion of the anodized metal body M. In this case, generally, the generated pore structure 21 is thin with respect to the remaining portion 10 of the anodized metal body M. In the drawing, the pore structure 21X is enlarged for easy visual recognition. Make an illustration.

The anodic oxidation, for example, is such that the anodized metal body M is an anode, and carbon or aluminum or the like is a cathode (counter electrode), which is immersed in an anodic oxidation electrolyte and applied between the anode and the cathode. Voltage is implemented.

The electrolytic solution is not limited, and an acidic electrolytic solution containing one or more kinds of acids such as sulfuric acid, phosphoric acid, chromic acid, oxalic acid, aminesulfonic acid, benzenesulfonic acid, and decylsulfonic acid can be preferably used.

If the anodized metal body M is anodized, as shown in Fig. 2B, an oxidation reaction is performed from the surface (upper in the figure) in a direction substantially perpendicular to the surface to form a metal oxide film.

The metal oxide film formed by the anodic oxidation is a structure in which a plurality of columnar bodies 21C having a substantially hexagonal columnar shape are arranged adjacent to each other without a gap. At a substantially central portion of each of the columnar bodies 21C, a needle-shaped non-through hole 21A whose opening extends in the depth direction from the surface is formed. A barrier layer 21B is formed 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, and the opening is slightly inclined.

<Step (AY)>

When there is a condition of the remaining portion 10 of the anodized metal body M after the step (AX), the remaining portion 10 and the barrier layer 21B are removed, and after the step (AX), the remaining portion of the metal body M is not anodized. In the case of the portion 10, the barrier layer 21B is removed, and the non-through hole 21A is formed as the through hole 21H.

The remaining portion 10 of the anodized metal body M can be removed, for example, by reverse electrolytic stripping of a voltage applied in the opposite direction in the method of anodizing.

The remaining portion 10 of the anodized metal body M and the barrier layer 21B can also be removed by being immersed in an acidic liquid such as phosphoric acid.

The remaining portion 10 of the anodized metal body M and the barrier layer 21B can be physically removed by cutting or the like.

As described above, the pore structure 21 having the plurality of through holes 21H as shown in FIG. 2C can be obtained.

(Step (B))

As described below, the conductor 22 is formed inside a part of the through holes 21H of the plurality of through holes 21H to form the plugging portion SA.

<Step (BX)>

The conductor film 30 composed of the first conductor film 31 and the second conductor film 32 is formed on one surface (lower surface) 21S of the pore structure 21 obtained in the step (A).

In this step, the first conductor film 31 and the second conductor film 32 can be formed on the surface 21S of the pore structure 21, and the first conductor film 31 covers the through hole 21H in which the conductor 22 is formed. The opening portion 21D is capable of plating the material of the conductor 22, and the second conductor film 32 covers the opening 21D in which the through hole 21H of the conductor 22 is not formed, and the first conductor film 31 is connected thereto. It is formed, and it is difficult to plate the material of the conductor 22.

In the pore structure 21, the surface on which the conductor film 30 is formed may be provided on the side of the opening portion of the non-through hole 21A, or may be on the side of the barrier layer 21B.

As shown in FIG. 2D and FIG. 2E, the first conductor film 31 can be formed, and then the second conductor film 32 can be formed. In this case, the first conductor film 31 can cover 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. The pattern is formed by dividing into a plurality of regions. For example, the first conductor film 31 can be patterned by metal deposition or the like using a mask such as a metal mesh. The second conductor film 32 can cover the opening portion 21D of the through hole 21H in which the conductor 22 is not formed, and the pattern unit of the first conductor film 31 formed by dividing the plurality of regions can be connected to each other. And formed. In the illustrated example, the second conductor film 32 is a full-surface film having no pattern.

Contrary to the above procedure, the second conductor film 32 can be formed to form the first conductor film 31. In this case, as shown in FIG. 3, the second conductor film 32 can cover the opening 21D of the through hole 21H in which the conductor 22 is not formed, and does not cover the inside of the conductor 22. The pattern of the opening 21D of the hole 21H is formed by dividing into a plurality of regions. The first conductor film 31 can cover the opening portion 21D of the through hole 21H in which the conductor 22 is formed inside, and the pattern unit of the second conductor film 32 formed by dividing the plurality of regions can be connected to each other. form.

<Step (BY)>

Then, as shown in FIG. 2F, the electroconductive film 30 composed of the first conductor film 31 and the second conductor film 32 is used as an electrode layer, and the pore structure 21 is plated. Thereby, the conductor 22 can be selectively formed inside the through hole 21H in which the first conductor film 31 is formed directly below, and the plugging portion SA can be formed.

In the step (BY), 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 is used. The plating solution can be plated by a plating method known hitherto.

In the step (BY), it is preferable to perform plating by a DC plating method using a plating solution containing at least one first metal element and at least one second metal element, and the first metal element can be individually penetrated. The second metal element is plated in the hole 21H, and the second metal element has a higher melting point than the first metal element, and cannot be plated in the through hole 21H alone, but can induce eutectoid precipitation with the first metal element.

Hereinafter, this method is referred to as "induced eutectoid alloy plating method".

In this method, an electrical conductor 22 comprising an induced eutectoid alloy is formed.

The difference between the induced eutectoid alloy plating method and the DC plating method known so far will be described with reference to FIGS. 11A and 11B.

The left diagram of Fig. 11A is a schematic cross-sectional view showing a case where electroplating is being performed by inducing an eutectoid alloy plating method.

Fig. 11B is a schematic cross-sectional view showing a case where electroplating is being performed by a DC plating method known hitherto.

Heretofore, plating of a plurality of through holes of a fine pore structure has generally been carried out using a plating liquid containing an easily plateable and inexpensive metal such as Ni.

In the case of FIG. 11B, the case where Ni is used is illustrated as an example.

The plating efficiency of Ni is as high as about 80%. Here, the "plating efficiency" is a parameter obtained from the amount of precipitation (mole) with respect to the amount of electricity.

In the DC plating method, the plating speed in the through holes affects the diffusion speed of metal ions.

As shown in FIG. 11B, in the DC plating method hitherto, the growth rate of the conductor 22 formed in the plurality of through holes 21H is uneven due to the uneven diffusion speed of the metal ions, and is more The length of the conductors 22 in the through holes 21H is uneven.

Therefore, in the conventional manufacturing method, generally, the length of the conductor 22 in the plurality of through holes 21H is uniformized by surface polishing or the like after plating.

In the case of the induced eutectoid alloy plating method, as described above, the use of at least one first metal element and at least one second metal element is used. The plating solution is subjected to electroplating by a DC plating method; the at least one first metal element is individually capable of being plated in the through hole 21H, and the at least one second metal element is higher in melting point than the first metal element Further, it is not possible to plate in the through hole 21H alone, but it is possible to induce eutectoid precipitation with the first metal element.

It is considered that in the plating solution, a metal counter ion to which a ligand is bonded is formed around the ion of the first metal element, and the ligand includes the second metal element.

In the case of FIG. 11A, the state of the first metal element Ni and the second metal element Mo is illustrated as an example. In this case, for example, as shown in the right diagram of FIG. 11A, mis-ions in which a plurality of ions (polymolybdate ions) of MoO _{6 are} coordinated are formed around the Ni ions.

The wrong ions require energy because of the energy required to unravel the structure, and a high overvoltage is required in order to precipitate metal ions. In the case of plating under a high overvoltage, the plating efficiency is low because the hydrogen generation reaction is preferentially performed.

For example, in the case of Mo-Ni eutectoid, the plating efficiency is about 6%.

As far as the plating method is concerned, it is preferred that the plating efficiency is high.

In the case of the induced eutectoid alloy plating method, electroplating is strongly performed by a system having low plating efficiency. As a result, as shown in FIG. 11A, the metal ion (metal dislocation ion) consumption rate is reduced as a whole, and metal ions (metal dislocation 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 is performed at the electron supply rate control, and the growth rate of the conductors 22 in the plurality of through holes 21H can be made uniform.

For the induction of the eutectoid alloy plating method, and the plating effect using Ni or the like In the case of a material having a high rate, it is required to have high energy in electroplating, but by increasing the applied voltage or increasing the plating time, etc., the conductor 22 of a desired length can be grown.

In the electroplating in the induced eutectoid alloy plating method, since the conductor 22 is grown in a specific direction (the extending direction of the through hole 21H), the conductor 22 having good crystallinity can be grown.

The electroplating of the Mo-Ni alloy on the flat plate is described in Non-Patent Documents 3 and 4 of the "Background Art", but the application system for the fine pore structure composed of the anodized metal film has hitherto been used. Unknown.

In addition, the conductor 22 can be selectively formed in the inside of the through hole 21H of a part of the plurality of through holes 21H, and when the plugging portion SA is formed, a method other than the above may be employed.

(Step (C))

Next, as shown in Fig. 2G or Fig. 2H, at least a portion of the unsealed portion NSA is removed.

In the method of removing the unsealed portion NSA, it is preferred to use a solution for dissolving and removing the liquid (hereinafter referred to as a solution) in which the anodized portion is dissolved.

The solution may be a sodium hydroxide aqueous solution or a mixed aqueous solution of phosphoric acid or chromic acid.

For example, at least a part of the unsealed portion NSA can be removed by immersing the structure obtained after the step (B) in the solution.

In this step, the solution liquid enters the through hole 21H in which the unsealed portion NSA of the conductor 22 is not formed inside, and the dissolution removal of the anodized portion of the unsealed portion NSA proceeds in the depth direction from the opening side. When the same solution is used, the more the immersion time is, the unsealed portion is removed to Deeper.

Since the conductor 22 is formed in the through hole 21H of the plugging portion SA, the solution does not enter, and when the immersion time of the solution is relatively short, the anodized portion of the plug portion SA is not dissolved and removed. Or even if it is dissolved and removed, the amount is small. When the immersion time of the solution liquid becomes relatively long, the anodized portion of the plugged portion SA is partially removed, and the top portion of the conductor 22 having the plugged portion SA protrudes from the pore structure 21 . Moreover, the protruding top portions of the conductors 22 constituting the one plugging portion SA are in close contact with each other (see the SEM photograph of Example 2 in Fig. 7).

The anisotropic conductor films 1 to 3 were produced as described above.

The closer the direction in which the conductor 22 extends is to the voltage application direction, the electron emission performance is effectively expressed. According to the anodic oxidation method, the fine pore structure 21 in which a plurality of through holes 21H are arranged in a regular array can be formed in a simple procedure, and the plurality of through holes 21H are in a direction parallel or close to the direction in which the voltage is applied. extend. According to the anodic oxidation method, it is easy to control the size (length and diameter) and the number density of the through holes 21H, and it is easy to increase the area. Anodizing is a low cost method.

According to the method of the present embodiment, it is possible to selectively form the conductor 22 in the inside of the through hole 21H of a part of the plurality of through holes 21H without complicated program control, and it is also possible to easily control the conduction function as the emitter. The planar pattern of the body 22.

Since the anisotropic conductor films 1 to 3 can be manufactured without using a photoresist, there is no cause for the front end of the conductor 22 formed inside the through hole 21H. It is contaminated or deteriorated by removing the solvent used for the hydrophobizing agent, photoresist or photoresist pattern, and the performance as an emitter is lowered.

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, the foreign matter can be completely removed. Therefore, damage of 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, the pressure reduction in the through hole 21H of the unsealed portion NSA in the FE device or the like is unnecessary. In the case where the unsealed portion NSA is partially left, the length of the through hole 21H of the unsealed portion NSA is also shortened, and the inside of the through hole 21H of the unsealed portion NSA in the FE device or the like is easily decompressed.

When the above effects are combined with each other, the durability of the FE device or the like can be improved as compared with the case where the unsealing portion NSA is not removed (partially removed). The anisotropic conductor films 1 to 3.

As described above, according to the present embodiment, it is possible to provide an anisotropic conductor film 1 to 3 including the pore structure 21 and the conductor 22, and a method for producing the same, which can be lifted The pore structure 21 is composed of an anodized metal film having a plurality of through holes 21H which are selectively formed in a part of the plurality of through holes 21H when used for durability in an FE device or the like. The inside of the through hole 21H.

"FE device"

Referring to the drawings, the field emission of one embodiment of the present invention is directed The structure of the lamp (Field Emission Lump: FEL, illumination device) will be described.

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

FEL4 series has: 0

The cathode substrate (first electrode substrate) 100 includes a substrate body 110 and a cathode layer (conductor film 30), and an anode substrate (second electrode substrate) 200 having a substrate body 210 and an anode layer 220.

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 on the inner surface of the substrate body 110 in the anisotropic conductor film 1 shown in FIGS. 1A and 1B.

As the substrate body 110, a glass substrate or the like having a light-transmitting conductor film such as a metal plate or ITO (Indium Tin Oxide) can be used.

The cathode substrate 100 can be obtained by welding the substrate body 110 to the anisotropic conductor film 1 of the above-described embodiment or by 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 is selectively formed in the pore structure 21 The conductor 22 inside a part of the through hole 21H is an emitter (electron source).

In Fig. 4A, the structure of the anisotropic conductor film 1 is simplified, but it is the same as that shown in Figs. 1A and 1B.

Further, positively formed in one pattern unit 31P of the first conductor film 31 The number of through holes 21H above and having the conductors 22 formed therein is more illustrated than in FIGS. 1A and 1B.

The anode layer 220 is a light-transmitting conductor film such as ITO (Indium Tin Oxide) which is formed on the entire inner surface of the substrate body 210.

As the substrate body 210, a glass substrate or the like is used.

A phosphor layer 230 is formed on the inner surface of the anode layer 220.

As the material of the phosphor layer 230, a known material can be used.

The material of the phosphor layer 230 is not particularly limited, and examples thereof include: 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 and CsVO ₃ .

The color of the phosphor layer 230 is arbitrary.

When the state of the white light source is used, a plurality of known materials having different luminescent colors such as a blue material, a green material, and a red material can be arbitrarily combined, and white light can be obtained as a material of the phosphor layer 230.

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

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

In the FEL 4 of the present embodiment, an emitter gap is provided in the emitter layer including the plurality of conductors 22, and the emitter gap can be controlled in a wide range. As a result, the emitter gap becomes too narrow, and the electric field applied to the tips of the respective emitters is shielded, and the electron emission performance can be suppressed from being lowered, and high electron emission performance can be exhibited.

FEL4 of the present embodiment, because of the anisotropic conductor film 1 At least a part of the plugging portion NSA is removed, and abnormal discharge in the anisotropic conductor film 1 is suppressed, and the durability is excellent.

In the present embodiment, the FEL has been described as an example. However, as shown in FIG. 4B, the red (R) phosphor layer 230R, the green (G) phosphor layer 230G, and the blue (B) phosphor are patterned. The light-emitting layer 230B is used as the phosphor layer 230, and can be applied to a field emission display (FED) when it is configured to be optically modulated at each dot.

In Fig. 4B, the symbol 5 is an FED.

In FIG. 4B, illustration of the cathode layer (conductor film 30) and the anode layer 220 is omitted.

[Examples]

Hereinafter, embodiments, reference examples, and comparative examples of the present invention will be described.

(Example 1)

The anisotropic conductor film shown in FIGS. 1A and 1B was produced in accordance with the method described in FIGS. 2A to 2G.

An aluminum plate having a thickness of 3 mm of 100 × 100 mm was anodized under the following conditions to form an aluminum oxide film having a plurality of needle-shaped non-through holes and a barrier layer.

. Counter electrode (cathode): aluminum

. Electrolyte: 0.3M sulfuric acid

. Bath temperature: 15~19°C

. Voltage: DC voltage 25V

. Time: 8 hours

The surface and the 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 obtained 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 obtained from the pore length of 100 pores.

The obtained alumina film was substantially uniformly opened with a plurality of needle-shaped non-through holes, and had an average pore diameter of 0.02 μm, an average pore length of 40 μm, and an average pore density of 300 particles/μm ² .

Next, in a state where the aluminum oxide film was connected to the cathode and the Pt-Ti electrode was connected to the anode, a direct current of 5 V was applied to peel off the aluminum oxide film from the Al substrate.

Next, by immersing the aluminum oxide film in phosphoric acid to dissolve the barrier layer at the bottom of the aluminum oxide film, a plurality of non-through holes of the aluminum oxide film are formed as through holes.

As described above, a pore structure having a thickness of 40 μm having a plurality of through holes was obtained.

Next, one of the fine pore structures (the surface having the barrier layer side) was made of a metal mesh having a mesh size of 8 μm and a wire diameter of 8 μm as a mask, and a vacuum vapor deposition apparatus (Vacuum Device Co., Ltd., "VE") was used. -2030"), a gold film (Au, first conductor film) having a thickness of 60 nm was formed. The vapor deposition conditions are as follows.

. Evaporation source: 99.9% gold wire (Nirako company)

. Vacuum degree: 1 × 10 ^-4 Pa or less

. Substrate temperature: 25 ° C

. Evaporation speed: 5nm/min.

Then, a gold vapor-deposited surface of the pore structure was used, and a 150 nm-thick aluminum film (Al film, first) was formed on the entire surface by using a vacuum vapor deposition apparatus ("VE-2030" manufactured by Vacuum Device Co., Ltd.). 2 conductor film). The vapor deposition conditions are as follows.

. Evaporation source: 99.99% aluminum wire (Nirako)

. Vacuum degree: 1 × 10 ^-4 Pa or less

. Substrate temperature: 25 ° C

. Evaporation speed: 10nm/min.

Next, a conductor film made of a gold film and an aluminum film was used as an electrode layer, and Ni was deposited on the pore structure. The plating conditions are as follows.

. Electrolytic bath: a mixture of 1.2 M nickel sulfate ‧ 6 hydrate, 0.2 M nickel chloride and 0.7 M boric acid

. Bath temperature: 32~37°C

. pH: 4.0~5.0

. Voltage: -0.9V vs.Ag/AgCl

. Processing time: 120 minutes

The SEM surface observation and SEM cross-section observation of the pore structure after electroplating were carried out.

The obtained SEM surface photograph is shown in Fig. 5.

In Fig. 5, the upper left image is a SEM surface photograph with a magnification of 3000 times. Corresponding to the pattern of the opening of the metal mesh used for the gold vapor deposition, it is seen that a plurality of substantially rectangular-shaped pattern units of 8 μm × 8 μm have a space of 8 μm and are formed in a matrix.

In Fig. 5, the right image is a SEM photograph of a magnification of 20,000 times. This photograph is a magnified portion of the above-described substantially rectangular-shaped pattern unit. This portion is a portion in which a gold film (first conductor film) is formed directly under the through hole. It can be seen that Ni is formed inside the through hole (sealing portion). In the SEM cross-sectional observation, the filling rate of Ni in the through-hole of the plugging portion is 70 to 100%. Further, since the SEM surface photograph of the upper right diagram is a surface, the filling hole of Ni is less than 100% of the through holes, but actually, Ni is formed inside.

In Fig. 5, the lower photograph is a SEM surface photograph at a magnification of 20,000 times. This photograph is a magnified portion of a lattice pattern other than the plurality of substantially rectangular-shaped pattern units described above. This portion is a portion in which an aluminum film (second conductor film) is formed directly under the through hole. All of the through holes remained hollow, and no Ni was formed in the through holes (unsealed portions).

As shown in FIG. 1A and FIG. 1B, it was confirmed that Ni was selectively formed inside the through hole of a part 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) aqueous sodium hydroxide solution for 10 minutes to remove a part of the unsealed portion.

The SEM oblique photograph and the SEM cross-sectional photograph of the unsealed portion after the dissolution treatment are shown in Fig. 6 . 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)

Except that the dissolution treatment conditions of the unsealed portion were changed to be immersed in a 0.4% by mass (0.1 mol/L) aqueous sodium hydroxide solution for 30 minutes, Example 1 was carried out in the same manner, and an anisotropic conductor film was obtained.

The SEM oblique photograph and the SEM cross-sectional photograph of the unsealed portion after the dissolution treatment are shown in Fig. 7 .

It was observed that the unsealed 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 of the unsealed portion of this example, the anodized alumina of the plugged portion is partially removed, and the top portion of the conductor formed in the plurality of through holes constituting one of the plugged portions is The anodized alumina protrudes in close contact with each other, and the front end portion of the plugged portion has a substantially tapered shape.

(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.

The SEM surface observation of the fine pore structure after plating was performed.

In the same manner as in the first embodiment, a pattern in which a plurality of substantially rectangular-shaped pattern units are formed in a matrix shape can be seen corresponding to the opening of the metal mesh used for gold vapor deposition.

In the same manner as in the first embodiment, the portion of the substantially rectangular-shaped pattern unit is a portion in which a gold film (first conductor film) is formed directly under the through-hole, and it is seen that Ni is formed in the through-hole (sealing portion). . In the SEM cross-sectional observation, the filling rate of Ni in the through-hole of the plugging portion is 70 to 100%.

A portion of the lattice pattern other than the plurality of substantially rectangular-shaped pattern units is a portion in which a titanium thin film (second conductive film) is formed directly under the through hole, and the through hole still maintains a void, and is not in the through hole. See Ni formation (unsealed portion).

In the same manner as in Example 1, it was confirmed that it was selectively in the pore structure. Ni is formed inside the through hole of a part of the plurality of through holes.

In the SEM observation after the dissolution treatment of the unsealed portion, in the same manner as in Example 2, it was observed that the unsealed portion was removed from the opening side to a depth of about 30 μm with respect to the through hole length of 40 μm. Further, in the same manner as in the second embodiment, it was observed that the anodized alumina of the plugged portion was partially removed, and the conductive system formed in the plurality of through holes constituting one of the plugged portions protruded closer to each other than the anodized alumina. The front end portion of the plugging portion is formed into a substantially tapered shape.

(Example 4)

An anisotropic conductor film was obtained in the same manner as in Example 2 except that a conductor film made of a gold film and an aluminum film was used as the electrode layer, and the pore structure was plated with Ag instead of Ni. The Ag plating conditions are as follows.

. Electrolytic bath: a mixture of 0.4M silver methane sulfonate, 0.5 M methane sulfonic acid and 1.5 M potassium hydroxide

. Bath temperature: 22~27°C

. pH: 7.5~8.5

. Current density: 0.5 mA/cm ²

. Processing time: 120 minutes

The SEM surface observation of the fine pore structure after plating was performed.

In the same manner as in the first embodiment, a pattern in which a plurality of substantially rectangular-shaped pattern units are formed in a matrix shape can be seen corresponding to the opening of the metal mesh used for gold vapor deposition.

In the same manner as in the first embodiment, the portion of the substantially rectangular-shaped pattern unit is a portion in which a gold film (first conductor film) is formed directly under the through hole. It can be seen that Ag is formed in the through hole (sealing portion). In the SEM cross-sectional observation, the filling rate of Ag in the through-hole of the plugging portion is 70 to 100%.

A portion of the lattice pattern other than the plurality of substantially rectangular-shaped pattern units is a portion in which an aluminum film (second conductive film) is formed directly under the through hole, and the through hole still maintains a void, and is not in the through hole. See Ni formation (unsealed portion).

In the same manner as in the first embodiment, it was confirmed that Ag was selectively formed inside the through holes of a part of the plurality of through holes of the pore structure.

In the SEM observation after the dissolution treatment of the unsealed portion, in the same manner as in Example 2, it was observed that the unsealed portion was removed from the opening side to a depth of about 30 μm with respect to the through hole length of 40 μm. Further, in the same manner as in the second embodiment, it was observed that the anodized alumina of the plugged portion was partially removed, and the conductive system formed in the plurality of through holes constituting one of the plugged portions protruded from the anodized alumina and mutually In close contact, the front end portion of the plugging portion is substantially tapered.

(Example 5)

The electroporation film composed of a gold film and an aluminum film was used as the electrode layer, and the pore structure was electroplated with a Mo—Ni alloy (Mo:Ni (mass ratio)=20:80) instead of Ni, and the same procedure as in Example 2 was carried out. The film was carried out to obtain an anisotropic conductor film. The plating conditions of the Mo-Ni alloy are 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: 8.0~11.0

. Current density: 5.0 mA/cm ²

. Processing time: 120 minutes

The SEM surface observation of the fine pore structure after electroplating was carried out.

In the same manner as in the first embodiment, a pattern in which a plurality of substantially rectangular-shaped pattern units are formed in a matrix shape can be seen corresponding to the opening of the metal mesh used for gold vapor deposition.

In the same manner 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 directly under the through hole, and a case where a Mo—Ni alloy is formed in the through hole can be seen. Hole). In the SEM cross-sectional observation, the filling ratio of Mo-Ni in the through-holes of all the plugged portions was 100%, and unevenness in the filling ratio was not observed. The SEM surface photograph was similar to the SEM photograph (upper right diagram of FIG. 13) of the plugged portion of Example 8 to be described later, and Mo-Ni was observed to reach the surface in all the through holes.

A portion of the lattice pattern other than the plurality of substantially rectangular-shaped pattern units is a portion in which an aluminum film (second conductive film) is formed directly under the through hole, and the through hole still maintains a void, and is not in the through hole. See Mo-Ni alloy formation (unsealed portion).

In the same manner as in the first embodiment, it was confirmed that a Mo-Ni alloy was selectively formed inside a through hole of a part of the plurality of through holes of the pore structure.

In the SEM observation after the dissolution treatment of the unsealed portion, in the same manner as in the example 2, it was observed that the unsealed portion was removed from the opening side to a depth of about 30 μm with respect to the through hole length of 40 μm. Further, in the same manner as in the second embodiment, it was observed that the anodized alumina of the plugged portion was partially removed, and the conductive system formed in the plurality of through holes constituting one of the plugged portions was formed. The anodized alumina protrudes in close contact with each other, and the tip end portion of the plugged portion becomes substantially tapered.

(Example 6)

A metal mesh having a mesh size of 16 μm and a wire diameter of 16 μm was used in the same manner as in Example 2 except that a mask used for forming a gold film (first conductive film) by a vapor deposition method was used. Anisotropic conductor film.

The SEM surface observation of the fine pore structure after plating was performed.

The obtained SEM surface photograph is shown in Fig. 8.

In the same manner as in the first embodiment, in the opening of the metal mesh used for the gold vapor deposition, a pattern of a plurality of substantially rectangular-shaped pattern cells of 16 μm × 16 μm in a space of 16 μm was formed.

In the same manner as in the first embodiment, the portion of the substantially rectangular-shaped pattern unit is a portion in which a gold film (first conductor film) is formed directly under the through-hole, and it is seen that Ni is formed in the through-hole (sealing portion). . In the SEM cross-sectional observation, the filling rate of Ni in the through-hole of the plugging portion was 70 to 100%.

A portion of the lattice pattern other than the plurality of substantially rectangular-shaped pattern units is a portion in which an aluminum film (second conductive film) is formed directly under the through-hole, and the through-hole still maintains a void, and the through-hole is not See Ni formation (unsealed portion).

In the same manner as in the first embodiment, it was confirmed that Ni was selectively formed inside the through holes of a part of the plurality of through holes of the pore structure.

In the SEM observation after the dissolution treatment of the unsealed portion, the same as in Example 2, it was observed that the length of the through-hole was 40 μm, and the pores were not sealed. The portion is removed from the opening side to a depth of about 30 μm. Further, in the same manner as in the second embodiment, it was observed that the anodized alumina of the plugged portion was partially removed, and the conductive system formed in the plurality of through holes constituting one of the plugged portions protruded closer to each other than the anodized alumina. The front end portion of the plugging portion is substantially tapered.

(Example 7)

An anisotropic conductor film as shown in FIG. 3 was produced in the same manner as in Example 2 except that the order of formation 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.

On one side of the obtained pore structure (the side having the side of the barrier layer), a metal mesh having a mesh size of 8 μm and a wire diameter of 8 μm was used as a mask, and a 60 nm thick aluminum was formed by a vacuum evaporation apparatus. Film (Al film, second conductor film). The vapor deposition conditions are as follows.

. Evaporation source: 99.99% aluminum wire (Nirako)

. Vacuum degree: 1×10-4Pa or less

. Substrate temperature: 25 ° C

. Evaporation speed: 10nm/min.

Then, the aluminum vapor-deposited surface of the pore structure was used, and a vacuum filming apparatus ("VE-2030" manufactured by Vacuum Device Co., Ltd.) was used to form a gold film having a thickness of 150 nm on the entire surface (Au film, first conductive). Body membrane). The vapor deposition conditions are as follows.

. Evaporation source: 99.99% gold wire (manufactured by Nirako Co., Ltd.)

. Vacuum degree: 1×10-4Pa or less

. Substrate temperature: 25 ° C

. Evaporation speed: 5nm/min.

Next, a conductor film made of an aluminum film and a gold film was used as an electrode layer, and Ni was plated and deposited on the pore structure under the same conditions as in Example 1.

The SEM surface observation of the fine pore structure after plating was performed.

The obtained SEM surface photograph is shown in Fig. 9.

The reverse pattern of Example 1 can be seen. A portion (8 μm × 8 μm) of the substantially rectangular pattern unit is a portion in which an aluminum film (second conductor film) is formed directly under the through hole, and the through hole still retains a void, and no Ni is formed in the through hole ( Unsealed part).

A portion of the lattice pattern other than the substantially rectangular-shaped pattern unit is a portion in which a gold film (first conductor film) is formed directly under the through-hole, and a case where Ni is formed in the through-hole (a plug-in portion) can be seen. In the SEM cross-sectional observation, the filling rate of Ni in the through-hole of the plugging portion is 70 to 100%.

As shown in FIG. 3, it was confirmed that Ni was selectively formed inside the through hole of a part of the plurality of through holes of the pore structure.

In the SEM observation after the dissolution treatment of the unsealed portion, in the same manner as in Example 2, it was observed that the unsealed portion was removed from the opening side to a depth of about 30 μm with respect to the through hole length of 40 μm. Further, in the same manner as in the second embodiment, it was observed that the anodized alumina in the plugged portion was partially removed, and the conductive system formed in the plurality of through holes constituting the one plugging portion protruded closer to each other than the anodized alumina. The front end portion of the plugging portion is formed into a substantially tapered shape.

(Comparative Example 1)

Except for one side of the pore structure (on the side of the barrier layer) In the vapor deposition method, a gold film (whole film) is formed as a first conductor film on substantially the entire surface without using a mask, and the second conductor film is not formed, and the unsealed portion is not dissolved. The anisotropic conductor film was produced in the same manner as in Example 1.

When SEM observation of the pore structure after electroplating was performed, it was confirmed that Ni was formed in the inside of all the through-holes of the pore structure (there is 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 used instead of Ni.

(I-V characteristics in vacuum and determination of electric field concentration factor β)

The I-V characteristics and the electric field concentration coefficient β in the vacuum were measured for the anisotropic conductor films obtained in Examples 1 to 7 and Comparative Examples 1 and 2.

The obtained ITO film-attached glass substrate was bonded to the obtained anisotropic conductor film by using indium as a cathode substrate.

A glass substrate with an ITO film was prepared as an anode substrate.

An alumina plate is disposed as a separator between the cathode substrate and the anode substrate.

The distance between the anisotropic conductor film and the anode substrate was 0.5 mm.

The obtained sample was placed in a vacuum chamber to have a vacuum of 1 × 10 -4 Pa or less. A DC power source ("HJPM-5N1.2-SP" manufactured by MATSUSADA PRECISION Co., Ltd.) was used to apply a voltage between the cathode electrode and the anode electrode.

The current density discharged to the vacuum is expressed by the following formula of Fowler-Nordheim.

I=sAF2/φ exp(-B3/2/F), F=β E=β V/d

However, in the above formula, the I-type electric field emission current, the s-type electric field emission area, the A-system constant, the electric field strength of the F-type conductor tip, the φ-system work function, the B-system constant, the β-system electric field concentration factor, and the E-system plate The electric field strength, the V-system applied voltage, and the distance between the d-based cathode substrate and the anode substrate.

The electric field concentration coefficient β (dimensionless) indicates a coefficient which is increased in comparison with the electric field strength of the flat plate in response to the shape of the tip end portion or the geometry of the element.

With respect to the anisotropic conductor film, the I-V characteristic in a vacuum was analyzed by the above-mentioned Fowler-Nordheim equation, and the electric field concentration coefficient β was measured.

Further, in each of the examples, the ratio of the current value after one hour from the initial current value (100 μA) was continuously applied for 1 hour.

The main manufacturing conditions and evaluation results of each example are shown in Tables 1 and 2.

In the initial state, in the examples 1 to 7, higher characteristics were obtained than in the comparative examples 1 and 2.

In Comparative Examples 1 and 2, the current value after the voltage application for 1 hour was 10% or less of the initial value, and the durability was insufficient. On the other hand, in Examples 1 to 7, even when the voltage was applied for 1 hour. After that, the current value is maintained at the same level as the initial value, and the durability is greatly improved.

(Manufacture of FEL)

FEL was produced 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 using indium by soldering to form 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 is disposed as a separator between the cathode substrate and the anode substrate.

The distance between the anisotropic conductor film and the anode substrate was set to 0.5 mm.

The obtained apparatus was placed in a vacuum chamber to have a vacuum of 1 × 10 -4 Pa or less. A DC power source ("HJPM-5N1.2-SP" manufactured by MATSUSADA PRECISION Co., Ltd.) was used to apply a voltage between the cathode electrode and the anode electrode.

For any of the FELs obtained by using the anisotropic conductor films of Examples 1 to 7 and Comparative Examples 1 and 2, blue-green luminescence was also visually confirmed.

A luminescence photograph according to an optical microscope of a device obtained by using the anisotropic conductor film of Example 1 is shown in FIG.

When the luminance of the device obtained by using the anisotropic conductor films of Examples 1 to 7 and Comparative Examples 1 and 2 was measured using a luminance meter ("BM-9" manufactured by TOPCON Co., Ltd.), either of them was 8000 cd/ m ² . Furthermore, here, the initial luminosity of the luminescence is consistent in each case.

The ratio of the luminance to the initial value at the time of continuous light emission of the FEL obtained by using the anisotropic conductor film of each example was evaluated. will The evaluation results are shown in Table 2.

In Comparative Examples 1 and 2, the luminance after one hour of continuous light emission was 10% or less of the initial value, and the durability was insufficient. On the other hand, in Examples 1 to 7, even after 1 hour of continuous light emission It also maintains the same degree of brightness as the initial one, showing a significant increase in durability.

(Reference example 1)

In the same manner as in Example 1, a pore structure (anodized alumina) having a plurality of through holes having a thickness of 50 μm was obtained.

Then, one side of the pore structure (the side having the side of the barrier layer) was formed on the entire surface by a vacuum vapor deposition apparatus ("VE-2030" manufactured by Vacuum Device Co., Ltd.), and the mask was formed without using a mask. A 60 nm thick gold film (Au film, conductor film). The vapor deposition conditions are as follows.

. Evaporation source: 99.9% gold wire (Nirako company)

. Vacuum degree: 1×10-4Pa or less

. Substrate temperature: 25 ° C

. Evaporation speed: 5nm/min.

Next, using a gold film as an electrode layer, a Mo-Ni alloy (Mo:Ni (mass ratio) = 36:64) was electroplated on the pore structure by a direct current method. The plating conditions are as follows.

. Electrolytic bath: a mixture of 0.2 M nickel sulfate ‧ 6 hydrate, 0.1 M sodium molybdate and 0.3 M sodium gluconate

. Counter electrode: Pt electrode

. Bath temperature: 25 ° C

. pH: use ammonia to adjust to 10

. Voltage: -1.8V vs.Ag/AgCl

. Processing time: 450 minutes

SEM observation of the pore structure in the middle of the plating was carried out.

The obtained SEM cross-sectional photograph is shown in Fig. 12.

In the figure, AAO represents a fine pore structure (anodized alumina), and AAO_Mo36-Ni64 (%) indicates that a Mo-Ni alloy is formed in a plurality of through holes of a fine pore structure (anodized alumina) AAO ( Mo: Ni (mass ratio) = 36: 64). In the figure, the solder is an alloy film mainly composed of Sn.

In addition, this SEM photograph is a photograph of a sample of the obtained anisotropic conductor film which is obtained by using an alloy solder containing Sn as a main component on a glass substrate with an ITO film.

It can be seen that the Mo-Ni alloy system grows to a height of 6.5 μm in the through hole of the fine pore structure. Although it is a mid-stage of electroplating, the length of the Mo-Ni alloy grown in the through-hole of the pore structure is not uneven and is very uniform.

SEM observation of the pore structure after plating was performed.

In the SEM cross-section observation, the filling ratio of Mo-Ni in all the through-holes was 100%, and no unevenness in filling ratio was observed.

The SEM surface photograph was similar to the SEM photograph (the upper right diagram of FIG. 13) of the plugged portion of Example 8 to be described later, and Mo-Ni was observed to reach the surface in all the through holes.

(Example 8)

In the same manner as in Example 1, a pore structure (anodized alumina) having a plurality of through holes having a thickness of 50 μm was obtained.

Next, one of the fine pore structures (the surface having the barrier layer side) was made of a metal mesh having a mesh size of 8 μm and a wire diameter of 8 μm as a mask, and a vacuum vapor deposition apparatus (Vacuum Device Co., Ltd., "VE") was used. -2030") A gold film (Au film, first conductor film) having a thickness of 60 nm was formed. The vapor deposition conditions are as follows.

. Evaporation source: 99.9% gold wire (Nirako company)

. Vacuum degree: 1×10-4Pa or less

. Substrate temperature: 25 ° C

. Evaporation speed: 5nm/min.

Then, a vacuum film deposition apparatus ("VE-2030" manufactured by Vacuum Device Co., Ltd.) was used to form a 150 nm thick aluminum film on the entire surface of the pore structure (Al film, second). Conductive film). The vapor deposition conditions are as follows.

. Evaporation source: 99.99% aluminum wire (Nirako)

. Vacuum degree: 1×10-4Pa or less

. Substrate temperature: 25 ° C

. Evaporation speed: 10nm/min.

Next, a conductor film made of a gold film and an aluminum film was used as an electrode layer, and a Mo-Ni alloy (Mo:Ni (mass ratio) = 36:64) was plated and deposited on the pore structure. The plating conditions are as follows.

. Electrolytic bath: a mixture of 0.2 M nickel sulfate ‧ 6 hydrate, 0.1 M sodium molybdate and 0.3 M sodium gluconate

. Counter electrode: Pt electrode

. Bath temperature: 25 ° C

. pH: Adjust to 10 using ammonia water

. Voltage: -1.8V vs.Ag/AgCl

. Processing time: 450 minutes

SEM observation of the pore structure after plating was performed.

The obtained SEM surface photograph is shown in Fig. 13.

In Fig. 13, the upper left image is a SEM surface photograph at a magnification of 1000 times. Corresponding to the pattern of the openings of the metal mesh used for the gold vapor deposition, it is seen that a plurality of substantially rectangular-shaped pattern units of 8 μm × 8 μm are formed in a matrix shape with a space of 8 μm.

In Fig. 13, the right image is a SEM photograph of a magnification of 60,000 times. This photograph is a magnified portion of the above-described substantially rectangular-shaped pattern unit. This portion is a portion in which a gold film (first conductor film) is formed directly under the through hole. It can be seen that Mo-Ni is formed inside the through hole (sealing portion). When the SEM cross-section was observed, the filling ratio of Mo-Ni in the through-holes of all the plugged portions was 100%, and the filling ratio was not uneven.

In Fig. 13, the lower image is a SEM surface photograph with a magnification of 150,000 times. This photograph is a magnified portion of a lattice pattern other than the plurality of substantially rectangular-shaped pattern units described above. This portion is a portion in which an aluminum film (second conductor film) is formed directly under the through hole. All of the through holes remained hollow, and no Mo-Ni was formed in the through holes (unsealed portions).

It was confirmed that Mo-Ni was selectively formed inside the through hole of a part of the plurality of through holes of the pore structure.

In the same manner as in the first to seventh embodiments, 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 remove at least the unsealed portion. portion.

(Comparative Example 3)

The structure before the dissolution treatment of the unsealed portion in Example 1 was used as Comparative Example 3 and was evaluated. The SEM photograph of Comparative Example 3 is shown in Fig. 5.

(XRD analysis)

XRD (X-ray diffraction) analysis was performed on the anisotropic conductor films obtained in Reference Example 1 and Comparative Example 1. The obtained XRD pattern is shown in FIGS. 14A and 14B.

In Reference Example 1, the Mo-Ni alloy was found to have a diffraction peak at the same position as Ni of Comparative Example 1. This peak is derived from the peak of Ni(220) crystal.

In Reference Example 1, the Mo-Ni alloy system was excellent in crystallinity similarly to Ni. Further, it is considered that the Mo system in the Mo-Ni alloy in Reference Example 1 exists in an amorphous state in the Ni (220) crystal.

(I-V characteristics in vacuum and determination of electric field concentration factor β)

The anisotropic conductor films obtained in Reference Example 1, Example 8, and Comparative Examples 1 and 3 were measured in the same manner as in Examples 1 to 7, and the I-V characteristics and the electric field concentration coefficient β in the vacuum were measured.

The main manufacturing conditions and evaluation results of each example are shown in Tables 3 and 4.

In the initial state, in the case of Reference Example 1, high characteristics were obtained as compared with Comparative Example 1, and in Comparative Example 8, high characteristics were obtained as compared with Comparative Example 3.

In Comparative Example 1, the halving time of the initial current density of 3 μA/cm ² was about 5 hours. On the other hand, in Reference Example 1 and Example 8, the halving time was extended to 10 hours or more. It can be seen that the durability of the conductor (emitter) in the through hole is greatly improved.

(Manufacture of FEL)

The anisotropic conductor film obtained in Example 8 was used in the same manner as in Examples 1 to 7, and FEL was produced.

In the same manner as in Examples 1 to 7, the blue-green luminescence was confirmed by visual observation. When the luminance of the obtained device was measured using a luminance meter ("BM-9" manufactured by TOPCON Co., Ltd.), it was 6000 cd/m ² .

This application is based on the Japanese application No. 2013-247354, which was filed on November 29, 2013, and the Japanese application No. 2013-259330, which was filed on December 26, 2013. Priority is given to all of its disclosures.

The present invention is not limited to the above-described embodiments and examples, and may be modified as appropriate without departing from the spirit of the invention.

[Industrial availability]

The anisotropic conductor film of the present invention and the method for producing the same can be preferably applied to an electron emission element used in an FE device such as FEL or FED.

1‧‧‧ anisotropic conductor film

21‧‧‧Pore structure

21H‧‧‧through hole

21D‧‧‧ openings

21S‧‧‧ face

22‧‧‧Electrical conductor (emitter, electron source)

30‧‧‧Electrical film (cathode layer)

31‧‧‧1st conductor film

32‧‧‧2nd conductor film

SA‧‧‧Blocking Department

NSA‧‧‧Unsealed

Claims (19)

An anisotropic conductor film comprising an anisotropic conductor film having a pore structure and an electric conductor, the pore structure being anodized by a plurality of through holes extending in a cross direction with respect to a plane direction In the case of a metal film, the conductive system is selectively formed inside a through hole of a part of the plurality of through holes, and at least a portion of the unsealed portion in which the conductor is not formed inside the through hole is removed. The anisotropic conductor film of claim 1, wherein the top of the conductor is protruded from the pore structure. The anisotropic conductor film of claim 1, wherein the conductive system formed inside the through hole contains a material selected from the group consisting of Ag, Au, Cd, Co, Cu, Fe, Mo, Ni, Sn, W, and Zn. A metal or a metal compound of at least one metal element constituting the group. The anisotropic conductor film of claim 1, wherein the conductive system formed inside the through hole comprises an induction eutectoid type alloy. The anisotropic conductor film according to claim 4, wherein the induced eutectoid alloy contains at least one first metal element and at least one second metal element, and the first metal element can be individually in the through hole In the plating, the second metal element has a higher melting point than the first metal element, and is not plated in the through hole alone, but can induce eutectoid precipitation with the first metal element. The anisotropic conductor film according to claim 1, wherein the first conductor film and the second conductor film are provided on one of the pore structure, and the first conductor film is formed to cover the conductive material The opening of the through hole of the body is capable of plating a material of the conductor, and the second conductor film covers an opening of the through hole in which the conductor is not formed, and the first conductive is connected It is formed by a body film, and it is difficult to plate the material of the above-mentioned conductor. The anisotropic conductor film according to claim 6, wherein the first conductor film covers an opening of the through hole in which the conductor is formed, and does not cover the through hole in which the conductor is not formed inside. The pattern of the opening of the hole is formed by dividing into a plurality of regions, and the second conductor film is formed so as to cover the opening portion of the through hole in which the conductor is not formed inside, and the second conductor film is formed into a plurality of regions. The pattern units of the first conductor film are formed to be connected to each other. The anisotropic conductor film according to claim 6, wherein the second conductor film covers the opening of the through hole in which the conductor is not formed inside, and does not cover the through hole in which the conductor is formed inside The pattern of the opening of the hole is formed by dividing into a plurality of regions, and the first conductor film is formed by covering an opening of the through hole in which the conductor is formed inside, and is formed by dividing the region into a plurality of regions. The pattern units of the second conductor film are formed to be connected to each other. The anisotropic conductor film of claim 6, wherein the first conductor film comprises a material selected from the group consisting of Au, Ag, Cu, Fe, Ni, Sn, and Zn. a metal or a metal compound of at least one metal element of the group; the second conductor film includes at least one metal element selected from the group consisting of Al, Mg, Si, Ti, Mo, and W Metal or metal compound, or stainless steel. A method for producing an anisotropic conductor film, which is the method for producing an anisotropic conductor film according to any one of claims 1 to 9, which has the following steps: a step of preparing the pore structure ( A); a step (B) of forming the conductive body inside a part of the plurality of through holes; and a step (C) of removing at least a part of the unsealed portion. The method for producing an anisotropic conductor film according to claim 10, wherein the step (A) comprises the step (AX) of anodizing at least a portion of the anodized metal body to obtain a plurality of non-through holes. An anodized metal film with a barrier layer; and step (AY), when the remaining portion of the anodized metal body is present after the step (AX), the remaining portion is removed from the barrier layer When there is no remaining portion of the anodized metal body after the step (AX), the barrier layer is removed to form the non-through hole as the through hole. The method for producing an anisotropic conductor film according to claim 10, wherein the step (B) includes a step (BX) of forming a first conductor film and a second conductor film on one of the pore structure bodies, The first conductor film is covered An opening of the through hole of the conductor is formed inside, and a material of the conductor can be plated, and the second conductor film covers an opening of the through hole in which the conductor is not formed. The first conductor film is connected to be formed, and it is difficult to plate the material of the conductor; and in the step (BY), the first conductor film and the second conductor film are used as an electrode layer. Electroplating is performed on the above-mentioned fine pore structure. The method for producing an anisotropic conductor film according to claim 10, wherein in the step (B), a plating solution containing at least one first metal element and at least one second metal element is used in the plurality of through-layers Electroplating is performed inside a part of the through holes of the holes, and the first metal element can be plated alone in the through holes, and the second metal element has a higher melting point than the first metal element, and the single metal element cannot be used alone. Although the inside of the through hole is plated, it is possible to induce eutectoid precipitation with the first metal element. The method for producing an anisotropic conductor film according to claim 10, wherein in the step (C), at least a part of the unsealed portion is dissolved and removed. A device comprising the anisotropic conductor film according to any one of claims 1 to 9. An electron emission device comprising the anisotropic conductor film of claim 1, and comprising an electron source and an electrode layer, wherein the electron source is formed of the conductor formed in the through hole, the electrode layer It is formed on one side of the pore structure and is electrically connected to the electron source. An electron emission component having an anisotropy as claimed in claim 6 The conductor film is formed and includes an electron source and an electrode layer. The electron source is formed of the conductor formed in the through hole, and the electrode layer includes the first conductor film and the second conductor film. A field emission lamp comprising a first electrode substrate and a second electrode substrate, wherein the first electrode substrate includes the electron emission element of claim 16 or 17, and the second electrode substrate is interposed between the first electrode substrate The vacuum space is disposed opposite to each other and includes an electrode layer and a phosphor layer. A field emission display comprising a first electrode substrate and a second electrode substrate, wherein the first electrode substrate is displayed by modulation of light emitted from the phosphor layer, the first electrode substrate comprising the request item 16 or In the electronic discharge device of FIG. 17, the second electrode substrate is disposed to face the first electrode substrate with a vacuum space interposed therebetween, and includes an electrode layer and a phosphor layer.