WO2022138150A1 - Manufacturing method for structure - Google Patents

Abstract

Provided is a manufacturing method for a structure having excellent workability. This manufacturing method for a structure has: a pattern formation step for forming an electrically insulating pattern film on one surface of an electrically insulating film which has multiple through-holes extending in a thickness direction; a first metal layer formation step for forming a first metal layer in regions of the one surface other than the regions where the pattern film is formed; a filling step for filling, with a metal, through-holes in contact with the first metal layer among the multiple through-holes; and a second metal layer formation step for forming a second metal layer in regions of the other surface of the insulating film where the first metal layer is present on the one surface located on the opposite side.

Description

Structure manufacturing method

The present invention is a structure in which a metal is filled in the through holes in a pattern and metal layers are formed on both sides of the anodized film having a plurality of through holes extending in the thickness direction. Regarding the manufacturing method of.

Conventionally, metal foil has been used for various purposes such as electrically conductive members. Metal leaf is also used for decoration and the like. Examples of the metal foil include aluminum foil, copper foil, titanium foil and the like. The thickness of the metal foil is about several hundred μm, for example, about 200 μm.

As described above, the metal foil has a thickness of about several hundred μm, and is easily deformed when drilling or cutting, and has poor workability. At present, there is no metal foil with excellent workability. Therefore, even when the metal foil is individualized, it cannot be properly individualized.
An object of the present invention is to provide a method for producing a structure having excellent processability.

In order to achieve the above object, one aspect of the present invention is to provide electrical insulation on one surface of an electrically insulating insulating film having a plurality of through holes extending in the thickness direction. A pattern forming step of forming a pattern film to have, a first metal layer forming step of forming a first metal layer in a region other than the pattern film forming region on one surface, and a plurality of through holes. , The filling step of filling the through hole in contact with the first metal layer with metal, and the second metal layer in the region where the first metal layer exists on one of the other surfaces of the insulating film on the opposite side. The present invention provides a method for manufacturing a structure, which comprises a second metal layer forming step for forming the structure.
In addition, another aspect of the present invention is to form a patterned film having electrical insulating properties on one surface of an insulating film having electrical insulating properties having a plurality of through holes extending in the thickness direction. A first metal layer is formed in a pattern forming step, a filling step of filling through holes other than those in contact with the pattern film among a plurality of through holes, and a region of one surface other than the pattern film forming region. The second metal forming the second metal layer in the region where the first metal layer exists on the opposite surface of the other surface of the insulating film and the first metal layer forming step of forming the first metal layer. It provides a method for manufacturing a structure having a layer forming step.

It is preferable that the first metal layer in the first metal layer forming step and the second metal layer in the second metal layer forming step are made of the same metal.
It is preferable that the first metal layer in the first metal layer forming step and the second metal layer in the second metal layer forming step are made of Cu.
In the first metal layer forming step, it is preferable to form the first metal layer on one surface by covering the pattern film.
The insulating film is preferably an anodized film.

According to the present invention, it is possible to provide a structure having excellent workability.

It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the structure of embodiment of this invention. It is a schematic plan view which shows one step of the 1st example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the structure of embodiment of this invention. It is a schematic sectional drawing which shows an example of the structure obtained by the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows the other example of the structure obtained by the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the anodic oxide film used in the manufacturing method of the structure of the embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the anodic oxide film used in the manufacturing method of the structure of the embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the anodic oxide film used in the manufacturing method of the structure of the embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the anodic oxide film used in the manufacturing method of the structure of the embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the anodic oxide film used in the manufacturing method of the structure of the embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 3rd example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 3rd example of the manufacturing method of the structure of embodiment of this invention. It is a schematic cross-sectional view which shows one step of the 3rd example of the manufacturing method of the structure of embodiment of this invention.

Hereinafter, a method for manufacturing the structure of the present invention will be described in detail based on the preferred embodiments shown in the accompanying drawings.
It should be noted that the figures described below are exemplary for explaining the present invention, and the present invention is not limited to the figures shown below.
In the following, "-" indicating the numerical range includes the numerical values described on both sides. For example, when ε _a is a numerical value α _b to a numerical value β _c , the range of ε _a is a range including the numerical value α _b and the numerical value β _c , and is expressed in mathematical symbols as α _b ≤ ε _a ≤ β _c .
Humidity and time include error ranges generally acceptable in the art, unless otherwise stated.

The thickness of the metal foil is about several hundred μm, and the metal foil is easily deformed and difficult to process when drilling or cutting. However, as a result of diligent studies, metal layers were formed on both sides of the metal filled in a pattern and the insulating film filled with metal in a plurality of through holes extending in the thickness direction of the insulating film such as an anodized film. It was found that the provision is excellent in processability and that the metal can be individualized into an arbitrary pattern, which led to the present invention. Hereinafter, the method for manufacturing the structure will be specifically described.

[First example of a method for manufacturing a structure]
1 and 3 to 7 are schematic cross-sectional views showing a first example of the method for manufacturing a structure according to an embodiment of the present invention in order of steps. FIG. 2 is a schematic plan view showing one step of the first example of the method for manufacturing a structure according to an embodiment of the present invention, and is a plan view of FIG.
In the method for manufacturing the structure, for example, the laminated body 10 shown in FIG. 1 is prepared. The laminate 10 has an insulating film 14 having an electrically insulating property formed on the substrate 12. The insulating film 14 is composed of, for example, an anodized film. The substrate 12 is, for example, a metal substrate. For the substrate 12, for example, an aluminum substrate is used as the metal substrate. In this case, the anodic oxide film 34 (see FIG. 11), which is the insulating film 14, is an aluminum anodic oxide film.
The insulating film 14 shown in FIG. 1 has a plurality of through holes 15 extending in the thickness direction. The bottom surface 15c of the through hole 15 is exposed on the substrate 12.

A pattern film 16 having electrical insulation is formed on one surface of the insulating film 14, for example, the surface 14a. As shown in FIG. 2, the pattern film 16 is, for example, a ring-shaped pattern and has a closed shape. The pattern film 16 divides the surface 14a of the insulating film 14 into a first region 18a surrounded by the pattern film 16 and a second region 18b outside the pattern film 16. Both the first region 18a and the second region 18b are regions other than the region where the pattern film 16 is formed.

For example, a photolithography method is used as the pattern forming step for forming the pattern film 16. In this case, for example, a resist film (not shown) is formed on the entire surface 14a of the insulating film 14.
Next, if the resist film is a negative type, only the region where the pattern film 16 is formed is exposed in a pattern on the resist film. After the exposure, the unexposed portion is removed by a developing process to form the pattern film 16 shown in FIGS. 1 and 2. As described above, the pattern film 16 is composed of, for example, a resist film.
Further, if the resist film is a positive type, the exposed portion is removed by the development process, so that the exposure pattern has a different light-shielding region from the negative type. When the resist film is of the positive type, a pattern that shields the region where the pattern film 16 is formed is used, and only the region other than the region where the pattern film 16 is formed is exposed in a pattern.

The resist film is not particularly limited, and a known negative or positive resist film used in the photolithography method can be used.
As the exposure light of the resist film used for forming the pattern film 16, light having a wavelength corresponding to the resist film is appropriately used.
When the pattern of the pattern film 16 is exposed, for example, a photomask is used, but the present invention is not limited thereto. For the exposure of the pattern film 16, an electron beam lithography method for drawing a pattern using an electron beam without using a mask can also be used.

Next, as shown in FIG. 3, a first metal layer forming step of forming the first metal layer 20 on the surface 14a of the insulating film 14 is carried out. In the first metal layer forming step, the first metal layer 20 is formed on the surface 14a of the insulating film 14 in the first region 18a and the second region 18b, which are regions other than the formation region of the pattern film 16. In the first metal layer forming step, for example, the first metal layer 20 is formed to have the same thickness as the pattern film 16.
The first metal layer 20 in the first region 18a and the first metal layer 20 in the second region 18b are electrically insulated by the pattern film 16.
The first metal layer 20 is formed by, for example, a plating method, a vapor deposition method, or a sputtering method. The first metal layer 20 is made of, for example, Cu. The thickness hm of the first metal layer 20 (see FIG. 9) can be adjusted by adjusting the film formation time. When the first metal layer 20 is formed beyond the pattern film 16, for example, the excess is removed by polishing to adjust the thickness hm of the first metal layer 20 (see FIG. 9). ..

Next, the conductive layer 21 that covers the surface 20a of the first metal layer 20 is formed. The conductive layer 21 is also formed on the pattern film 16 and is formed so as to straddle the first metal layer 20 of the first region 18a and the second region 18b. The conductive layer 21 electrically connects the first metal layer 20 in the first region 18a and the first metal layer 20 in the second region 18b, and conduction is possible.
For the conductive layer 21, for example, a vapor deposition method, a sputtering method or a plating method is used. The conductive layer 21 is not particularly limited as long as it has conductivity, and may be made of a metal or an alloy, and the conductive layer 21 is made of, for example, Au or Cu. When the conductive layer 21 is composed of Au, it is formed by, for example, a sputtering method. From the viewpoint of ensuring conductivity, the thickness of the conductive layer 21 is preferably 500 nm or more, and the upper limit of the thickness of the conductive layer 21 is preferably 1 μm.
The conductive layer 21 may be the same metal as the first metal layer 20 from the viewpoint of suppressing an increase in electrical resistance at the bonding interface between the first metal layer 20 and the conductive layer 21. For example, when the first metal layer 20 is formed of Cu, the conductive layer 21 is formed of Cu.

Next, as shown in FIG. 5, the substrate 12 is removed, and the bottom surface 15c of the through hole 15 is exposed on the back surface 14b of the insulating film 14. The step of removing the substrate 12 is called a substrate removing step.
When the substrate 12 is removed, the support 24 is provided on the laminated structure of the insulating film 14, the pattern film 16, the first metal layer 20, and the conductive layer 21 by using the resin base material 22. By attaching the support 24, the process of removing the substrate 12 and the like can be easily performed.

The structure of the resin base material 22 is not particularly limited as long as the above-mentioned laminated structure and the support 24 can be adhered to each other. For example, Q-chuck (registered trademark) (manufactured by Maruishi Sangyo Co., Ltd.) ), Or a double-sided type Riva Alpha (registered trademark) manufactured by Nitto Denko KK can be used.
Since the laminated structure can be easily handled in the above-mentioned substrate removing step, it is preferable that the support 24 has the same outer shape as the above-mentioned laminated structure.
For the support 24, for example, a silicon substrate is used. The support 24 is not limited to the silicon substrate, and for example, a ceramic substrate such as SiC, SiC, GaN and alumina (Al ₂ O ₃ ), a glass substrate, a fiber-reinforced plastic substrate, and a metal substrate may be used. can. The fiber reinforced plastic substrate also includes a FR-4 (Flame Retardant Type 4) substrate, which is a printed wiring board.

Next, of the plurality of through holes 15 of the insulating film 14, a filling step of filling the through holes 15 in contact with the first metal layer 20 with metal is carried out. By the filling step, the through hole 15 in contact with the first metal layer 20 is filled with metal to form a columnar body 26. In the filling step, it is preferable not to fill the through hole 15 with which the pattern film 16 having electrical insulating property comes into contact with metal.
In the filling step, for example, the through hole 15 is filled with metal by using electrolytic plating. In electrolytic plating, the first metal layer 20 is used as an electrode for electrolytic plating. Plating proceeds from the first metal layer 20 exposed in the through hole 15 as a starting point. As a result, as shown in FIG. 6, of the plurality of through holes 15 of the insulating film 14, the inside of the through holes 15 with which the first metal layer 20 is in contact is filled with metal, and the first metal layer 20 is in contact with the inside. The columnar body 26 is formed. The columnar body 26 is made of metal and has conductivity.

Next, a second metal layer forming step of forming the second metal layer 28 in the region where the first metal layer 20 exists on the opposite surface of the other surface of the insulating film 14 is carried out. .. For example, on the opposite surface of the back surface 14b of the insulating film 14, that is, on the surface 14a of the insulating film 14, the second is in the region 18c (see FIGS. 6 and 7) in which the first metal layer 20 is present. Metal layer 28 is formed. The above-mentioned region 18c is a region facing the above-mentioned first region 18 and the second region 18b with the insulating film 14 interposed therebetween.
In the second metal layer forming step of forming the second metal layer 28 described above, for example, the first metal layer 20 is used as an electrode for electrolytic plating, and the second metal layer 28 is formed by a plating method. .. The second metal layer 28 is made of, for example, Cu. Further, the thickness hj of the second metal layer 28 (see FIG. 9) can be adjusted by adjusting the film formation time.
As described above, for example, the first metal layer 20 and the second metal layer 28 are made of the same metal, and both are made of Cu (copper). By the above steps, the structure 30 shown in FIG. 7 is obtained.
When the second metal layer 28 is formed by the plating method as described above, it can be formed without using the pattern film, and the pattern film is unnecessary. Therefore, it is not necessary to align the pattern film, and the second metal layer 28 can be easily formed.

In the structure 30, the columnar body 26 is formed in the region of the insulating film 14 in which the first metal layer 20 and the second metal layer 28 are present. Further, the first metal layer 20 and the second metal layer 28 are not provided in the region of the insulating film 14 in which the pattern film 16 is present, and the through holes 15 of the insulating film 14 are not filled with metal. .. That is, the columnar body 26 is not formed in the region of the insulating film 14 in which the pattern film 16 is present.
The structure 30 has a structure having a first metal layer 20 other than the pattern film 16, an insulating film 14 on which the columnar body 26 is formed, and a second metal layer 28, so that the strength can be increased as compared with the metal foil. It is not easily deformed when drilling or cutting, and its workability is superior to that of metal foil. As described above, the structure 30 having excellent workability can be obtained.
Further, the structure 30 has conductivity in the thickness direction Dt between the first metal layer 20 other than the pattern film 16, the insulating film 14 on which the columnar body 26 is formed, and the second metal layer 28. The conductivity is sufficiently low in the direction in which the columnar bodies 26 orthogonal to the thickness direction Dt are lined up. Moreover, in the structure 30, where the columnar body 26 is not provided in the insulating film 14, the columnar body 26 is provided because the first metal layer 20 and the second metal layer 28 are not provided either. It can be easily separated into individual pieces by using the insulating film 14 which does not exist, and has excellent workability.

Here, FIG. 8 is a schematic cross-sectional view showing an example of the structure obtained by the method for manufacturing the structure according to the embodiment of the present invention, and FIG. 9 is a schematic cross-sectional view obtained by the method for manufacturing the structure according to the embodiment of the present invention. It is a schematic cross-sectional view which shows the other example of a structure. In FIGS. 8 and 9, the same components as the structure 30 shown in FIG. 7 are designated by the same reference numerals, and detailed description thereof will be omitted.
As the structure of the structure 30, for example, the resin base material 22 and the support 24 may be removed by heating to a predetermined temperature, as shown in FIG.
Further, the structure 30 may have a structure in which the resin base material 22 and the support 24 are removed, and then the conductive layer 21 is removed as shown in FIG. For removing the conductive layer 21, for example, wet etching using a chemical solution, physical polishing using a grindstone, or CMP (chemical mechanical polishing) is used.

Further, in the structure 30 in which the conductive layer 21 is removed as shown in FIG. 9, for example, after connecting the object to be connected to the second metal layer 28, the first metal layer 20 and the columnar body are described above. The insulating film 14 on which the 26 is formed and the laminated structure 29 of the second metal layer 28 can be separated into individual pieces. Therefore, the structure 30 shown in FIG. 9 is provided on the above-mentioned support 24, and after the connection target is connected to the laminated structure 29, the connection target is connected from the support 24. The body 29 can be taken out individually. The structure 30 is foil-shaped, and the laminated structure 29 as a part thereof is also foil-shaped.
Further, since the region of the insulating film 14 where the columnar body 26 is provided can be adjusted by the pattern of the pattern film 16, the structure 30 can adjust the shape and size of the laminated structure 29 to be individualized.
Further, by providing a plurality of pattern films 16 having the same shape and size to form the structure 30, a plurality of the same laminated structure 29 can be formed in a series of steps of the method for manufacturing the structure 30. Further, by forming the structure 30 by providing a plurality of various pattern films 16 having different shapes and sizes at least one, a laminated structure 29 having different shapes and sizes from at least one can be formed. A plurality of bodies 30 can be formed in a series of steps of the manufacturing method. Moreover, by arranging the pattern film 16 on the surface 14a of the insulating film 14 without waste, the wasted space in the structure 30 can be reduced, and a plurality of laminated structures 29 can be formed with high utilization efficiency.

The structure 30 may be configured by removing the pattern film 16. When the pattern film 16 is composed of a resist film, the pattern film 16 can be removed by a known method for removing the resist film after exposure. As a method for removing the resist film, for example, there is a method using a chemical solution. In addition to this, for example, a photoexcited ashing method in which the resist film is peeled off by irradiating light such as ultraviolet rays with a chemical reaction between the gas and the resist film, and the gas is turned into plasma at a high frequency or the like and the plasma is used to make the resist film. The pattern film 16 can be removed by using a plasma ashing method for peeling.

<First example of a method for producing an anodized film>
10 to 12 are schematic cross-sectional views showing the manufacturing method of the first example of the anodized film used in the manufacturing method of the structure of the embodiment of the present invention in the order of steps.
In FIGS. 10 to 12, the same components as those shown in FIGS. 1 and 2 are designated by the same reference numerals, and detailed description thereof will be omitted.
In the method for manufacturing the first example of the anodic oxide film constituting the insulating film 14 of the structure, in the structure 30 shown in FIG. 7, the insulating film 14 is composed of the aluminum anodic oxide film 34 as an example. explain. An aluminum substrate is used to form the aluminum anodized film 34. Therefore, in the first example of the method for manufacturing a structure, first, as shown in FIG. 10, an aluminum substrate 32 is prepared.

The size and thickness of the aluminum substrate 32 are appropriately determined according to the thickness of the anodized film 34 of the structure 30 (see FIG. 7), that is, the thickness of the insulating film 14, the apparatus to be processed, and the like. The aluminum substrate 32 is, for example, a rectangular plate material. It should be noted that the present invention is not limited to the aluminum substrate, and a metal substrate capable of forming an insulating film can be used.
The thickness of the insulating film 14 is the length of the insulating film 14 in the thickness direction Dt, and is the same as the height H of the columnar body 26 (see FIG. 7). The thickness of the insulating film 14 is the length of the insulating film 14 in the thickness direction Dt. Further, the thickness of the insulating film 14 is the same as the thickness ht of the structure 30 (see FIG. 7).

Next, the surface 32a (see FIG. 10) on one side of the aluminum substrate 32 is anodized. As a result, the surface 32a (see FIG. 10) on one side of the aluminum substrate 32 is anodized, and as shown in FIG. 11, an anodized film having a plurality of through holes 15 extending in the thickness direction Dt of the aluminum substrate 32. 34 is formed. A barrier layer 35 exists at the bottom of each through hole 15. The above-mentioned anodizing step is called an anodizing treatment step.
The anodic oxide film 34 having the plurality of through holes 15 has a barrier layer 35 at the bottom of each of the through holes 15 as described above, but the barrier layer 35 shown in FIG. 11 is removed. As a result, an anodized film 34 (see FIG. 12) having a plurality of through holes 15 without a barrier layer 35 is obtained. As a result, the laminated body 10 is obtained. The laminated body 10 shown in FIG. 12 has the same configuration as the laminated body 10 shown in FIG.
The step of removing the barrier layer 35 is referred to as a barrier layer removing step.
In the barrier layer removing step, the barrier layer 35 of the anodic oxide film 34 is removed by using an alkaline aqueous solution containing ions of the metal M1 having a hydrogen overvoltage higher than that of aluminum.
The surface 34a of the anodizing film 34 corresponds to the surface 14a of the insulating film 14.

[Second example of manufacturing method of structure]
13 to 15 are schematic cross-sectional views showing a second example of the method for manufacturing a structure according to an embodiment of the present invention in order of steps. 16 and 17 are schematic cross-sectional views showing a second example of a method for manufacturing an anodized film used in the method for manufacturing a structure according to an embodiment of the present invention in order of steps. In FIGS. 13 to 17, the same components as those shown in FIGS. 1 to 9 are designated by the same reference numerals, and detailed description thereof will be omitted.

In the second example of the method for manufacturing the structure, the steps shown below are different from those in the first example of the method for manufacturing the structure.
As shown in FIG. 13, the pattern film 16 is formed on the surface 14a of the insulating film 14 having a plurality of through holes 15 extending in the thickness direction Dt. Since the method for forming the pattern film 16 is the same as the method for forming the pattern film 16 shown in FIGS. 1 and 2, detailed description thereof will be omitted.
Next, as shown in FIG. 14, the first metal layer 20 is formed on the surface 14a of the insulating film 14 in regions other than the pattern film 16, that is, in the first region 18a and the second region 18b. Since the method for forming the first metal layer 20 is the same as the method for forming the first metal layer 20 shown in FIG. 3, detailed description thereof will be omitted.
Next, as shown in FIG. 15, a conductive layer 21 that covers the surface 20a of the first metal layer 20 is formed. Since the method for forming the conductive layer 21 is the same as the method for forming the conductive layer 21 shown in FIG. 4, detailed description thereof will be omitted.

Next, as shown in FIG. 5, a support 24 is provided on the laminated structure of the insulating film 14, the pattern film 16, the first metal layer 20, and the conductive layer 21 by using the resin base material 22. Hereinafter, as shown in FIG. 6, among the through holes 15 of the insulating film 14, the through holes 15 in contact with the first metal layer 20 are filled with metal to form a columnar body 26 having conductivity.
Next, as shown in FIG. 7, a second metal layer 28 is formed on the surface 14a of the insulating film 14 in a region where the first metal layer 20 exists to obtain a structure 30.
As for the structure 30, as shown in FIG. 8, the resin base material 22 and the support 24 may be removed. As shown in FIG. 9, the conductive layer 21 may be removed, and further, the pattern film 16 may be removed.

<Second example of manufacturing method of anodized film>
In the second example of the method for producing an anodized film, the steps shown below are different from those in the first example of the method for producing an anodized film.
In the second example of the method for producing an anodized film, the aluminum substrate 32 is removed from the aluminum substrate 32 on which the anodized film 34 shown in FIG. 11 is formed, and as shown in FIG. 16, a plurality of through holes are formed. Anodized film 34 on which 15 is formed is obtained. Since the removal of the aluminum substrate 32 can utilize the substrate removal step, detailed description thereof will be omitted.

Next, the through hole 15 of the anodic oxide film 34 shown in FIG. 16 is enlarged in diameter and the barrier layer 35 is removed, and as shown in FIG. 17, the through hole 15 penetrates the anodic oxide film 34 in the thickness direction Dt. To form a plurality. By forming the substrate 12 on one surface of the anodized film 34 shown in FIG. 17, the laminate 10 shown in FIG. 1 or FIG. 18 described later can be obtained. The substrate 12 is formed of, for example, aluminum or gold. The substrate 12 may be formed by a sputtering method, a plating method, or the like.
For example, a pore wide treatment is used to increase the diameter of the through hole 15. The pore-wide treatment is a treatment in which the anodized oxide film is immersed in an acid aqueous solution or an alkaline aqueous solution to dissolve the anodized oxide film and expand the pore diameter of the through hole 15. In the pore-wide treatment, sulfuric acid, phosphoric acid, and nitrate are used. , An aqueous solution of an inorganic acid such as hydrochloric acid or a mixture thereof, or an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like can be used.

[Third example of a method for manufacturing a structure]
18 to 20 are schematic cross-sectional views showing a third example of the method for manufacturing a structure according to an embodiment of the present invention in order of steps. In FIGS. 18 to 20, the same components as those shown in FIGS. 1 to 9 are designated by the same reference numerals, and detailed description thereof will be omitted.
In the third example of the method for manufacturing the structure, the steps shown below are different from those in the first example of the method for manufacturing the structure.
For the laminated body 10 shown in FIG. 1, for example, the substrate 12 is used as an electrode, and the through hole 15 of the insulating film 14 is filled with metal by a plating method. By the metal filling step, as shown in FIG. 18, among the plurality of through holes 15, the through holes 15 other than those to which the pattern film 16 is in contact are filled with the metal to form the columnar body 26. That is, the through holes 15 in the first region 18a and the second region 18b are filled with metal to form the columnar body 26. In this case, the through hole 15 in contact with the pattern film 16 is not filled with metal because the plating solution is not supplied into the through hole 15 and the plating does not proceed. That is, the columnar body 26 is not formed in the through hole 15 in which the pattern film 16 is in contact.

Next, as shown in FIG. 19, on the surface 14a of the insulating film 14, the first region 18a and the second region 18b, which are regions other than the region where the pattern film 16 is formed, that is, the region where the pattern film 16 is formed, are formed. First, the first metal layer 20 is formed. In the first metal layer forming step, the method for forming the first metal layer 20 is the same as the method for forming the first metal layer 20 shown in FIG. 3, and therefore detailed description thereof will be omitted.
Next, as shown in FIG. 20, a conductive layer 21 that covers the surface 20a of the first metal layer 20 is formed. Since the method for forming the conductive layer 21 is the same as the method for forming the conductive layer 21 shown in FIG. 4, detailed description thereof will be omitted.

Next, as shown in FIG. 5, a support 24 is provided on the laminated structure of the insulating film 14, the pattern film 16, the first metal layer 20, and the conductive layer 21 by using the resin base material 22. Hereinafter, as shown in FIG. 6, among the through holes 15 of the insulating film 14, the through holes 15 in contact with the first metal layer 20 are filled with metal to form a columnar body 26 having conductivity.
Next, the second metal layer 28 is formed in the region 18c where the first metal layer 20 exists on the surface 14a of the insulating film 14, and the structure 30 shown in FIG. 7 is obtained. Since the method for forming the second metal layer 28 is the same as the second metal layer forming step for forming the second metal layer 28 described above, detailed description thereof will be omitted.
As for the structure 30, as shown in FIG. 8, the resin base material 22 and the support 24 may be removed. As shown in FIG. 9, the conductive layer 21 may be removed, and further, the pattern film 16 may be removed.

Although the conductive layer 21 is formed, the present invention is not limited to this, and for example, the first metal layer 20 may be formed so as to cover the pattern film 16 and also serve as the conductive layer 21. This makes it possible to omit the step of forming the conductive layer 21.

Hereinafter, each step of the structure manufacturing method and the structure of the structure will be described.
[Insulating film]
The insulating film has an electrical insulating property, and is made of, for example, an inorganic material. For example, one having an electrical resistivity of about 10 ¹⁴ Ω · cm can be used.
In addition, "consisting of an inorganic material" is a regulation for distinguishing from a polymer material, and is not limited to an insulating base material composed only of an inorganic material, but an inorganic material as a main component (50% by mass). The above).

As described above, the insulating film is composed of, for example, an anodic oxide film having electrical insulating properties. As the anodic oxide film, for example, an aluminum anodic oxide film is used because micropores having a desired average diameter are formed and through holes and conductors are easily formed as described above. However, the anodic oxide film of aluminum is not limited, and an anodic oxide film of valve metal can be used. Therefore, valve metal is used as the metal substrate.
Here, examples of the valve metal include, for example, the above-mentioned aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony and the like. Of these, an anodized aluminum film is preferable because it has good dimensional stability and is relatively inexpensive. Therefore, it is preferable to manufacture the structure using an aluminum substrate.

[Metal substrate]
The metal substrate is used for manufacturing a structure and is a substrate for forming an insulating film. As the metal substrate, for example, as described above, a metal substrate on which an anodic oxide film can be formed is used, and a metal substrate composed of the above-mentioned valve metal can be used. For example, as described above, an aluminum substrate is used as the metal substrate because it is easy to form an anodic oxide film as an insulating film.

[Aluminum substrate]
The aluminum substrate used to form the insulating film 14 is not particularly limited, and specific examples thereof include a pure aluminum plate; an alloy plate containing aluminum as a main component and containing a trace amount of a foreign element; low-purity aluminum (for example, for example). A substrate on which high-purity aluminum is vapor-deposited on (recycled material); a substrate on which the surface of silicon wafer, quartz, glass, etc. is coated with high-purity aluminum by a method such as vapor deposition or sputtering; a resin substrate on which aluminum is laminated; etc. ..

Of the aluminum substrate, the surface on one side on which the anodizing film is formed by the anodizing treatment preferably has an aluminum purity of 99.5% by mass or more, more preferably 99.9% by mass or more, and 99. It is more preferably .99% by mass or more. When the aluminum purity is in the above range, the regularity of the arrangement of the micropores formed by the anodizing treatment becomes sufficient. That is, the regularity of the arrangement of the through holes is sufficient.
The aluminum substrate is not particularly limited as long as it can form an anodized film, and for example, JIS (Japanese Industrial Standards) 1050 material is used.

It is preferable that the surface of one side of the aluminum substrate to be anodized is previously heat-treated, degreased and mirror-finished.
Here, regarding the heat treatment, the degreasing treatment, and the mirror finish treatment, the same treatments as those described in paragraphs [0044] to [0054] of JP-A-2008-270158 can be applied.
The mirror finish treatment before the anodic oxidation treatment is, for example, electrolytic polishing, and for the electrolytic polishing, for example, an electrolytic polishing liquid containing phosphoric acid is used.

[Anodizing process]
Although a conventionally known method can be used for the anodic oxidation treatment, self-regulation is performed from the viewpoint of increasing the regularity of the arrangement of micropores, that is, the arrangement of pores, and ensuring the anisotropic conductivity of the structure. It is preferable to use the method or constant voltage processing.
Here, regarding the self-regularization method and the constant voltage treatment of the anodizing treatment, the same treatments as those described in paragraphs [0056] to [0108] and [FIG. 3] of JP-A-2008-270158 are performed. Can be applied.

[Holding process]
The method for manufacturing the structure may include a holding step. The holding step is a voltage of 95% or more and 105% or less of the holding voltage selected from the range of 1 V or more and less than 30% of the voltage in the above-mentioned anodizing treatment step after the above-mentioned anodizing treatment step for a total of 5 minutes or more. This is the process of holding. In other words, the holding step is a total of 95% or more and 105% or less of the holding voltage selected from the range of 1 V or more and less than 30% of the voltage in the above-mentioned anodic oxidation treatment step after the above-mentioned anodic oxidation treatment step. This is a step of performing electrolytic treatment for 5 minutes or more.
Here, the "voltage in the anodizing treatment" is a voltage applied between the aluminum and the counter electrode, and for example, if the electrolysis time by the anodizing treatment is 30 minutes, the voltage maintained for 30 minutes. The average value.

From the viewpoint of controlling the thickness of the side wall of the anodizing film, that is, the thickness of the barrier layer to an appropriate thickness with respect to the depth of the pores, the voltage in the holding step is 5% or more and 25% or less of the voltage in the anodizing treatment. It is preferably present, and more preferably 5% or more and 20% or less.

Further, for the reason that the in-plane uniformity is further improved, the total holding time in the holding step is preferably 5 minutes or more and 20 minutes or less, more preferably 5 minutes or more and 15 minutes or less, and 5 minutes or more. It is more preferably 10 minutes or less.
The holding time in the holding step may be 5 minutes or more in total, but is preferably 5 minutes or more continuously.

Further, the voltage in the holding step may be set by continuously or stepwise reducing the voltage from the voltage in the anodic oxidation treatment step to the voltage in the holding step, but for the reason of further improving the in-plane uniformity, the anodic oxidation treatment is performed. It is preferable to set the voltage to 95% or more and 105% or less of the above-mentioned holding voltage within 1 second after the completion of the step.

The above-mentioned holding step can also be performed continuously with the above-mentioned anodizing treatment step, for example, by lowering the electrolytic potential at the end of the above-mentioned anodizing treatment step.
In the above-mentioned holding step, with respect to conditions other than the electrolytic potential, the same electrolytic solution and treatment conditions as those of the above-mentioned conventionally known anodizing treatment can be adopted.
In particular, when the holding step and the anodizing treatment step are continuously performed, it is preferable to perform the treatment using the same electrolytic solution.

The anodic oxide film having a plurality of micropores has a barrier layer (not shown) at the bottom of the micropores as described above. It has a barrier layer removing step for removing the barrier layer.

[Barrier layer removal process]
The barrier layer removing step is a step of removing the barrier layer of the anodic oxide film by using, for example, an alkaline aqueous solution containing ions of a metal M1 having a hydrogen overvoltage higher than that of aluminum.
By the barrier layer removing step described above, the barrier layer is removed, and a conductor layer made of the metal M1 is formed at the bottom of the micropores.
Here, the hydrogen overvoltage means the voltage required for hydrogen to be generated. For example, the hydrogen overvoltage of aluminum (Al) is −1.66 V (Journal of the Chemical Society of Japan, 1982, (8)). , P1305-1313). An example of the metal M1 having a higher hydrogen overvoltage than that of aluminum and the value of the hydrogen overvoltage thereof are shown below.
<Metal M1 and hydrogen (1NH ₂ SO ₄ ) overvoltage>
-Platinum (Pt): 0.00V
-Gold (Au): 0.02V
-Silver (Ag): 0.08V
-Nickel (Ni): 0.21V
-Copper (Cu): 0.23V
-Tin (Sn): 0.53V
-Zinc (Zn): 0.70V

[Other examples of barrier layer removal process]
In addition to the above-mentioned steps, the barrier layer removing step may be a step of removing the barrier layer of the anodized film and exposing a part of the substrate to the bottom of the through hole.
In this case, the barrier layer removing step is not particularly limited to the above-mentioned method, and for example, the barrier layer is electrochemically dissolved at a potential lower than the potential in the above-mentioned anodizing treatment of the above-mentioned anodizing treatment step. Method (hereinafter, also referred to as “electrolytic removal treatment”); Method of removing the barrier layer by etching (hereinafter, also referred to as “etching removal treatment”); Method in which these are combined (particularly, electrolytic removal treatment is performed). Later, a method of removing the remaining barrier layer by an etching removal process); and the like can be mentioned.

<Electrolytic removal treatment>
The above-mentioned electrolytic removal treatment is not particularly limited as long as it is an electrolytic treatment performed at a potential lower than the potential (electrolytic potential) in the above-mentioned anodic oxidation treatment of the above-mentioned anodic oxidation treatment step.
In the present invention, the above-mentioned electrolytic dissolution treatment can be continuously performed with the above-mentioned anodizing treatment, for example, by lowering the electrolytic potential at the end of the above-mentioned anodizing treatment step.

For the above-mentioned electrolytic removal treatment, the same electrolytic solution and treatment conditions as those of the above-mentioned conventionally known anodizing treatment can be adopted except for the conditions other than the electrolytic potential.
In particular, when the above-mentioned electrolytic removal treatment and the above-mentioned anodizing treatment are continuously performed as described above, it is preferable to perform the treatment using the same electrolytic solution.

(Electrolytic potential)
The electrolytic potential in the above-mentioned electrolysis removal treatment is preferably lowered continuously or stepwise (step-like) to a potential lower than the electrolysis potential in the above-mentioned anodizing treatment.
Here, the reduction width (step width) when the electrolytic potential is gradually lowered is preferably 10 V or less, more preferably 5 V or less, and 2 V or less from the viewpoint of the withstand voltage of the barrier layer. It is more preferable to have it.
Further, the voltage drop rate when the electrolytic potential is continuously or stepwise lowered is preferably 1 V / sec or less, more preferably 0.5 V / sec or less, and 0.2 V / sec, from the viewpoint of productivity and the like. Seconds or less is more preferable.

<Etching removal process>
The above-mentioned etching removal treatment is not particularly limited, but may be a chemical etching treatment that dissolves using an acid aqueous solution or an alkaline aqueous solution, or may be a dry etching treatment.

(Chemical etching process)
To remove the barrier layer by chemical etching treatment, for example, the structure after the above-mentioned anodic oxidation treatment step is immersed in an acid aqueous solution or an alkaline aqueous solution, and the inside of the micropores is filled with the acid aqueous solution or the alkaline aqueous solution, and then anodic oxidation is performed. Only the barrier layer can be selectively dissolved by a method of contacting the surface of the film on the opening side of the micropore with a pH buffer solution or the like.

Here, when an acid aqueous solution is used, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or oxalic acid, or a mixture thereof. The concentration of the aqueous acid solution is preferably 1 to 10% by mass. The temperature of the aqueous acid solution is preferably 15 to 80 ° C, more preferably 20 to 60 ° C, and further preferably 30 to 50 ° C.
On the other hand, when an alkaline aqueous solution is used, it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass. The temperature of the alkaline aqueous solution is preferably 10 to 60 ° C, more preferably 15 to 45 ° C, and further preferably 20 to 35 ° C.
Specifically, for example, 50 g / L, 40 ° C. phosphoric acid aqueous solution, 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution, 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution and the like are preferably used. Be done.
As the pH buffer solution, a buffer solution corresponding to the above-mentioned acid aqueous solution or alkaline aqueous solution can be appropriately used.

The immersion time in the acid aqueous solution or the alkaline aqueous solution is preferably 5 to 120 minutes, more preferably 8 to 120 minutes, further preferably 8 to 90 minutes, and 10 to 90 minutes. It is particularly preferable to have it. Of these, 10 to 60 minutes is preferable, and 15 to 60 minutes is more preferable.

(Dry etching process)
For the dry etching treatment, it is preferable to use a gas type such as a Cl ₂ / Ar mixed gas.

It can also be formed by expanding the diameter of the through hole and removing the barrier layer. In this case, a pore wide treatment is used to expand the diameter of the through hole. The pore-wide treatment is a treatment in which the anodized oxide film is immersed in an acid aqueous solution or an alkaline aqueous solution to dissolve the anodized oxide film and expand the pore diameter of the through hole. An aqueous solution of an inorganic acid such as hydrochloric acid or a mixture thereof, or an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like can be used.
The barrier layer at the bottom of the through hole can also be removed by the pore wide treatment, and by using the sodium hydroxide aqueous solution in the pore wide treatment, the diameter of the through hole is expanded and the barrier layer is removed.

[Pattern formation process]
As described above, the pattern forming step is formed by using, for example, a photolithography method. In this case, the pattern film is composed of, for example, a resist film and has electrical insulating properties. As the electrical insulating property of the pattern film, it is sufficient that the insulating property can be maintained against the voltage applied by the plating method when filling the metal.
The pattern of the pattern film is not limited to the ring shape shown in FIG. 2, but may be a polygon such as a triangle, a quadrangle, a pentagon, or a hexagon, or a closed shape such as a shape composed of curvature. You can select according to the shape you want to piece. Further, the pattern of the pattern film is not limited to the closed shape, and may be, for example, a cross shape or the like.
As described above, the pattern film 16 can be removed by, for example, a known method for removing the resist film after exposure. As a method for removing the resist film, for example, a method using a chemical solution, a photoexcited ashing method, and a plasma ashing method can be used.

[Filling process]
<Metal used in the filling process>
In the filling step, the metal to be filled as a conductor inside the above-mentioned through hole 15 in order to form a columnar body, and the metal constituting the metal layer are made of a material having an electrical resistivity of ¹⁰³ Ω · cm or less. It is preferable to have. Specific examples of the above-mentioned metals are preferably gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and zinc (Zn). ..
As the conductor, copper (Cu), gold (Au), aluminum (Al), nickel (Ni) are preferable, and copper (Cu) and gold (Au) are preferable from the viewpoint of electrical conductivity and formation by a plating method. ) Is more preferable, and copper (Cu) is even more preferable.

<Plating method>
As the plating method for filling the inside of the pores with metal, for example, an electrolytic plating method or an electroless plating method can be used.
Here, it is difficult to selectively deposit (grow) a metal in the pores with a high aspect ratio by a conventionally known electrolytic plating method used for coloring or the like. It is considered that this is because the precipitated metal is consumed in the pores and the plating does not grow even if electrolysis is performed for a certain period of time or longer.
Therefore, when metal is filled by the electrolytic plating method, it is necessary to allow a rest time during pulse electrolysis or constant potential electrolysis. The rest time is required to be 10 seconds or more, preferably 30 to 60 seconds.
It is also desirable to add ultrasonic waves to promote the agitation of the electrolyte.

Further, the electrolytic voltage is usually 20 V or less, preferably 10 V or less, but it is preferable to measure the precipitation potential of the target metal in the electrolytic solution to be used in advance and perform constant potential electrolysis within the potential of + 1 V. When performing constant potential electrolysis, it is desirable that cyclic voltammetry can be used in combination, and a potentiostat device such as Solartron, BAS Co., Ltd., Hokuto Denko Co., Ltd., IVIUM Co., Ltd. can be used.

(Plating liquid)
As the plating solution, a conventionally known plating solution can be used.
Specifically, when precipitating copper, an aqueous solution of copper sulfate is generally used, but the concentration of copper sulfate is preferably 1 to 300 g / L, more preferably 100 to 200 g / L. preferable. Further, the precipitation can be promoted by adding hydrochloric acid to the electrolytic solution. In this case, the hydrochloric acid concentration is preferably 10 to 20 g / L.
When depositing gold, it is desirable to use a sulfuric acid solution of tetrachlorogold and perform plating by AC electrolysis.

The plating solution preferably contains a surfactant.
As the surfactant, known ones can be used. Sodium lauryl sulfate, which is conventionally known as a surfactant to be added to the plating solution, can be used as it is. Both ionic (cationic / anionic / bidirectional) and nonionic (nonionic) hydrophilic portions can be used, but the point of avoiding the generation of bubbles on the surface of the object to be plated. A cation beam activator is desirable. The concentration of the surfactant in the plating solution composition is preferably 1% by mass or less.
In the electroless plating method, it takes a long time to completely fill the pores composed of pores having a high aspect with metal, so it is desirable to fill the pores with metal by using the electrolytic plating method.

[Substrate removal process]
The substrate removing step is a step of removing the substrate from the insulating film. When the insulating film is an anodized aluminum film, this is a step of removing the aluminum substrate. The method for removing the aluminum substrate is not particularly limited, and for example, a method for removing by melting is preferable.

<Dissolution of aluminum substrate>
For the above-mentioned dissolution of the aluminum substrate, it is preferable to use a treatment liquid in which the anodic oxide film is difficult to dissolve and aluminum is easily dissolved.
Such a treatment liquid preferably has a dissolution rate in aluminum of 1 μm / min or more, more preferably 3 μm / min or more, and further preferably 5 μm / min or more. Similarly, the dissolution rate for the anodic oxide film is preferably 0.1 nm / min or less, more preferably 0.05 nm / min or less, and even more preferably 0.01 nm / min or less.
Specifically, it is preferably a treatment liquid containing at least one metal compound having a lower ionization tendency than aluminum and having a pH (hydrogen ion index) of 4 or less or 8 or more, and the pH is 3 or less or It is more preferably 9 or more, and further preferably 2 or less or 10 or more.

The treatment liquid for dissolving aluminum is based on an acid or alkaline aqueous solution, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum. , A gold compound (for example, platinum chloride acid), these fluorides, these chlorides and the like are preferably blended.
Of these, an acid aqueous solution base is preferable, and a chloride blend is preferable.
In particular, a treatment liquid obtained by blending a hydrochloric acid aqueous solution with mercury chloride (hydrochloric acid / mercury chloride) and a treatment liquid obtained by blending a hydrochloric acid aqueous solution with copper chloride (hydrochloric acid / copper chloride) are preferable from the viewpoint of treatment latitude.
The composition of the treatment liquid for dissolving aluminum is not particularly limited, and for example, a bromine / methanol mixture, a bromine / ethanol mixture, aqua regia, or the like can be used.

The acid or alkali concentration of the treatment liquid for dissolving aluminum is preferably 0.01 to 10 mol / L, more preferably 0.05 to 5 mol / L.
Further, the treatment temperature using the treatment liquid for dissolving aluminum is preferably −10 ° C. to 80 ° C., preferably 0 ° C. to 60 ° C.

Further, the above-mentioned melting of the aluminum substrate is performed by bringing the aluminum substrate after the above-mentioned plating step into contact with the above-mentioned treatment liquid. The contact method is not particularly limited, and examples thereof include a dipping method and a spraying method. Above all, the dipping method is preferable. The contact time at this time is preferably 10 seconds to 5 hours, more preferably 1 minute to 3 hours.

A support may be provided on the anodized film 34, for example. The support preferably has the same outer shape as the anodized film 34. By attaching a support, handleability is increased.

[First metal layer forming step and second metal layer forming step]
The first metal layer forming step is a step of forming the insulating film 14 on the surface 14a of the first region 18a and the second region 18b, which are regions other than the forming region of the pattern film 16, as shown in FIG. .. As described above, the first metal layer 20 is formed by, for example, a thin-film deposition method or a sputtering method.
The second metal layer forming step is a step of forming the second metal layer in the region where the first metal layer 20 exists on the opposite surface 14a on the back surface 14b of the insulating film 14 as shown in FIG. be. In the second metal layer forming step, as described above, for example, the second metal layer 28 is formed by a plating method using the first metal layer 20 as an electrode. In this case, since the columnar body 26 is the starting point of plating, the second metal layer 28 is formed in the region where the columnar body 26 exists. Therefore, the second metal layer 28 can be formed without the need to provide a pattern film, and further, the alignment between the first metal layer 20 and the second metal layer 28 is unnecessary.

The first metal layer in the first metal layer forming step and the second metal layer in the second metal layer forming step are preferably made of the same metal, for example, made of Cu (copper). ing.
The fact that the above-mentioned first metal layer and the second metal layer are composed of the same metal means that when the two metals of the first metal layer and the second metal layer are compared, it is single. In the case of metal, it means that the types of constituent elements are the same. In the case of an alloy, when comparing the main components having a content of 50% by mass or more, it means that the types of the elements of the main components are the same.
Regarding whether the first metal layer and the second metal layer are the same metal or different metals, the first metal layer and the second metal layer are taken out, and the first metal layer and the first metal layer are used. The second metal layer can be distinguished by identifying the metal components of the first metal layer and the second metal layer by measuring each of them using a fluorescent X-ray (XRF) analyzer. ..

The thickness hm of the first metal layer 20 (see FIG. 9) and the thickness hj of the second metal layer 28 (see FIG. 9) are preferably 1 to 50 μm, preferably 5 to 20 μm. Is more preferable.
The thickness hm of the first metal layer 20 and the thickness hj of the second metal layer 28 may be the same or different. The same thickness of the thickness hm of the first metal layer 20 and the thickness hj of the second metal layer 28 is 0.9 ≦ (thickness hm) / (thickness hj) ≦ 1.1. The difference between the thickness hm of the first metal layer 20 and the thickness hj of the second metal layer 28 means that 0.9 ≦ (thickness hm) / (thickness hj) ≦ 1.1.

<Pore wide processing>
The pore-wide treatment is a treatment in which the aluminum substrate is immersed in an acid aqueous solution or an alkaline aqueous solution to dissolve the anodic oxide film and expand the diameter of the through hole 15. The barrier layer is removed by the pore-wide treatment to penetrate the pores of the anodized film 34.

When an aqueous acid solution is used for the pore wide treatment, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, or hydrochloric acid, or a mixture thereof. The concentration of the aqueous acid solution is preferably 1 to 10% by mass. The temperature of the aqueous acid solution is preferably 25 to 40 ° C.
When an alkaline aqueous solution is used for the pore wide treatment, it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass. The temperature of the alkaline aqueous solution is preferably 20 to 35 ° C.
Specifically, for example, a 50 g / L, 40 ° C. phosphoric acid aqueous solution, a 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution, or a 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution is preferably used. ..
The immersion time in the acid aqueous solution or the alkaline aqueous solution is preferably 8 to 60 minutes, more preferably 10 to 50 minutes, and even more preferably 15 to 30 minutes.

[Example of structure]
Hereinafter, the configuration of the structure will be described more specifically.
For example, the structure 30 shown in FIG. 9 has a plurality of columnar bodies 26, an insulating film 14 provided along the thickness direction in a state where the plurality of columnar bodies 26 are electrically insulated from each other, and an insulating film 14. It has a first metal layer 20 and a second metal layer 28 provided on both sides in the thickness direction Dt. Each of the plurality of columnar bodies 26 is composed of a conductor. The first metal layer 20 is provided on the surface 14a of the insulating film 14. The second metal layer 28 is provided on the back surface 14b of the insulating film 14.

The insulating film 14 of the structure 30 has an electrically insulating insulating film 14. The plurality of columnar bodies 26 are arranged on the insulating film 14 in a state of being electrically insulated from each other. In this case, for example, the insulating film 14 has a plurality of through holes 15 penetrating in the thickness direction Dt. The columnar body 26 is provided in the plurality of through holes 15.
The plurality of columnar bodies 26 may be arranged in a state of being electrically insulated from each other.
Further, the structure 30 has, for example, a rectangular outer shape. The outer shape of the structure 30 is not limited to a rectangle, and may be, for example, a circle. The outer shape of the structure 30 can be shaped according to the intended use, ease of manufacture, and the like.
It is preferable that the first metal layer 20 and the second metal layer 28 provided on both sides of the insulating film 14 in the thickness direction Dt are made of the same metal. In this case, the first metal layer 20, the second metal layer 28, and the columnar body 26 may be made of the same metal or may be made of different metals.
The columnar body 26, the first metal layer 20, and the second metal layer 28 may be made of different metals.

As described above, the structure 30 has a first metal layer 20 other than the pattern film 16, an insulating film 14 on which the columnar body 26 is formed, and a second metal layer 28, so that the structure 30 is compared with the metal foil. As a result, the strength is high and the workability is superior to that of metal foil.
Further, the structure 30 is not provided with the columnar body 26 in the insulating film 14, and can be easily separated into individual pieces. Moreover, since the region where the columnar body 26 is provided in the insulating film 14 can be adjusted by the pattern film 16 as described above, the shape and size of the laminated structure 29 to be individualized can be adjusted.
The thickness ht of the structure 30 is preferably in the range of 5 to 500 μm, more preferably in the range of 10 to 300 μm, and further preferably 1 μm or more and 30 μm or less. If the thickness of the structure is within the above range, the workability is excellent.

[Insulating film]
The insulating film is a state in which a plurality of columnar bodies 26 made of a conductor are electrically insulated from each other. The insulating film has a plurality of through holes 15.
The length of the insulating film 14 in the thickness direction Dt is the same as the height H of the columnar body 26 described above, and further is the same as the thickness ht of the structure 30. The length of the insulating film 14 in the thickness direction Dt, that is, the thickness of the insulating film 14 is preferably 10 to 300 μm, more preferably 20 to 30 μm.
The spacing between the columns in the insulating film is preferably 5 nm to 800 nm, more preferably 10 nm to 200 nm, and even more preferably 20 nm to 60 nm. When the distance between the columns in the insulating film is within this range, the insulating film sufficiently functions as an electrically insulating partition wall of the column 26.
Here, the distance between the columns means the width between the adjacent columns, and the cross section of the structure 30 is observed with an electrolytic discharge scanning electron microscope at a magnification of 200,000 times, and the intervals between the adjacent columns are observed. The average value of the width measured at 10 points.
As will be described later, the insulating film is composed of, for example, an anodized film 34 (see FIG. 9). The anodized film 34 has a plurality of through holes 15 (see FIG. 9). The through hole 15 of the anodizing film 34 is the through hole 15 of the insulating film 14 (see FIG. 9).

<Average diameter of through hole>
The average diameter of the through holes is preferably 1 μm or less, more preferably 5 to 500 nm, further preferably 20 to 400 nm, even more preferably 40 to 200 nm, and 50 to 100 nm. Most preferably. When the average diameter d of the through hole 15 is 1 μm or less and is within the above range, a columnar body 26 having the above average diameter can be obtained.
The average diameter of the through holes 15 is obtained by photographing the surface of the anodic oxide film 34 from directly above at a magnification of 100 to 10000 times using a scanning electron microscope. In the photographed image, at least 20 through holes having an annular shape around them are extracted, the diameters thereof are measured and used as the opening diameter, and the average value of these opening diameters is calculated as the average diameter of the through holes.
As the magnification, the magnification in the above-mentioned range can be appropriately selected so that a photographed image capable of extracting 20 or more through holes can be obtained. For the opening diameter, the maximum value of the distance between the ends of the through hole portion was measured. That is, since the shape of the opening of the through hole is not limited to a substantially circular shape, when the shape of the opening is non-circular, the maximum value of the distance between the ends of the through hole portion is set as the opening diameter. Therefore, for example, even in the case of a through hole having a shape in which two or more through holes are integrated, this is regarded as one through hole, and the maximum value of the distance between the ends of the through hole portions is set as the opening diameter. ..

[Columnar body]
As described above, the plurality of columnar bodies 26 are provided in a state of being electrically insulated from each other, and are made of a conductor.
The conductor constituting the columnar body 26 is made of metal. Specific examples of the metal preferably include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni) and the like. From the viewpoint of electrical conductivity, copper, gold, aluminum, and nickel are preferable, copper and gold are more preferable, and copper is most preferable.
The height H (see FIG. 9) of the columnar body 26 in the thickness direction Dt is preferably 10 to 300 μm, more preferably 20 to 30 μm.

<Shape of columnar body>
The average diameter d (see FIG. 9) of the columnar body 26 is preferably 1 μm or less, more preferably 5 to 500 nm, further preferably 20 to 400 nm, and more preferably 40 to 200 nm. It is more preferably 50 to 100 nm, and most preferably 50 to 100 nm.
The density of the columnar body 26 is preferably 20,000 pieces / mm ² or more, more preferably 2 million pieces / mm ² or more, further preferably 10 million pieces / mm ² or more, and 50 million pieces / mm 2. The number of pieces / mm ² or more is particularly preferable, and the number of pieces / mm ² or more is most preferable.
Further, the distance p between the centers of the adjacent columnar bodies 26 (see FIG. 9) is preferably 20 nm to 500 nm, more preferably 40 nm to 200 nm, and further preferably 50 nm to 140 nm.
The average diameter d of the columnar body is obtained by photographing the surface of the insulating film from directly above at a magnification of 100 to 10000 times using a scanning electron microscope. In the photographed image, at least 20 columnar bodies having an annular shape around them are extracted, the diameter thereof is measured and used as the opening diameter, and the average value of these opening diameters is calculated as the average diameter of the columnar bodies.
As the magnification, the magnification in the above range can be appropriately selected so that a photographed image capable of extracting 20 or more columnar bodies can be obtained. For the opening diameter, the maximum value of the distance between the ends of the columnar body portion was measured. That is, since the shape of the opening of the columnar body is not limited to a substantially circular shape, when the shape of the opening is non-circular, the maximum value of the distance between the ends of the columnar body portion is set as the opening diameter. Therefore, for example, even in the case of a columnar body having a shape in which two or more columnar bodies are integrated, this is regarded as one columnar body, and the maximum value of the distance between the ends of the columnar body portions is set as the opening diameter. ..

Regarding the size of each part of the structure 30, unless otherwise specified, the structure 30 is cut in the thickness direction Dt, and the cross section of the cut cross section is observed using an FE-SEM (Field Emission-Scanning Electron Microscope). Is the average value obtained by measuring 10 points corresponding to each size.

The present invention is basically configured as described above. Although the method for manufacturing the structure of the present invention has been described in detail above, the present invention is not limited to the above-described embodiment, and various improvements or changes may be made without departing from the gist of the present invention. Of course.

10 Laminated body 12 Substrate 14 Insulation film 14a Front surface 14b Back surface 15 Through hole 15c Bottom surface 16 Pattern film 18a First region 18b Second region 18c region 20 First metal layer 20a Surface 21 Conductive layer 22 Resin base material 24 Support 26 Columnar Body 28 Second metal layer 29 Laminated structure 30 Structure 32 Aluminum substrate 32a Surface 34 Anodized film 34a Surface 35 Barrier layer Dt Thickness direction H Height d Average diameter hj Thickness hm Thickness ht Thickness p Center distance

Claims (6)

A pattern forming step of forming an electrically insulating pattern film on one surface of an electrically insulating insulating film having a plurality of through holes extending in the thickness direction.
A first metal layer forming step of forming a first metal layer in a region other than the pattern film forming region of one of the above surfaces,
Among the plurality of through holes, a filling step of filling the through holes in contact with the first metal layer with metal,
A structure having a second metal layer forming step of forming a second metal layer in a region where the first metal layer exists on the opposite surface of the other surface of the insulating film. Manufacturing method. A pattern forming step of forming an electrically insulating pattern film on one surface of an electrically insulating insulating film having a plurality of through holes extending in the thickness direction.
Among the plurality of through holes, a filling step of filling the through holes other than those with which the pattern film is in contact with metal, and
A first metal layer forming step of forming a first metal layer in a region other than the pattern film forming region of one of the above surfaces,
A structure having a second metal layer forming step of forming a second metal layer in a region where the first metal layer exists on the opposite surface of the other surface of the insulating film. Manufacturing method. The first metal layer in the first metal layer forming step and the second metal layer in the second metal layer forming step are made of the same metal, according to claim 1 or 2. How to manufacture the structure of. Any one of claims 1 to 3, wherein the first metal layer in the first metal layer forming step and the second metal layer in the second metal layer forming step are made of Cu. The method for manufacturing a structure according to item 1. The method for producing a structure according to any one of claims 1 to 4, wherein in the first metal layer forming step, the first metal layer is formed on one of the surfaces so as to cover the pattern film. .. The method for manufacturing a structure according to any one of claims 1 to 5, wherein the insulating film is an anodized film.

Images