Anisotropically conductive member, method for manufacturing anisotropically conductive member, structure, and method for manufacturing structure

Abstract

To provide an anisotropic conductive member capable of bonding electronic devices of different types with high reliability, a manufacturing method for the same, a structure, and a manufacturing method for the same.SOLUTION: The anisotropic conductive member has a plurality of conductors that penetrates in the direction of the thickness of an insulator film and is provided in a state of being electrically insulated from each other and an organic layer covering at least one surface of the insulator film. In a state where the surfaces are exposed, the organic layer has a portion where the thickness from the insulator film surface is thick and a portion where the thickness from the insulator film surface is thin.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an anisotropically conductive member having a plurality of conductors that penetrate an insulating film in the thickness direction and are provided in a state where they are electrically insulated from one another, and an organic layer that covers at least one surface of the insulating film, a method for manufacturing an anisotropically conductive member, a structure, and a method for manufacturing a structure, and in particular to an anisotropically conductive member having an organic layer that, when its surface is exposed, has a thick portion and a thin portion from the surface of the insulating film, a method for manufacturing an anisotropically conductive member, a structure, and a method for manufacturing a structure. [Background technology]

[0002] Structures formed by filling a plurality of through holes in an insulating substrate with a conductive material such as a metal are one of the fields that have attracted attention in recent years in nanotechnology, and are expected to be used, for example, as anisotropically conductive members. Anisotropically conductive materials can be inserted between an electronic component such as a semiconductor element and a circuit board and electrically connected to the electronic component by simply applying pressure between the electronic component and the circuit board. Therefore, they are widely used as electrical connecting members for electronic components such as semiconductor elements, and as testing connectors for functional testing. In particular, downsizing of electronic components such as semiconductor elements is remarkable. Conventional methods for directly connecting wiring boards, such as wire bonding, flip-chip bonding, and thermocompression bonding, may not be able to fully guarantee the stability of electrical connections of electronic components. Therefore, interposers and anisotropically conductive materials have been attracting attention as electronic connection materials.

[0003] For example, Patent Document 1 describes an anisotropic conductive bonding member comprising an insulating substrate, a plurality of conductive paths made of a conductive member, and a resin layer provided on the entire surface of the insulating substrate. The resin layer contains a thermosetting resin. The conductive paths are insulated from each other and penetrate the insulating substrate in the thickness direction. The conductive paths have protruding portions that protrude from the surface of the insulating substrate, and the ends of the protruding portions are embedded in the resin layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-37509 Summary of the Invention [Problem to be solved by the invention]

[0005] Currently, attempts are being made to connect multiple electronic devices to a single interposer to perform high-speed signal processing. When multiple electronic devices are of the same type, it is called homogeneous, and when multiple electronic devices are of different types, it is called heterogeneous. When multiple electronic devices are different types, the height or spacing of the electrodes of the electronic devices may vary depending on the type of electronic device. When multiple electronic devices are bonded to an anisotropically conductive member instead of an interposer, a configuration in which a resin layer of uniform thickness is provided on the entire surface of an insulating substrate, such as the anisotropically conductive member of Patent Document 1, may result in insufficient bonding due to the uniform thickness of the resin layer, depending on the combination of multiple electronic devices to be bonded, and sufficient bonding strength may not be obtained. As a result, sufficient reliability may not be achieved regarding the bonding of the electronic devices.

[0006] An object of the present invention is to provide an anisotropically conductive member capable of bonding different types of electronic devices with high reliability, a method for manufacturing an anisotropically conductive member, a structure, and a method for manufacturing a structure. [Means for solving the problem]

[0007] In order to achieve the above-mentioned object, one aspect of the present invention provides an anisotropically conductive member having a plurality of conductors that penetrate an insulating film in the thickness direction and are electrically insulated from each other, and an organic layer that covers at least one surface of the insulating film, wherein the organic layer has a thick portion and a thin portion from the surface of the insulating film when the surface is exposed.

[0008] The organic layer preferably has a thickness that changes continuously between a thick portion and a thin portion. The organic layer preferably has a first layer disposed on the insulating film side, and organic members disposed in a scattered manner on the first layer. The organic layer preferably has a multi-layer structure. The organic layer preferably has a smaller contact angle on the side opposite to the insulating film than on the insulating film side. The organic layer preferably has a smaller contact angle with the organic member than with the first layer.

[0009] One aspect of the present invention provides a method for manufacturing an anisotropically conductive member having a plurality of conductors that penetrate an insulating film in the thickness direction and are electrically insulated from one another, and an organic layer that covers at least one surface of the insulating film, the method including a step of forming an organic layer by varying the amount of a composition that forms the organic layer applied to at least one surface of the insulating film.

[0010] In the step of forming the organic layer, it is preferable to form the organic layer by changing the amount of the composition that forms the organic layer to be applied, thereby continuously changing the thickness between thick and thin portions of the organic layer. The step of forming the organic layer preferably includes a step of forming a first layer on the insulating film side, and a step of forming organic members on the first layer in a dotted manner. The organic layer preferably has a multi-layer structure. It is preferable that the organic member has a smaller contact angle than the first layer. The organic layer preferably has layers with different contact angles, and in the step of forming the organic layer, a layer with a smaller contact angle is formed on the opposite side of the insulating film to form an organic layer with a partially different thickness. The step of forming the organic layer preferably includes a step of forming a first layer of uniform thickness, and a step of forming a second layer partially on the surface of the first layer. Preferably, the second layer has a smaller contact angle than the first layer. The step of forming the organic layer preferably includes a step including at least one of an ink-jet method and a coating method. The step of forming the organic layer preferably includes a step of forming a base layer of uniform thickness, and a step of subjecting the base layer to pattern etching treatment to change the thickness of parts of the base layer.

[0011] One aspect of the present invention provides a structure in which a plurality of electronic devices are electrically connected to an anisotropically conductive member, the plurality of electronic devices having a plurality of electrodes electrically connected to the anisotropically conductive member, and the plurality of electronic devices differ from each other in at least one of the height, width, and distance between the electrodes. The plurality of electronic devices preferably differ from one another in at least one of their functions and semiconductor types. The electronic devices preferably have different thicknesses.

[0012] One aspect of the present invention provides a method for manufacturing a structure in which a plurality of electronic devices are electrically connected to an anisotropically conductive member, the plurality of electronic devices having a plurality of electrodes electrically connected to the anisotropically conductive member, the plurality of electronic devices differing in at least one of the height, width, and distance between the electrodes, and the plurality of electronic devices differing in height, the method comprising the steps of placing the plurality of electronic devices on the anisotropically conductive member in ascending order of height, and joining the plurality of electronic devices. The plurality of electronic devices preferably differ from one another in at least one of their functions and semiconductor types. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide an anisotropically conductive member, a method for manufacturing an anisotropically conductive member, a structure, and a method for manufacturing a structure that provide highly reliable bonding even when different types of electronic devices are bonded together. [Brief explanation of the drawings]

[0014] [Figure 1]1 is a schematic cross-sectional view showing a first example of an anisotropically conductive member according to an embodiment of the present invention. [Figure 2] 1 is a schematic plan view showing a first example of an anisotropically conductive member according to an embodiment of the present invention. [Figure 3] FIG. 3 is a schematic cross-sectional view showing a second example of an anisotropically conductive member according to an embodiment of the present invention. [Figure 4] FIG. 3 is a schematic cross-sectional view showing a third example of an anisotropically conductive member according to an embodiment of the present invention. [Figure 5] FIG. 3 is a schematic cross-sectional view showing a fourth example of an anisotropically conductive member according to an embodiment of the present invention. [Figure 6] FIG. 10 is a schematic cross-sectional view showing a fifth example of an anisotropically conductive member according to an embodiment of the present invention. [Figure 7] FIG. 10 is a schematic cross-sectional view showing a sixth example of an anisotropically conductive member according to an embodiment of the present invention. [Figure 8] FIG. 10 is a schematic cross-sectional view showing a seventh example of an anisotropically conductive member according to an embodiment of the present invention. [Figure 9] 1 is a schematic cross-sectional view showing a step of a first example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. [Figure 10] 1 is a schematic cross-sectional view showing a step of a first example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. [Figure 11] 1 is a schematic cross-sectional view showing a step of a first example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. [Figure 12] 5 is a schematic cross-sectional view showing a step of a second example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. FIG. [Figure 13] 5A to 5C are schematic cross-sectional views showing a step in a third example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. [Figure 14] FIG. 4 is a schematic cross-sectional view showing a step of a fourth example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. [Figure 15] FIG. 10 is a schematic cross-sectional view showing a step of a fifth example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. [Figure 16]FIG. 10 is a schematic cross-sectional view showing a step of a sixth example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. [Figure 17] FIG. 10 is a schematic cross-sectional view showing a step of a seventh example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. [Figure 18] FIG. 10 is a schematic cross-sectional view showing a step of a seventh example of a method for producing an anisotropically conductive member according to an embodiment of the present invention. [Figure 19] 2 is a schematic cross-sectional view showing one step of an example of a method for manufacturing an anisotropically conductive layer that constitutes an anisotropically conductive member according to an embodiment of the present invention. FIG. [Figure 20] 2 is a schematic cross-sectional view showing one step of an example of a method for manufacturing an anisotropically conductive layer that constitutes an anisotropically conductive member according to an embodiment of the present invention. FIG. [Figure 21] 2 is a schematic cross-sectional view showing one step of an example of a method for manufacturing an anisotropically conductive layer that constitutes an anisotropically conductive member according to an embodiment of the present invention. FIG. [Figure 22] 2 is a schematic cross-sectional view showing one step of an example of a method for manufacturing an anisotropically conductive layer that constitutes an anisotropically conductive member according to an embodiment of the present invention. FIG. [Figure 23] 2 is a schematic cross-sectional view showing one step of an example of a method for manufacturing an anisotropically conductive layer that constitutes an anisotropically conductive member according to an embodiment of the present invention. FIG. [Figure 24] 2 is a schematic cross-sectional view showing one step of an example of a method for manufacturing an anisotropically conductive layer that constitutes an anisotropically conductive member according to an embodiment of the present invention. FIG. [Figure 25] 2 is a schematic cross-sectional view showing one step of an example of a method for manufacturing an anisotropically conductive layer that constitutes an anisotropically conductive member according to an embodiment of the present invention. FIG. [Figure 26] 1 is a schematic diagram showing a first example of a structure according to an embodiment of the present invention. [Figure 27] FIG. 2 is a schematic diagram showing a second example of a structure according to an embodiment of the present invention. [Figure 28] 5A to 5C are schematic diagrams showing an example of a method for manufacturing a second example of a structure according to an embodiment of the present invention. [Figure 29] FIG. 2 is a schematic diagram showing a lower chip. [Figure 30] FIG. 2 is a schematic diagram showing a first test chip. [Figure 31]FIG. 10 is a schematic diagram showing a second test chip. [Figure 32] FIG. 10 is a schematic diagram showing a third test chip. [Figure 33] FIG. 10 is a schematic diagram showing a bonding state between a lower chip and a first test chip, a second test chip, and a third test chip. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, an anisotropically conductive member, a method for manufacturing an anisotropically conductive member, a structure, and a method for manufacturing a structure of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings. It should be noted that the drawings described below are illustrative for explaining the present invention, and the present invention is not limited to the drawings shown below. In the following, "to" indicating a numerical range includes the values ​​written on both sides. For example, if ε is between α and β, the range of ε includes α and β, and expressed in mathematical notation, α≦ε≦β. Unless otherwise specified, the terms "angle expressed by a specific numerical value," "parallel," and "perpendicular" include a generally acceptable error range in the relevant technical field. Unless otherwise specified, the temperature and time include error ranges generally accepted in the relevant technical field. Furthermore, the term "same" includes a generally acceptable margin of error in the relevant technical field. Furthermore, terms such as "over the entire surface" include a generally acceptable margin of error in the relevant technical field.

[0016] [First example of anisotropic conductive material] Fig. 1 is a schematic cross-sectional view showing a first example of an anisotropically conductive member according to an embodiment of the present invention, and Fig. 2 is a schematic plan view showing the first example of an anisotropically conductive member according to an embodiment of the present invention. Fig. 2 is a plan view seen from the surface 12a side of the insulating film 12 in Fig. 1, and the organic layer 20 shown in Fig. 1 is omitted. The anisotropically conductive member 10 shown in FIG. 1 includes an insulating film 12 having electrical insulation properties, a plurality of conductors 14 that penetrate the insulating film 12 in the thickness direction Dt and are electrically insulated from one another, and an organic layer 20 that covers at least one surface of the insulating film 12.

[0017] The plurality of conductors 14 are arranged in the insulating film 12 while being electrically insulated from one another. In this case, for example, the insulating film 12 has a plurality of pores 13 penetrating in the thickness direction Dt. The conductors 14 are provided in the plurality of pores 13. The conductors 14 protrude from the front surface 12a of the insulating film 12. The conductors 14 also protrude from the back surface 12b of the insulating film 12. The conductor 14 may protrude from one surface of the insulating film 12 in the thickness direction Dt, and in this case, it is preferable to provide the organic layer 20 on the surface of the insulating film 12 from which the conductor 14 protrudes. The insulating film 12 and the plurality of conductors 14 form an anisotropic conductive layer 16. The insulating film 12 is formed, for example, of an anodic oxide film 15. A front surface 12a and a back surface 12b of the insulating film 12 are surfaces that face each other in the thickness direction Dt of the insulating film 12.

[0018] The anisotropically conductive member 10 has anisotropic conductivity and is conductive in the thickness direction Dt, but the conductivity in a direction parallel to the surface 12a of the insulating film 12 is sufficiently low. The anisotropically conductive member 10 has, for example, a rectangular outer shape as shown in Fig. 2. The outer shape of the anisotropically conductive member 10 is not limited to a rectangular shape and may be, for example, a circular shape. The outer shape of the anisotropically conductive member 10 can be a shape that depends on the application, ease of production, etc.

[0019] The anisotropically conductive member 10 shown in FIG. 1 has an organic layer 20 covering at least one surface of the insulating film 12 as described above. When the surface 20a is exposed, the organic layer 20 has portions 20b where the thickness from the surface of the insulating film 12 varies. In the anisotropically conductive member 10 shown in FIG. 1, the portions 20b where the thickness varies form recesses 20c and protrusions 20d in the organic layer 20. The thickness of the organic layer 20 is not uniform. The portions of the organic layer 20 where the thickness is thinner are the recesses 20c, and the portions where the thickness is thicker are the protrusions 20d. The organic layer 20 has thick and thin portions. On the surface 12a side of the insulating film 12, the average thickness hm from the surface 12a of the insulating film 12 to the surface 20a of the convex portions 20d of the organic layer 20 is thicker than the average thickness hj of the portions 20b where the thickness varies partially on the surface 12a side of the insulating film 12. The average thickness hj is the thickness from the surface 12a of the insulating film 12 to the surface 20a of the concave portions 20c of the organic layer 20. Similarly, on the back surface 12b side of the insulating film 12, the average thickness hm from the back surface 12b of the insulating film 12 to the surface 20a of the convex portion 20d of the organic layer 20 is thicker than the average thickness hj of the portion 20b where the thickness of the back surface 12b side of the insulating film 12 varies.

[0020] The organic layer 20 fixes the electrodes of the electronic device to be connected to the conductor 14, and the organic layer 20 is filled around the electrodes when the electronic device is bonded. The organic layer 20 has a thickness corresponding to the thickness of the electrodes of the electronic devices connected to the conductor 14. The organic layer 20 is thicker at the convex portions 20d than at the concave portions 20c. In this case, an electronic device with a larger electrode size can be bonded to the convex portions 20d, and an electronic device with a smaller electrode size can be bonded to the concave portions 20c. In this way, electronic devices with different electrode sizes can be bonded, and different types of electronic devices can be bonded. In this case, the organic layer 20 is configured so that, when the surface 20a is exposed, there is a portion 20b whose thickness from the surface of the insulating film 12 varies. The organic layer 20 has a thin portion and a thick portion from the surface of the insulating film 12, so that the organic layer 20 can fill the periphery of the electrodes when bonding the electronic devices. Therefore, when different types of electronic devices are bonded to the anisotropically conductive member 10, the different types of electronic devices can be bonded with high reliability. The electrode size of an electronic device refers to at least one of the height, width, and distance between electrodes. Furthermore, the anisotropically conductive member 10 is bonded to the surface 20a of the organic layer 20 in a state where there is nothing thereon.

[0021] [Second example of anisotropic conductive material] Fig. 3 is a schematic cross-sectional view showing a second example of an anisotropically conductive member according to an embodiment of the present invention. In Fig. 3, the same components as those shown in Fig. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted. The anisotropically conductive member 10a differs from the anisotropically conductive member 10 shown in FIG. 1 in the configuration of the organic layer 20, but other configurations are the same as those of the anisotropically conductive member 10 shown in FIG. The organic layer 20 of the anisotropically conductive member 10a has a first layer 21 disposed on the insulating film 12 side and organic members 22a disposed in a scattered manner on the first layer 21, and is a composite layer 22 of the first layer 21 and the organic members 22a. The first layer 21 is formed on each of the front surface 20a and the back surface 12b of the insulating film 12. The organic members 22a are disposed in a scattered layer form on the first layer 21. The organic members 22a are formed by, for example, an inkjet method.

[0022] The surface formed by connecting the highest points of the scattered organic members 22a corresponds to the surface 20a of the organic layer 20. In addition, the areas on the first layer 21 where the organic members 22a are not arranged, excluding the spaces between the organic members 22a, also correspond to the surface 20a of the organic layer 20. The areas where the organic members 22a are arranged correspond to the convex portions 20d of the organic layer 20 described above, and the areas where the organic members 22a are not arranged correspond to the concave portions 20c of the organic layer 20 described above. Similar to the anisotropically conductive member 10 (see FIG. 1), the organic layer 20 of the anisotropically conductive member 10a has a configuration in which, when the surface 20a is exposed, there are portions 20b where the thickness from the surface of the insulating film 12 varies partially, and the organic layer 20 has portions where the thickness from the surface of the insulating film 12 is thin and portions where the thickness is thick.

[0023] In the anisotropically conductive member 10a, an electronic device with a large electrode size is bonded to the region corresponding to the protrusion 20d where the organic member 22a is arranged, and an electronic device with a small electrode size is bonded to the first layer 21. When different types of electronic devices are bonded to the anisotropically conductive member 10a, similar to the anisotropically conductive member 10 (see FIG. 1), the different types of electronic devices can be bonded with high reliability. It is preferable that the organic member 22a has a smaller contact angle than the first layer 21. This is preferable because when the organic layer 20 is heated during bonding of the electronic device, the organic member 22a spreads easily, and when the electronic device is bonded, the organic member 22a easily fills the area around the electrode. Note that the contact angle is the contact angle with respect to water.

[0024] [Third example of anisotropic conductive material] Fig. 4 is a schematic cross-sectional view showing a third example of an anisotropically conductive member according to an embodiment of the present invention. In Fig. 4, the same components as those shown in Fig. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted. The anisotropically conductive member 10b differs from the anisotropically conductive member 10 shown in FIG. 1 in the configuration of the organic layer 20, but other configurations are the same as those of the anisotropically conductive member 10 shown in FIG. The organic layer 20 of the anisotropically conductive member 10b has a first layer 21 disposed on the insulating film 12 side, and a second layer 23 disposed on the first layer 21. The organic layer 20 has a multilayer structure of the first layer 21 and the second layer 23. The first layer 21 is formed on the entire surface 20a and the entire back surface 12b of the insulating film 12. The second layer 23 is partially disposed on the first layer 21. The second layer 23 is formed by, for example, an inkjet method or a coating method.

[0025] The surfaces of the first layer 21 and the second layer 23 correspond to the surface 20a of the organic layer 20. The second layer 23 corresponds to the convex portion 20d of the organic layer 20 described above, and the portion of the first layer 21 where the second layer 23 is not disposed corresponds to the concave portion 20c of the organic layer 20. Similar to the anisotropically conductive member 10 (see FIG. 1), the organic layer 20 of the anisotropically conductive member 10b has a configuration in which, when the surface 20a is exposed, there is a portion 20b where the thickness from the surface of the insulating film 12 varies, and the organic layer 20 has a portion where the thickness from the surface of the insulating film 12 is thin and a portion where the thickness is thick.

[0026] In the anisotropically conductive member 10b, an electronic device with a large electrode size is bonded to an area corresponding to the protrusion 20d formed of the second layer 23, and an electronic device with a small electrode size is bonded to the first layer 21. When different types of electronic devices are bonded to the anisotropically conductive member 10b, similar to the anisotropically conductive member 10 (see FIG. 1), the anisotropically conductive member 10b can bond the different types of electronic devices with high reliability. Furthermore, by forming the organic layer 20 into a multilayer structure, the layers constituting the organic layer 20 can be configured with layers having different contact angles and surface energies. For example, by forming the outermost surface of the organic layer 20 with a material having a small contact angle, the organic layer 20 is likely to spread when heated during bonding of the electronic device, which is preferable because the organic layer 20 can be easily filled around the electrodes when the electronic device is bonded. The contact angle is the angle of contact with water, and is measured by dropping water onto the surface of the organic layer according to the method of JIS (Japanese Industrial Standards) R3257, Testing Method for Wettability of Substrate Glass Surfaces. The contact angle is measured using a fully automatic contact angle meter DMo-902 (trade name, manufactured by Kyowa Interface Science Co., Ltd.).

[0027] [Fourth example of anisotropic conductive material] Fig. 5 is a schematic cross-sectional view showing a fourth example of an anisotropically conductive member according to an embodiment of the present invention. In Fig. 5, the same components as those shown in Fig. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted. The anisotropically conductive member 10c differs from the anisotropically conductive member 10 shown in FIG. 1 in the configuration of the organic layer 20, but other configurations are the same as those of the anisotropically conductive member 10 shown in FIG. The organic layer 20 of the anisotropically conductive member 10c has a first layer 21 disposed on the insulating film 12 side and a second layer 24 disposed on the first layer 21. The organic layer 20 has a multilayer structure of the first layer 21 and the second layer 24. The first layer 21 is formed on the entire surface of the front surface 20a and the entire back surface 12b of the insulating film 12. The second layer 24 is disposed on the entire surface of the first layer 21, and the second layer 24 has a thickness that varies from the surface of the insulating film 12 to a different extent, with the organic layer 20 having a thinner portion and a thicker portion from the surface of the insulating film 12. The second layer 24 is formed by, for example, an inkjet method or a nanoimprint method.

[0028] The surface of the second layer 24 corresponds to the surface 20a of the organic layer 20. The thicker portions of the second layer 24 correspond to the convex portions 20d of the organic layer 20 described above, and the thinner portions of the second layer 24 correspond to the concave portions 20c of the organic layer 20. Similar to the anisotropically conductive member 10 (see FIG. 1), the organic layer 20 of the anisotropically conductive member 10c has a configuration in which, when the surface 20a is exposed, there are portions 20b where the thickness from the surface of the insulating film 12 varies, and the organic layer 20 has portions where the thickness from the surface of the insulating film 12 is thinner and portions where the thickness is thicker.

[0029] In the anisotropically conductive member 10c, an electronic device with a large electrode size is bonded to an area corresponding to the protrusion 20d formed of the second layer 23, and an electronic device with a small electrode size is bonded to the first layer 21. When different types of electronic devices are bonded to the anisotropically conductive member 10c, similar to the anisotropically conductive member 10 (see FIG. 1), the different types of electronic devices can be bonded with high reliability. Furthermore, by forming the organic layer 20 into a multilayer structure, the layers constituting the organic layer 20 can be configured with layers having different contact angles and surface energies. For example, by forming the outermost surface of the organic layer 20 with a material having a small contact angle, the organic layer 20 is likely to spread when heated during bonding of the electronic device, which is preferable because the organic layer 20 can be easily filled around the electrodes when the electronic device is bonded.

[0030] [Fifth example of anisotropic conductive material] Fig. 6 is a schematic cross-sectional view showing a fifth example of an anisotropically conductive member according to an embodiment of the present invention. In Fig. 6, the same components as those shown in Fig. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted. The anisotropically conductive member 10d differs from the anisotropically conductive member 10 shown in FIG. 1 in the configuration of the organic layer 20, but other configurations are the same as those of the anisotropically conductive member 10 shown in FIG. The organic layer 20 of the anisotropically conductive member 10b has thick and thin portions, and the thickness changes continuously between the thick and thin portions 20f. The thick portions are convex portions 20d, and the thin portions are concave portions 20c. The organic layer 20 has an inclined portion 20e between the concave portions 20c and the convex portions 20d 20f. The inclined portion 20e changes so that its thickness increases monotonically from the concave portions 20c toward the convex portions 20d. The inclined portion 20e has an inclination angle θ. The inclination angle θ of the organic layer 20 is the angle between the inclined portion 20e and a line horizontal to the front surface 20a or the back surface 12b of the insulating film 12, and the relationship of "index indicating the slope of the slope" of the organic layer 20 = 1 / tan θ holds. The index indicating the slope of the slope is preferably 5 or less, and more preferably 1 or less. If the index indicating the slope of the slope is 5 or less, adjacent chips can be placed close to each other, and even if there is a misalignment depending on the installation accuracy of the electronic device to be connected, the influence of the sloped portion is reduced. For example, if the sloped portion has a film thickness of 10 μm, the connection loss is suppressed to 2 μm or less, thereby reducing the influence of the connection loss.

[0031] The inclination angle θ of the inclined portion 20e is determined by obtaining a cross-sectional image obtained by cutting the anisotropically conductive member 10d including the organic layer 20 in the thickness direction Dt of the insulating film 12, identifying the front surface 20a or the back surface 12b of the insulating film 12 and the inclined portion 20e in the cross-sectional image, drawing a line perpendicular to the front surface 20a or the back surface 12b of the insulating film 12, and identifying the inclination angle θ formed with the inclined portion 20e. The identified inclination angle θ is obtained using a known method.

[0032] The organic layer 20 of the anisotropically conductive member 10d has a configuration in which, when the surface 20a is exposed, there is a portion 20b where the thickness from the surface of the insulating film 12 varies, similar to the anisotropically conductive member 10 (see Figure 1), and the organic layer 20 has a portion where the thickness from the surface of the insulating film 12 is thin and a portion where the thickness is thick. In the anisotropically conductive member 10d, similarly to the anisotropically conductive member 10 (see FIG. 1), an electronic device with a large electrode size is bonded to the convex portions 20d of the organic layer 20, and an electronic device with a small electrode size is bonded to the concave portions 20c. When different types of electronic devices are bonded to the anisotropically conductive member 10d, similarly to the anisotropically conductive member 10 (see FIG. 1), the different types of electronic devices can be bonded with high reliability. The organic layer 20 has a sloped portion 20e between the recessed portion 20c and the protruding portion 20d 20f, and the thickness of the sloped portion 20e increases monotonically from the recessed portion 20c to the protruding portion 20d, but this is not limited to a continuous change. The sloped portion 20e between the recessed portion 20c and the protruding portion 20d 20f may change in a convex or concave shape from the starting point to the end point, as long as the end point of the convex portion 20d is higher than the starting point of the recessed portion 20c. The surface shape of the sloped portion 20e may be an exponential function, a logarithmic function, or a quadratic function.

[0033] [Sixth example of anisotropic conductive material] Fig. 7 is a schematic cross-sectional view showing a sixth example of an anisotropically conductive member according to an embodiment of the present invention. In Fig. 7, the same components as those shown in Fig. 6 are given the same reference numerals, and detailed description thereof will be omitted. The anisotropically conductive member 10e differs from the anisotropically conductive member 10d shown in FIG. 6 in the configuration of the organic layer 20, but other configurations are the same as those of the anisotropically conductive member 10d shown in FIG. The organic layer 20 of the anisotropically conductive member 10d has a first layer 21 disposed on the insulating film 12 side and a second layer 25 partially disposed on the first layer 21. The organic layer 20 has a multilayer structure of the first layer 21 and the second layer 25. The first layer 21 is formed on the entire surface 20a and the entire back surface 12b of the insulating film 12. The second layer 25 is partially disposed on the first layer 21. The organic layer 20 also has an inclined portion 20e. The second layer 25 is formed, for example, by an inkjet method. The inclination angle θ of the inclined portion 20e is the angle between the inclined portion 20e and a line horizontal to the front surface 20a or the back surface 12b of the insulating film 12, and the relationship of "index indicating the slope of the slope" of the organic layer 20 = 1 / tan θ holds. The index indicating the slope of the slope is preferably 5 or less, and more preferably 1 or less. If the index indicating the slope of the slope is 5 or less, adjacent chips can be placed close to each other, and even if there is a misalignment depending on the installation accuracy of the electronic device to be connected, the influence of the sloped portion is reduced. For example, if the sloped portion has a film thickness of 10 μm, the connection loss is suppressed to 2 μm or less, thereby reducing the influence of the connection loss. The inclination angle θ of the inclined portion 20e is measured in the same manner as that of the anisotropically conductive member 10d described above.

[0034] The organic layer 20 of the anisotropically conductive member 10e has a configuration in which, when the surface 20a is exposed, there are portions 20b in which the thickness from the surface of the insulating film 12 varies, similar to the anisotropically conductive member 10 (see Figure 1), and the organic layer 20 has portions where the thickness from the surface of the insulating film 12 is thin and portions where the thickness is thick. In the anisotropically conductive member 10e, similarly to the anisotropically conductive member 10 (see FIG. 1), an electronic device with a large electrode size is bonded to the convex portions 20d of the organic layer 20, and an electronic device with a small electrode size is bonded to the concave portions 20c. When different types of electronic devices are bonded to the anisotropically conductive member 10e, similarly to the anisotropically conductive member 10 (see FIG. 1), the different types of electronic devices can be bonded with high reliability. Furthermore, by forming the organic layer 20 into a multilayer structure, the layers constituting the organic layer 20 can be configured with layers having different contact angles and surface energies. For example, by forming the outermost surface of the organic layer 20 with a material having a small contact angle, the organic layer 20 is likely to spread when heated during bonding of the electronic device, which is preferable because the organic layer 20 can be easily filled around the electrodes when the electronic device is bonded.

[0035] [Seventh example of anisotropic conductive material] Fig. 8 is a schematic cross-sectional view showing a sixth example of an anisotropically conductive member according to an embodiment of the present invention. In Fig. 8, the same components as those shown in Fig. 6 are given the same reference numerals, and detailed description thereof will be omitted. The anisotropically conductive member 10f differs from the anisotropically conductive member 10d shown in FIG. 6 in the configuration of the organic layer 20, but other configurations are the same as those of the anisotropically conductive member 10d shown in FIG. The organic layer 20 of the anisotropically conductive member 10f has a first layer 21 disposed on the insulating film 12 side and a second layer 26 disposed over the entire surface of the first layer 21. The organic layer 20 has a multilayer structure of the first layer 21 and the second layer 26. The first layer 21 is formed over the entire surface 20a and the entire surface 12b of the insulating film 12. The second layer 26 is disposed over the entire surface of the first layer 21, and the second layer 26 has a thickness that varies from the surface of the insulating film 12 to a thinner portion and a thicker portion. The organic layer 20 also has an inclined portion 20e. The second layer 26 is formed by, for example, an inkjet method or a nanoimprint method. The inclination angle θ is the angle between the inclined portion 20e and a line horizontal to the front surface 20a or rear surface 12b of the insulating film 12, and the relationship of "index indicating the slope of the slope" of the organic layer 20 = 1 / tan θ holds. The index indicating the slope of the slope is preferably 5 or less, and more preferably 1 or less. If the index indicating the slope of the slope is 5 or less, adjacent chips can be placed close to each other, and even if there is a misalignment depending on the installation accuracy of the electronic device to be connected, the influence of the sloped portion is reduced. For example, if the sloped portion has a film thickness of 10 μm, the connection loss is suppressed to 2 μm or less, thereby reducing the influence of the connection loss. The inclination angle θ of the inclined portion 20e is measured in the same manner as that of the anisotropically conductive member 10d described above.

[0036] The organic layer 20 of the anisotropically conductive member 10f has a configuration in which, when the surface 20a is exposed, there are portions 20b in which the thickness from the surface of the insulating film 12 varies, similar to the anisotropically conductive member 10 (see Figure 1), and the organic layer 20 has portions where the thickness from the surface of the insulating film 12 is thin and portions where the thickness is thick. In the anisotropically conductive member 10f, similarly to the anisotropically conductive member 10 (see FIG. 1), an electronic device with a large electrode size is bonded to the convex portions 20d of the organic layer 20, and an electronic device with a small electrode size is bonded to the concave portions 20c. When different types of electronic devices are bonded to the anisotropically conductive member 10e, similarly to the anisotropically conductive member 10 (see FIG. 1), the different types of electronic devices can be bonded with high reliability. Furthermore, by forming the organic layer 20 into a multilayer structure, the layers constituting the organic layer 20 can be configured with layers having different contact angles and surface energies. For example, by forming the outermost surface of the organic layer 20 with a material having a small contact angle, the organic layer 20 is likely to spread when heated during bonding of the electronic device, which is preferable because the organic layer 20 can be easily filled around the electrodes when the electronic device is bonded.

[0037] The structure of the structure will be described in more detail below. [Insulating film] The insulating film 12 electrically insulates the plurality of conductors 14, which are made of a conductive material, from one another. The insulating film has electrical insulating properties. The insulating film 12 also has a plurality of pores 13 in which the conductors 14 are formed. The composition of the insulating film will be described later. The length of the insulating film 12 in the thickness direction Dt, i.e., the thickness ht of the insulating film 12, is preferably in the range of 1 to 1000 μm, more preferably in the range of 5 to 500 μm, and even more preferably in the range of 10 to 300 μm. When the thickness ht of the insulating film 12 is in this range, the insulating film 12 becomes easy to handle. From the viewpoint of ease of winding, the thickness ht of the insulating film 12 is preferably 30 μm or less, and more preferably 5 to 20 μm.

[0038] The thickness of the insulating film was calculated as the average value of 10 measurements taken by cutting the insulating film in the thickness direction Dt using a focused ion beam (FIB), taking surface photographs of the cross section using a scanning electron microscope (SEM) at a magnification of 50,000 times.

[0039] <Average pore diameter> The average diameter of pores 13 is preferably 1 μm or less, more preferably 5 to 500 nm, even more preferably 20 to 400 nm, even more preferably 40 to 200 nm, and most preferably 50 to 100 nm. When the average diameter d of pores 13 is 1 μm or less and within the above range, a conductor 14 having the above average diameter can be obtained. The average diameter of the pores 13 is determined by photographing the surface of the insulating film 12 from directly above at a magnification of 100 to 10,000 times using a scanning electron microscope (SEM). At least 20 pores with a circular periphery are extracted from the photographed image, and their diameters are measured to determine the opening diameter. The average of these opening diameters is calculated as the average diameter of the pores. The magnification can be appropriately selected within the above-mentioned range so as to obtain a photographed image from which 20 or more pores can be extracted. The opening diameter is measured as the maximum distance between the ends of the pore portion. That is, the shape of the opening of the pore is not limited to a substantially circular shape, so when the opening shape is non-circular, the maximum value of the distance between the ends of the pore portion is taken as the opening diameter. Therefore, for example, even in the case of a pore having a shape in which two or more pores are integrated, this is considered to be a single pore, and the maximum value of the distance between the ends of the pore portion is taken as the opening diameter.

[0040] 〔conductor〕 As described above, the plurality of conductors 14 are provided in a state in which they are electrically insulated from one another by the insulating film 12, for example, the anodic oxide film 15. The plurality of conductors 14 are electrically conductive. The conductors are made of a conductive material. The conductive material is not particularly limited, and examples thereof include metals. Specific examples of metals include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), zinc (Zn), and cobalt (Co). From the viewpoint of electrical conductivity, copper, gold, aluminum, nickel, and cobalt are preferred, copper and gold are more preferred, and copper is most preferred. Metals have superior ductility and are more easily deformed than oxide conductors, and are also more easily deformed by compression during bonding, so it is preferable to form the conductor from a metal. The height of the conductor 14 in the thickness direction Dt is preferably 10 to 300 μm, and more preferably 20 to 30 μm.

[0041] <Conductor shape> The average diameter d of the conductor 14 is preferably 1 μm or less, more preferably 5 to 500 nm, even more preferably 20 to 400 nm, even more preferably 40 to 200 nm, and most preferably 50 to 100 nm. The density of the conductor 14 is 20,000 pieces / mm 2 It is preferable that the density is 2 million / mm or more. 2 More preferably, it is 10 million particles / mm 2 More preferably, it is 50 million particles / mm or more. 2 It is particularly preferable that the number is 100 million / mm or more. 2 More preferably, it is equal to or greater than this. Furthermore, the center-to-center distance p between adjacent conductors 14 is preferably 20 nm to 500 nm, more preferably 40 nm to 200 nm, and even more preferably 50 nm to 140 nm.

[0042] The average diameter of the conductors is measured by photographing the surface of the insulating film from directly above using a scanning electron microscope at a magnification of 100 to 10,000 times. At least 20 conductors with a ring-shaped periphery are extracted from the photographed image, and their diameters are measured to determine the opening diameter. The average of these opening diameters is then calculated as the average diameter of the conductors. The magnification can be appropriately selected within the above range so as to obtain a captured image from which 20 or more conductors can be extracted. Furthermore, if the shape of the opening is non-circular, the maximum distance between the ends of the conductor portions is taken as the opening diameter. Therefore, for example, even if a conductor has a shape in which two or more conductors are integrated, this is considered to be a single conductor, and the maximum distance between the ends of the conductor portions is taken as the opening diameter. The average diameter d of the conductor 14 is the same as the average diameter of the protrusions. The center-to-center distance p of adjacent conductors 14 is determined by further identifying the identified center positions (not shown) of the conductors in the photographed image of insulating film 12 obtained as described above. The distance between the center positions of adjacent conductors was determined at 10 locations. The average value of these distances was used as the center distance p of adjacent conductors 14. The center positions are the center positions of the areas corresponding to conductors 14 in the photographed image. Note that a known image analysis method is used to calculate the center positions of the areas in the photographed image.

[0043] <Protrusion> The protrusion is a part of the conductor and is columnar, and is preferably cylindrical in shape because this increases the contact area with the object to be joined. The average protrusion length ha of the protrusions 14a and the average length hb of the protrusions 14b are preferably 10 nm to 1000 nm, more preferably 50 nm to 500 nm. When the average protrusion length ha and the average length hb are 10 nm to 1000 nm, the adhesion between the organic layer 20 and the insulating film 12 is good. The average protrusion lengths ha and hb of the conductor 14 are preferably less than the average thickness hj of the protrusions 14a and 14b of the conductor 14 to the surfaces 20a of the recesses 20c of the organic layer 20. If the average protrusion length ha of the protrusions 14a and the average length hb of the protrusions 14b of the conductor 14 are both less than the average thickness hj of the protrusions 14a and 14b to the surfaces 20a of the recesses 20c of the organic layer 20, the protrusions 14a and 14b are both embedded in the organic layer 20, and the conductor 14 is protected by the organic layer 20. The average protrusion length ha of the protrusion 14a and the average length hb of the protrusion 14b are the average values ​​measured by obtaining cross-sectional images of the protrusions using a scanning electron microscope as described above, and measuring the height of the protrusions at 10 points based on the cross-sectional images.

[0044] The distance between adjacent protrusions of the conductor 14 is preferably 20 nm to 200 nm, and more preferably 40 nm to 100 nm. When the distance between adjacent protrusions is within the above range, the distance between the conductors 14 can be maintained on the front surface 12a or back surface 12b of the insulating film 12 of the conductor 14. This prevents short circuits in the conductor 14 when the electronic device is bonded, further increasing reliability during bonding.

[0045] [Organic layer] As described above, the organic layer covers at least one of the front and back surfaces of the insulating film, protecting the insulating film and the conductors. Furthermore, when the electronic device is bonded, the organic layer fills the periphery of the electrodes of the electronic device. In order to exert the above-mentioned functions, the organic layer preferably exhibits fluidity in a temperature range of 50°C to 200°C and cures at 200°C or higher. Furthermore, since the organic layer spreads easily when heated, it preferably has a small contact angle. The organic layer is, for example, a thermoplastic layer made of a thermoplastic resin or the like, and the organic layer will be described in detail later. The average thickness hm of the organic layer 20 is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less. When the average thickness hm of the organic layer 20 is 10 μm or less, the organic layer 20 can sufficiently protect the protruding portions of the conductors 14 and fill the area around the electrodes when bonding electronic devices. The average thickness hm of the organic layer 20 is the average distance from the surface 12a of the insulating film 12 or the average distance from the back surface 12b of the insulating film 12. The resin layer is cut in the thickness direction Dt of the anisotropically conductive member 10, and the cut cross section is observed using a scanning electron microscope. The average thickness hm of the organic layer 20 is the average value of 10 measured values ​​obtained by measuring the distance from the surface 12a of the insulating film 12 at 10 locations corresponding to the organic layer. The average thickness hm of the organic layer 20 is also the average value of 10 measured values ​​obtained by measuring the distance from the back surface 12b of the insulating film 12 at 10 locations corresponding to the organic layer.

[0046] [First to Seventh Examples of the Method for Manufacturing Anisotropically Conductive Member] 9 to 11 are schematic cross-sectional views showing the order of steps in a first example of a method for manufacturing an anisotropically conductive member according to an embodiment of the present invention. In Figs. 9 to 11, the same components as those in the anisotropically conductive member 10 shown in Fig. 1 are denoted by the same reference numerals, and detailed descriptions thereof will be omitted. In a first example of the method for manufacturing an anisotropically conductive member, first, an anisotropically conductive layer 16 is prepared as shown in Fig. 9. The anisotropically conductive layer 16 has an insulating film 12 and a plurality of conductors 14, and is configured in a state where the organic layer 20 of the anisotropically conductive member 10 is absent. The method for manufacturing the anisotropically conductive layer 16 will be described later.

[0047] 10, in the step of forming the organic layer, a base layer 27 having a uniform thickness is formed on the front surface 12a and the back surface 12b of the insulating film 12. For example, the base layer 27 is formed by using a spin coating method or a coating method. The base layer 27 will eventually become the organic layer 20 or the first layer 21. Therefore, the organic layer 20 or the first layer 21 is made of the same material as the base layer 27. The thickness of the base layer 27 is determined by the configuration and thickness of the organic layer 20, etc. Next, the base layer 27 is subjected to a pattern etching process to partially change the thickness and form recesses 20c (see FIG. 1) and protrusions 20d (see FIG. 1). This forms the organic layer 20 shown in FIG. 1, thereby obtaining the anisotropically conductive member 10. When the organic layer 20 is formed by the pattern etching process, the organic layer 20 is preferably made of a photosensitive composition. The pattern etching process is a process of performing pattern exposure using light having a wavelength corresponding to the base layer 27 as exposure light, followed by a development process. As described above, for example, the base layer 27 is subjected to a pattern etching process, and the organic layer 20 is formed by varying the amount of the composition that forms the organic layer 20. The composition that forms the organic layer 20 is, for example, a photosensitive composition.

[0048] In a first example of the method for manufacturing an anisotropically conductive member, as shown in Fig. 10, a base layer 27 of uniform thickness is formed on the front surface 12a and the back surface 12b of the insulating film 12, and then, as shown in Fig. 11, a mold 28 is disposed opposite the base layer 27. The mold 28 has protrusions 28a corresponding to the surface shape of the organic layer 20 to be formed. For example, after the base layer 27 is heated to a temperature equal to or higher than the glass transition temperature, a mold 28 is pressed against the base layer 27 to form the organic layer 20 shown in Fig. 1. The protrusions 28a of the mold 28 form the recesses 20c (see Fig. 1) and the protrusions 20d (see Fig. 1). This forms the organic layer 20 shown in Fig. 1, and the anisotropically conductive member 10 is obtained. The method for forming the organic layer 20 using the mold 28 described above is a processing method called nanoimprinting. In this way, for example, the nanoimprinting is applied to the base layer 27, and the base layer 27 is divided into thick and thin portions based on the mold 28. In other words, the organic layer 20 is formed by varying the amount of the composition that forms the organic layer 20. In this case, the composition that forms the organic layer 20 is the base layer 27.

[0049] In a second example of a method for manufacturing an anisotropically conductive member, an organic component 22a is formed by dotting a portion of a surface 27a of the base layer 27, as shown in FIG. 12, on the anisotropically conductive layer 16 on which the base layer 27 shown in FIG. 10 has been formed, using, for example, an inkjet method. This forms a composite layer 22 (see FIG. 3) of the first layer 21 and the organic component 22a, thereby forming the anisotropically conductive member 10a shown in FIG. 3. In this case, the base layer 27 becomes the first layer 21, and is therefore formed to a thickness corresponding to the first layer 21. In this way, the organic component 22a is formed by dotting the organic component 22a using, for example, an inkjet method, and the organic layer 20 is formed by varying the amount of the composition used to form the organic layer 20. In this case, the composition that forms the organic layer 20 is the organic component 22a. The size, spacing, and range of the organic members 22a are not particularly limited and may be determined appropriately. When the organic members 22a are scattered using the inkjet method, the density of the organic members 22a can be changed depending on the objects to be bonded. In addition, it is preferable that the organic members 22a have a smaller contact angle than the first layer 21.

[0050] In a third example of the method for manufacturing an anisotropically conductive member, a second layer 23 is formed partially on the surface 27a of the base layer 27 of the anisotropically conductive layer 16 shown in FIG. 10 , on which the base layer 27 is formed, as shown in FIG. 13 . This results in a multilayer organic layer 20 (see FIG. 4 ) made of the base layer 27 and the second layer 23, resulting in the anisotropically conductive member 10b shown in FIG. 4 . In this case, the base layer 27 becomes the first layer 21, and is therefore formed to a thickness corresponding to the first layer 21. Furthermore, it is preferable that the second layer 23 has a smaller contact angle than the base layer 27. In this case, a layer with a smaller contact angle is formed on the opposite side of the insulating film 12, thereby forming an organic layer 20 with a thickness that varies partially. As described above, the second layer 23 is formed partially on the surface 27a of the base layer 27, and the organic layer 20 is formed by varying the amount of the composition used to form the organic layer 20. In this case, the composition that forms the organic layer 20 is the second layer 23.

[0051] In a fourth example of the method for manufacturing an anisotropically conductive member, instead of forming the second layer 23 partially on the surface 27a of the base layer 27 as shown in Fig. 13, another layer 29 is formed on the entire surface of the first layer 21 as shown in Fig. 14. The other layer 29 is formed, like the base layer 27, by using, for example, a spin coating method or a coating method. Next, for example, the other layer 29 is heated to a temperature equal to or higher than the glass transition temperature, and then the mold 28 shown in FIG. 11 is pressed against the other layer 29 to form the second layer 24 (see FIG. 5). This forms the organic layer 20 (see FIG. 5) with a multilayer structure of the base layer 27 and the second layer 24, thereby obtaining the anisotropically conductive member 10c shown in FIG. 5. In this case, the base layer 27 becomes the first layer 21, and is therefore formed to a thickness corresponding to the first layer 21. The other layer 29 becomes the second layer 24, and is therefore formed to a thickness corresponding to the second layer 24. It is also preferable that the other layer 29 has a smaller contact angle than the base layer 27. In this way, for example, a nanoimprinting method is applied to the other layer 29, and the organic layer 20 is divided into thick and thin portions based on the mold 28. That is, the organic layer 20 is formed by varying the amount of composition applied to form the organic layer 20. In this case, the composition forming the organic layer 20 is the other layer 29. In a fourth example of the method for manufacturing an anisotropically conductive member, the second layer 24 can be formed on the base layer 27 by using, for example, an inkjet method.

[0052] In a fifth example of the method for manufacturing an anisotropically conductive member, an organic layer 20 (see FIG. 6) having an inclined portion 20e is formed on the front surface 12a and the back surface 12b of the insulating film 12 of the anisotropically conductive layer 16 shown in FIG. 9 by, for example, an inkjet method, thereby obtaining an anisotropically conductive member 10d shown in FIG. Thus, in the fifth example of the method for manufacturing an anisotropically conductive member, the process of forming the organic layer involves continuously changing the thickness between thick and thin portions, thereby forming an organic layer 20 (see Figure 6) having an inclined portion 20e as described above. In a fifth example of a method for manufacturing an anisotropically conductive member, other than the inkjet method, for example, a base layer 27 is formed on an anisotropically conductive layer 16 as shown in FIG. 10. Next, a mold 28 is used as shown in FIG. 11. The mold 28 has a convex portion (not shown) corresponding to the inclined portion 20e. After the base layer 27 is heated to a temperature equal to or higher than the glass transition temperature, the mold 28 is pressed against the base layer 27 to form an organic layer 20 having the inclined portion 20e as shown in FIG. 15. This results in an anisotropically conductive member 10d shown in FIG. 6.

[0053] In a sixth example of the method for manufacturing an anisotropically conductive member, a second layer 25 is partially formed on the surface 27a of the base layer 27 of the anisotropically conductive layer 16 shown in FIG. 10 by, for example, an inkjet method, as shown in FIG. 16. The second layer 25 has an inclined portion 20e. As a result, an organic layer 20 (see FIG. 7) having a multilayer structure of the base layer 27 and the second layer 25 is formed, and the anisotropically conductive member 10e shown in FIG. 7 is obtained. In this case, the base layer 27 becomes the first layer 21, and therefore is formed to a thickness corresponding to that of the first layer 21. Furthermore, it is preferable that the second layer 25 have a smaller contact angle than the base layer 27. In addition, in a sixth example of a method for manufacturing an anisotropically conductive member, for an anisotropically conductive layer 16 on which a base layer 27 shown in Figure 10 is formed, another layer 29 is formed on the entire surface of the base layer 27, as shown in Figure 14. Next, for example, the other layer 29 is heated to a temperature equal to or higher than the glass transition temperature, and then a mold 28 having a convex portion (not shown) corresponding to the inclined portion 20e is pressed against the other layer 29 to form the second layer 25. As a result, the second layer 26 (see FIG. 8) is formed on the entire surface of the first layer 21, and the organic layer 20 (see FIG. 8) having the inclined portion 20e is formed. In this way, the anisotropically conductive member 10f shown in FIG. 8 is obtained.

[0054] In a seventh example of the method for manufacturing an anisotropically conductive member, a base layer 37 having an inclined portion 37b shown in Fig. 17 is formed on the front surface 12a and rear surface 12b of the insulating film 12 of the anisotropically conductive layer 16 shown in Fig. 9 by, for example, an inkjet method. The base layer 37 having the inclined portion 37b can be formed by, other than the inkjet method, a nanoimprint method in which a mold 28 (see Fig. 11) is pressed against the base layer 27 (see Fig. 10) having the above-mentioned uniform thickness, or by performing a pattern etching process on the base layer 27 (see Fig. 10). Next, the second layer 38 is formed on the surface 37a of the base layer 37, for example, by inkjet printing or coating. In this case, the surface shape of the second layer 38 reflects the surface shape of the base layer 37. In this manner, it is also possible to form the organic layer 20 having a multilayer structure of the first layer 21 and the second layer 38 and having the inclined portion 20e. Even in this case, it is preferable that the second layer 38 has a smaller contact angle than the base layer 37. 10, when forming a base layer 27 etc. on both sides of the anisotropic conductive layer 16, if the base layer 27 etc. is formed on one side and then the base layer 27 etc. is formed on the other side by spin coating, it is preferable to attach a porous fluororesin sheet (made of polytetrafluoroethylene) to a stage (not shown) with the anisotropic conductive layer 16 on one side to prevent contamination. For example, C-Porous (registered trademark) manufactured by Chukoh Chemical Industry Co., Ltd. can be used as the porous fluororesin sheet.

[0055] [Example of a manufacturing method for anisotropic conductive layer] 19 to 25 are schematic cross-sectional views showing one step of an example of a method for manufacturing an anisotropically conductive layer that constitutes an anisotropically conductive member according to an embodiment of the present invention. In Fig. 19 to 25, the same components as those shown in Fig. 1 are denoted by the same reference numerals, and detailed description thereof will be omitted. In one example of a method for manufacturing the anisotropically conductive layer 16 that constitutes the anisotropically conductive member 10, an anisotropically conductive member 10 shown in FIG. 1 in which the insulating film 12 is composed of an anodized aluminum film will be described. To form the anodized aluminum film, an aluminum substrate is used. Therefore, in one example of a method for manufacturing a structure, an aluminum substrate 30 is first prepared, as shown in FIG. The size and thickness of the aluminum substrate 30 are determined appropriately depending on the thickness ht (see FIG. 1) of the insulating film 12 of the anisotropically conductive member 10 (see FIG. 1) to be finally obtained, the processing equipment, etc. The aluminum substrate 30 is, for example, a rectangular plate material. However, it is not limited to an aluminum substrate, and any metal substrate on which an electrically insulating insulating film 12 can be formed can be used.

[0056] Next, one surface 30a (see FIG. 19) of the aluminum substrate 30 is anodized. As a result, one surface 30a (see FIG. 19) of the aluminum substrate 30 is anodized, and an insulating film 12 having a plurality of pores 13 extending in the thickness direction Dt of the aluminum substrate 30, i.e., an anodized film 15, is formed as shown in FIG. 20. A barrier layer 31 exists at the bottom of each pore 13. The above-mentioned anodization process is called an anodization process. As described above, the insulating film 12 having the plurality of pores 13 has a barrier layer 31 at the bottom of each pore 13, but the barrier layer 31 shown in Fig. 20 is removed. As a result, an insulating film 12 having the plurality of pores 13 without the barrier layer 31 (see Fig. 21) is obtained. The step of removing the barrier layer 31 described above is called a barrier layer removal step.

[0057] In the barrier layer removal step, an alkaline aqueous solution containing ions of a metal M1 having a higher hydrogen overvoltage than aluminum is used to remove the barrier layer 31 of the insulating film 12, and at the same time, a metal layer 35a (see FIG. 21) made of a metal (metal M1) is formed on a surface 32d (see FIG. 21) of the bottom 32c (see FIG. 21) of the pore 13. As a result, the aluminum substrate 30 exposed in the pore 13 is covered with the metal layer 35a. This facilitates the progress of plating when the pore 13 is filled with metal, suppressing insufficient filling of the metal into the pore, suppressing incomplete filling of the metal into the pore, and suppressing defective formation of the conductor 14. The alkaline aqueous solution containing ions of the metal M1 may further contain an aluminum ion-containing compound (sodium aluminate, aluminum hydroxide, aluminum oxide, etc.). The content of the aluminum ion-containing compound, converted into the amount of aluminum ions, is preferably 0.1 to 20 g / L, more preferably 0.3 to 12 g / L, and even more preferably 0.5 to 6 g / L.

[0058] Next, plating is performed on the surface 12a of the insulating film 12, which has a plurality of pores 13 extending in the thickness direction Dt. In this case, the metal layer 35a can be used as an electrode for electrolytic plating. Metal 35b is used for plating, and plating proceeds starting from the metal layer 35a formed on the surface 32d (see FIG. 21) of the bottom 32c (see FIG. 21) of the pore 13. As a result, as shown in FIG. 22, the metal 35b constituting the conductor 14 is filled inside the pore 13 of the insulating film 12. By filling the inside of the pore 13 with the metal 35b, the conductor 14 having conductivity is formed. The metal layer 35a and the metal 35b are collectively referred to as the filled metal 35. The process of filling the pores 13 of the insulating film 12 with metal 35b is called the metal filling process. As mentioned above, the conductor 14 is not limited to being made of metal, and any conductive material can be used. Electrolytic plating is used in the metal filling process, and the metal filling process will be described in detail later. Note that the surface 12a of the insulating film 12 corresponds to one side of the insulating film 12. After the metal filling step, as shown in FIG. 23 , the surface 12a of the insulating film 12 on the side where the aluminum substrate 30 is not provided is partially removed in the thickness direction Dt, and the metal 35 filled in the metal filling step is made to protrude from the surface 12a of the insulating film 12. That is, the conductor 14 is made to protrude from the surface 12a of the insulating film 12. This results in a protruding portion 14a. The step of making the conductor 14 protrude from the surface 12a of the insulating film 12 is called a surface metal protrusion step. After the surface metal protrusion step, the aluminum substrate 30 is removed as shown in Fig. 24. The step of removing the aluminum substrate 30 is called a substrate removal step.

[0059] 25, after the substrate removal step, the surface of the insulating film 12 on which the aluminum substrate 30 was provided, i.e., the back surface 12b, is partially removed in the thickness direction Dt, and the metal 35 filled in the metal filling step, i.e., the conductor 14, is made to protrude beyond the back surface 12b of the insulating film 12. This results in a protruding portion 14b. In this way, an anisotropic conductive layer 16 is obtained. The above-mentioned front surface metal protruding step and back surface metal protruding step may be both steps, or may be either one of the front surface metal protruding step and the back surface metal protruding step. The front surface metal protruding step and the back surface metal protruding step correspond to the "protruding step", and both the front surface metal protruding step and the back surface metal protruding step are protruding steps. As shown in FIG. 25, the conductor 14 protrudes from each of the front surface 12a and the back surface 12b of the insulating film 12, and has a protruding portion 14a and a protruding portion 14b. In the anisotropic conductive layer 16, when the conductor 14 does not protrude from the rear surface 12b of the insulating film 12, the anisotropic conductive layer 16 is in the state shown in FIG.

[0060] In the above-described barrier layer removal process, the barrier layer is removed using an alkaline aqueous solution containing ions of metal M1, which has a higher hydrogen overvoltage than aluminum. This not only removes the barrier layer 31, but also forms a metal layer 35a of metal M1, which is less likely to generate hydrogen gas than aluminum, on the aluminum substrate 30 exposed at the bottom of the pores 13. As a result, the in-plane uniformity of the metal filling is improved. This is thought to be because hydrogen gas generation by the plating solution is suppressed, facilitating the progress of metal filling by electrolytic plating. Furthermore, it has been found that the uniformity of metal filling during plating can be significantly improved by providing a holding step in the barrier layer removal step, in which a voltage (holding voltage) selected from a range of less than 30% of the voltage used in the anodizing treatment step is maintained at 95% to 105% for a total of 5 minutes or more, and by combining this with the application of an alkaline aqueous solution containing ions of metal M1. For this reason, it is preferable to provide a holding step. Although the detailed mechanism is unknown, it is thought that in the barrier layer removal process, an alkaline aqueous solution containing ions of metal M1 is used, which forms a layer of metal M1 beneath the barrier layer, thereby preventing damage to the interface between the aluminum substrate and the anodized film and improving the uniformity of the dissolution of the barrier layer.

[0061] In the barrier layer removal step, metal layer 35a made of a metal (metal M1) is formed at the bottom of pore 13, but the present invention is not limited to this, and only barrier layer 31 is removed to expose aluminum substrate 30 at the bottom of pore 13. In the exposed state, aluminum substrate 30 may be used as an electrode for electrolytic plating.

[0062] [Anodic oxide film] As described above, an anodized film made of aluminum is used because it allows pores with a desired average diameter to be formed and makes it easy to form a conductor. However, the anodized film is not limited to an aluminum anodized film, and an anodized film made of a valve metal can also be used. Therefore, a valve metal is used as the metal substrate. Here, specific examples of valve metals include the above-mentioned aluminum, as well as tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, and antimony. Among these, an anodized aluminum film is preferred because it has good dimensional stability and is relatively inexpensive. For this reason, it is preferable to manufacture a structure using an aluminum substrate. The thickness of the anodic oxide film is the same as the thickness ht of the insulating film 12 described above.

[0063] [Metal substrate] The metal substrate is used in the manufacture of a structure, and is a substrate on which an anodized film is formed. As the metal substrate, for example, as described above, a metal substrate on which an anodized film can be formed is used, and a substrate made 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 anodized film as an anodized film.

[0064] [Aluminum substrate] The aluminum substrate used to form the insulating film 12 is not particularly limited, and specific examples include a pure aluminum plate; an alloy plate containing aluminum as the main component and trace amounts of other elements; a substrate in which high-purity aluminum is vapor-deposited onto low-purity aluminum (e.g., recycled material); a substrate in which high-purity aluminum is coated on the surface of a silicon wafer, quartz, glass, etc. by a method such as vapor deposition or sputtering; a resin substrate laminated with aluminum; and the like.

[0065] The surface of the aluminum substrate on which the anodized film is formed by anodizing treatment preferably has an aluminum purity of 99.5% by mass or more, more preferably 99.9% by mass or more, and even more preferably 99.99% by mass or more. When the aluminum purity is within the above range, the micropore arrangement becomes sufficiently regular. The aluminum substrate is not particularly limited as long as it can form an anodic oxide film, and for example, JIS (Japanese Industrial Standards) 1050 material is used.

[0066] It is preferable that the surface of one side of the aluminum substrate to be anodized has been previously subjected to heat treatment, degreasing treatment and mirror finishing treatment. Here, the heat treatment, degreasing treatment, and mirror finish treatment can be the same as the treatments described in paragraphs

[0044] to

[0054] of JP-A-2008-270158. The mirror finish treatment before the anodizing treatment is, for example, electrolytic polishing, and for the electrolytic polishing, for example, an electrolytic polishing solution containing phosphoric acid is used.

[0067] [Anodizing Treatment Process] The anodization treatment can be carried out by a conventionally known method, but from the viewpoint of increasing the regularity of the micropore arrangement and ensuring the anisotropic conductivity of the structure, it is preferable to use a self-ordering method or constant voltage treatment. Here, the self-ordering method of anodizing treatment and constant voltage treatment can be the same as the treatments described in paragraphs

[0056] to

[0108] and [FIG. 3] of JP-A-2008-270158.

[0068] [Holding process] The method for manufacturing a structure may include a holding step, which is a step of holding, after the anodizing treatment step, a voltage of 95% to 105% of a holding voltage selected from the range of 1 V or more and less than 30% of the voltage used in the anodizing treatment step for a total of 5 minutes or more. In other words, the holding step is a step of performing electrolysis, after the anodizing treatment step, at a voltage of 95% to 105% of a holding voltage selected from the range of 1 V or more and less than 30% of the voltage used in the anodizing treatment step for a total of 5 minutes or more. Here, "voltage in anodizing treatment" refers to the voltage applied between the aluminum and the counter electrode. For example, if the electrolysis time in anodizing treatment is 30 minutes, this refers to the average voltage maintained over that 30 minutes.

[0069] From the viewpoint of controlling the thickness of the sidewall of the anodized film, i.e., the thickness of the barrier layer to an appropriate thickness relative to the depth of the pores, the voltage in the holding step is preferably 5% to 25% of the voltage in the anodizing treatment, and more preferably 5% to 20%.

[0070] Furthermore, in order to further improve in-plane uniformity, 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 even more preferably 5 minutes or more and 10 minutes or less. The holding time in the holding step may be a total of 5 minutes or more, but is preferably 5 minutes or more continuously.

[0071] Furthermore, the voltage in the holding step may be set by decreasing continuously or stepwise from the voltage in the anodizing treatment step to the voltage in the holding step, but 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 end of the anodizing treatment step, in order to further improve the in-plane uniformity.

[0072] The above-mentioned holding step can also be carried out consecutively with the above-mentioned anodizing step, for example, by lowering the electrolytic potential at the end of the above-mentioned anodizing step. In the above-mentioned holding step, the same electrolytic solution and treatment conditions as those in the above-mentioned conventionally known anodizing treatment can be used, except for the electrolytic potential. In particular, when the holding step and the anodizing step are carried out successively, it is preferable to carry out the treatment using the same electrolyte.

[0073] As described above, an anodic oxide film having a plurality of micropores has a barrier layer (not shown) at the bottom of the micropores, and the method includes a barrier layer removal step for removing this barrier layer.

[0074] [Barrier layer removal step] The barrier layer removal step is a step of removing the barrier layer of the anodic oxide film using, for example, an alkaline aqueous solution containing ions of a metal M1 having a higher hydrogen overvoltage than aluminum. By the above-mentioned barrier layer removal step, the barrier layer is removed, and a conductive layer made of metal M1 is formed at the bottom of the micropores. Here, hydrogen overvoltage refers to the voltage required to generate hydrogen, and for example, the hydrogen overvoltage of aluminum (Al) is −1.66 V (Journal of the Chemical Society of Japan, 1982, (8), pp. 1305-1313). Examples of metals M1 with a higher hydrogen overvoltage than aluminum and their hydrogen overvoltage values ​​are shown below. <Metal M1 and hydrogen (1N H2SO4) 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

[0075] The pores 13 can also be formed by enlarging the diameter of the micropores and removing the barrier layer. In this case, a pore-widening treatment is used to enlarge the diameter of the micropores. The pore-widening treatment involves immersing the anodized film in an acidic or alkaline aqueous solution to dissolve the anodized film and enlarge the pore size of the micropores. For the pore-widening treatment, an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, or hydrochloric acid, or a mixture thereof, or an aqueous solution of sodium hydroxide, potassium hydroxide, or lithium hydroxide can be used. The pore widening treatment can also remove the barrier layer at the bottom of the micropores. By using an aqueous sodium hydroxide solution in the pore widening treatment, the micropores are enlarged and the barrier layer is removed.

[0076] [Metal filling process] <Metals used in the metal filling process> In the metal filling step, in order to form a conductor, the metal filled as a conductor inside the pores 13 and the metal constituting the metal layer have an electrical resistivity of 10 3 It is preferable that the material has a resistivity of Ω·cm or less. Specific examples of the above-mentioned metals include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and zinc (Zn). From the viewpoint of electrical conductivity and formation by plating, the conductor is preferably copper (Cu), gold (Au), aluminum (Al), or nickel (Ni), more preferably copper (Cu) or gold (Au), and even more preferably copper (Cu).

[0077] <Plating method> As a plating method for filling the inside of the pores with a metal, for example, electrolytic plating or electroless plating can be used. However, it is difficult to selectively deposit (grow) metal in pores with a high aspect ratio using conventional electroplating methods used for coloring, etc. This is thought to be because the deposited metal is consumed in the pores and the plating does not grow even if electrolysis is performed for a certain period of time. Therefore, when filling metal by electroplating, it is necessary to provide a rest period between pulse electrolysis or constant potential electrolysis. The rest period must be 10 seconds or more, and preferably 30 to 60 seconds. It is also desirable to apply ultrasonic waves to promote stirring of the electrolyte.

[0078] Furthermore, the electrolysis voltage is usually 20 V or less, preferably 10 V or less, but it is preferable to measure the deposition potential of the target metal in the electrolyte solution to be used in advance and perform constant-potential electrolysis at a potential within +1 V of that potential. When performing constant-potential electrolysis, it is desirable to use a device that can also be used with cyclic voltammetry, and potentiostat devices such as those manufactured by Solartron, BAS Corporation, Hokuto Denko Corporation, and IVIUM can be used.

[0079] (plating solution) As the plating solution, a conventionally known plating solution can be used. Specifically, when depositing copper, an aqueous solution of copper sulfate is generally used, and the concentration of copper sulfate is preferably 1 to 300 g / L, more preferably 100 to 200 g / L. Furthermore, the addition of hydrochloric acid to the electrolytic solution can promote the deposition. In this case, the concentration of hydrochloric acid is preferably 10 to 20 g / L. When gold is to be deposited, it is desirable to use a sulfuric acid solution of gold tetrachloride and carry out plating by AC electrolysis.

[0080] The plating solution preferably contains a surfactant. Known surfactants can be used. Sodium lauryl sulfate, which is a surfactant conventionally added to plating solutions, can also be used as is. Both ionic (cationic, anionic, zwitterionic) and nonionic surfactants with hydrophilic moieties can be used, but cationic surfactants are preferred to avoid the generation of bubbles on the surface of the object to be plated. The concentration of surfactant in the plating solution composition should preferably be 1% by mass or less. In electroless plating, it takes a long time to completely fill the pores with metal, which are pores with high aspect ratios, so it is preferable to use electrolytic plating to fill the pores with metal.

[0081] [Substrate removal process] The substrate removal step is a step of removing the aluminum substrate after the metal filling step. The method for removing the aluminum substrate is not particularly limited, and a suitable example is a method of removing the aluminum substrate by dissolution.

[0082] <Dissolving aluminum substrate> The dissolution of the aluminum substrate is preferably carried out using a treatment liquid that does not easily dissolve the anodized film but easily dissolves aluminum. Such a treatment solution preferably has a dissolution rate for aluminum of 1 μm / min or more, more preferably 3 μm / min or more, and even more preferably 5 μm / min or more.Similarly, the dissolution rate for anodized films 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, the treatment liquid preferably contains at least one metal compound that has a lower ionization tendency than aluminum, and has a pH (hydrogen ion exponent) of 4 or less or 8 or more, more preferably a pH of 3 or less or 9 or more, and even more preferably a pH of 2 or less or 10 or more.

[0083] The treatment solution for dissolving aluminum is preferably an acid or alkaline aqueous solution based on which compounds of, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum, or gold (e.g., chloroplatinic acid), or fluorides or chlorides thereof are blended. Among these, an acid aqueous solution base is preferred, and it is preferable to blend a chloride. In particular, a treatment solution in which mercury chloride is blended into an aqueous hydrochloric acid solution (hydrochloric acid / mercury chloride) and a treatment solution in which copper chloride is blended into an aqueous hydrochloric acid solution (hydrochloric acid / copper chloride) are preferred 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, etc. can be used.

[0084] The acid or alkali concentration of the treatment solution for dissolving aluminum is preferably 0.01 to 10 mol / L, more preferably 0.05 to 5 mol / L. Furthermore, the treatment temperature using a treatment liquid that dissolves aluminum is preferably from -10°C to 80°C, and more preferably from 0°C to 60°C.

[0085] The aluminum substrate is dissolved by contacting the aluminum substrate after the plating step with the treatment solution. The contacting method is not particularly limited, and examples thereof include immersion and spraying. Of these, the immersion method is preferred. The contact time is preferably 10 seconds to 5 hours, more preferably 1 minute to 3 hours.

[0086] Incidentally, for example, a support may be provided on the insulating film 12. The support preferably has the same outer shape as the insulating film 12. By attaching a support, handling becomes easier.

[0087] [Protrusion process] To partially remove the insulating film 12, for example, an acidic or alkaline aqueous solution is used that dissolves the insulating film 12, i.e., aluminum oxide (Al2O3), but not the metal that constitutes the conductor 14. The insulating film 12 having the pores 13 filled with the metal is brought into contact with the acidic or alkaline aqueous solution to partially remove the insulating film 12. The method for bringing the acidic or alkaline aqueous solution into contact with the insulating film 12 is not particularly limited, and examples include a dipping method and a spraying method. Of these, the dipping method is preferred.

[0088] 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, or hydrochloric acid, or a mixture thereof. Among these, an aqueous solution that does not contain chromic acid is preferable from the viewpoint of excellent safety. The concentration of the acid aqueous solution is preferably 1 to 10 mass %. The temperature of the acid aqueous solution is preferably 25 to 60°C. When an alkaline aqueous solution is used, it is preferable to use an aqueous solution of at least one alkali 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 mass %. The temperature of the alkaline aqueous solution is preferably 20 to 35°C. Specifically, for example, a 50 g / L, 40° C. aqueous solution of phosphoric acid, a 0.5 g / L, 30° C. aqueous solution of sodium hydroxide, or a 0.5 g / L, 30° C. aqueous solution of potassium hydroxide is preferably used.

[0089] The immersion time in the acid or alkali aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and even more preferably 15 to 60 minutes. Here, when short-term immersion treatments are repeated, the immersion time refers to the total immersion time. Note that a washing treatment may be performed between each immersion treatment.

[0090] Furthermore, the metal 35, i.e., the conductor 14, is caused to protrude from the front surface 12a or the back surface 12b of the insulating film 12, preferably by 10 nm to 1000 nm, more preferably by 50 nm to 500 nm, from the front surface 12a or the back surface 12b of the insulating film 12. That is, the protrusion amount of the protrusion 14a from the front surface 12a and the protrusion amount of the conductor 14 from the back surface 12b of the protrusion 14b are each preferably 10 nm to 1000 nm, more preferably 50 nm to 500 nm. The heights of the protrusions 14a and 14b of the conductor 14 are equal to the average protrusion length ha of the protrusion 14a and the average length hb of the protrusion 14b.

[0091] When the height of the protruding portion of the conductor 14 needs to be strictly controlled, it is preferable to fill the inside of the pore 13 with a conductive material such as a metal, process the insulating film 12 and the end of the conductive material such as a metal so that they are flush with each other, and then selectively remove the anodic oxide film. After the above-mentioned metal filling or protruding step, a heat treatment can be carried out in order to reduce distortion in the conductor 14 that occurs due to the metal filling. The heat treatment is preferably carried out in a reducing atmosphere from the viewpoint of suppressing oxidation of the metal, and more preferably in an atmosphere with an oxygen concentration of 20 Pa or less, more preferably in a vacuum. Here, vacuum refers to a state of space in which at least one of the gas density and the atmospheric pressure is lower than that of the atmosphere. Furthermore, the heat treatment is preferably carried out while applying stress to the insulating film 12 for the purpose of correction.

[0092] [Example of structure] The structure has a plurality of electronic devices electrically connected to an anisotropically conductive member. The plurality of electronic devices have a plurality of electrodes electrically connected to the anisotropically conductive member, and the plurality of electronic devices are configured to differ from each other in at least one of the height, width, and distance between the electrodes. The height, width, and inter-electrode distance of the electrodes of an electronic device are specified in the specifications of the electronic device or by actual measurement. In the case of actual measurement, for example, the electrodes are magnified using a laser microscope or a stereo microscope, and the height, width, and inter-electrode distance of the electrodes are measured. The plurality of electronic devices may differ from each other in at least one of function and semiconductor type, and may also differ from each other in thickness. The functions of an electronic device are distinguished by the operation of the electronic device, and examples of functions include calculations such as a central processing unit (CPU) or a graphics processing unit (GPU), storage such as a memory, conversion such as a converter, filtering, and sensing. When these functions are integrated into a single chip or unit, the functions of the integrated chip or unit are identified. When the identified functions are different, the electronic devices are different. The semiconductor species refers to the composition of the semiconductor, and includes silicon carbide (SiC), gallium nitride (GaN), gallium oxide, diamond, silicon (Si), and gallium arsenide (GaAs). The thickness of the electronic devices is the length from the end face of the electrode of the electronic device that comes into contact with the outside to the end face opposite the electrode of the electronic device. For example, in the semiconductor memory 52 shown in FIG. 27 (described later), the thickness is the length from the end face 52c of the electrode 52a to the end face 52d opposite the electrode 52a. In the sensor 53, the thickness is the length from the end face 53c of the electrode 53a to the end face 53d opposite the electrode 53a. The sensor 53 is thicker than the semiconductor memory 52.

[0093] FIG. 26 is a schematic diagram showing a first example of a structure according to an embodiment of the present invention, and FIG. 27 is a schematic diagram showing a second example of a structure according to an embodiment of the present invention. 26, a structure 40 has a plurality of semiconductor memories 42 stacked in a stacking direction Ds by anisotropically conductive members 10 and electrically connected to each other. A CPU 44 is electrically connected to one surface of the anisotropically conductive member 10 that is different from the surface to which the semiconductor memories 42 are connected. A sensor 45 and an RF (Radio Frequency) device 46 are electrically connected side by side to the other surface of the anisotropically conductive member 10 to which the CPU 44 is electrically connected. Furthermore, the CPU 44 is electrically connected onto the wiring board 47 via the anisotropically conductive member 10. The stack of the semiconductor memories 42 is also electrically connected onto the wiring board 47 via the anisotropically conductive member 10. In this manner, in the structure 40, a plurality of electronic devices are electrically connected to the anisotropically conductive member. The semiconductor memories 42, the CPU 44, the sensor 45, and the RF device 46 are electrically connected, and the structure 40 functions as, for example, a communication module.

[0094] As described above, the electronic devices of the structure 40 differ in at least one of the electrode height, electrode width, and inter-electrode distance. For example, the electrode 45a of the sensor 45 has a wider electrode width than the electrode 46a of the RF device 46. The CPU 44 has an electrode 44a and an electrode 44b, but the electrode 44a has a wider electrode width than the electrode 44b.

[0095] 27, in the structure 50, a semiconductor memory 52 and a sensor 53 are arranged side by side and electrically connected on the front surface 11a of the anisotropically conductive member 10. A resin layer 59 is filled around the electrodes 52a and 52b of the semiconductor memory 52, and a resin layer 59 is filled around the electrode 53a of the sensor 53. A CPU 54 is electrically connected to the back surface 11b of the anisotropically conductive member 10. A resin layer 59 is filled around the electrodes 54a, 54b, and 54c of the CPU 54. The resin layer 59 is made of an organic layer 20. As shown in FIG. 27, in the structure 50, the semiconductor memory 52 and the sensor 53 are stacked together with the CPU 54 in the stacking direction Ds. The semiconductor memory 52 has an electrode 52a and an electrode 52b, but the electrode width of the electrode 52a is narrower than that of the electrode 52b. The electrode 53a of the sensor 53 is wider and taller than both the electrodes 52a and 52b of the semiconductor memory 52. ​​As described above, the sensor 53 is thicker than the semiconductor memory 52. The CPU 54 has an electrode 54a, an electrode 54b, and an electrode 54c. The electrodes 54a, 54b, and 54c have the same height, but the electrode 54a is narrower than the electrodes 54b and 54c, and the electrode 54c is the widest. It should be noted that the structure 40 shown in FIG. 26 and the structure 50 shown in FIG. 27 are not limited to the anisotropically conductive member 10, and other anisotropically conductive members 10a to 10f may also be used.

[0096] [Example of manufacturing method for structure] FIG. 28 is a schematic diagram showing an example of a method for manufacturing a structure according to an embodiment of the present invention. In the method for manufacturing a structure, an anisotropically conductive member 10 is prepared as shown in Fig. 28. The organic layer 20 has portions 20b of different thicknesses, and has recessed portions 20c and protruding portions 20d. The anisotropically conductive member 10 is bonded to an electronic device with the surface 20a exposed. When the first electronic device 56 and the second electronic device 57 are bonded to the surface 11a of the anisotropically conductive member 10, the electrode 57a of the second electronic device 57 is taller than that of the first electronic device 56. For this reason, the first electronic device 56 is placed facing the recessed portion 20c of the organic layer 20, and the second electronic device 57 is placed facing the protruding portion 20d. The third electronic device 58 is bonded to the rear surface 11b of the anisotropically conductive member 10. However, since the electrodes 58a, 58b, and 54c of the third electronic device 58 have the same electrode height, the organic layer 20 on the rear surface 11b side of the anisotropically conductive member 10 has a uniform thickness. A third electronic device 58 is placed facing the organic layer 20 on the rear surface 11b side of the anisotropically conductive member 10.

[0097] Next, the multiple electronic devices are bonded together by first placing the first electronic device 56 on the recessed portion 20c of the organic layer 20 on the surface 11a side of the anisotropically conductive member 10, and then placing the second electronic device 57 on the protruding portion 20d, as described above. Furthermore, the third electronic device 58 is placed on the organic layer 20 on the rear surface 11b side of the anisotropically conductive member 10. Next, the first electronic device 56, the second electronic device 57, and the third electronic device 58 are temporarily bonded together by, for example, applying a predetermined pressure to them, heating them to a predetermined temperature, and holding them for a predetermined time. Next, with all of the electronic devices, e.g., the first electronic device 56, the second electronic device 57, and the third electronic device 58, temporarily bonded to the anisotropically conductive member 10, a predetermined pressure is applied to each electronic device, the device is heated to a predetermined temperature, and the temperature is maintained for a predetermined time, thereby bonding all of the electronic devices together to the anisotropically conductive member 10. This bonding is called "main bonding." As a result, the electrodes of the first electronic device 56, the second electronic device 57, and the third electronic device 58 are electrically connected to the conductors 14 (see FIG. 1 ) of the anisotropically conductive member 10, thereby obtaining a structure. At this time, an organic layer 20 is filled around the electrodes of the first electronic device 56, the second electronic device 57, and the third electronic device 58, forming a resin layer 59 shown in FIG. 27.

[0098] The first electronic device 56, the second electronic device 57, and the third electronic device 58 may differ from each other in at least one of function and semiconductor type, and may also differ from each other in thickness. When bonding multiple electronic devices, it is preferable to bond the smaller electronic devices first from the viewpoint of handling. When the electronic devices are the same size, it is preferable to bond the thinner electronic device first.

[0099] In addition, if the temporary bonding strength is weak, misalignment will occur during the transport process and the process leading up to bonding, and therefore the temporary bonding strength is important. The temperature conditions and pressure conditions in the temporary bonding step are not particularly limited, and examples thereof include the temperature conditions and pressure conditions described below. The temperature and pressure conditions for this bonding are not particularly limited. By performing this bonding under appropriate conditions, the organic layer flows between the electrodes of the electronic device and is less likely to remain in the bonded portion. As described above, this bonding can reduce takt time and increase productivity by bonding multiple electronic devices at once. It should be noted that the method for manufacturing the structure is not limited to the anisotropically conductive member 10, and other anisotropically conductive members 10a to 10f can also be used.

[0100] [Electronic Devices] The electronic device is a semiconductor device, etc., but is not limited to a single semiconductor device, and may include a combination of multiple semiconductor devices that perform a specific function, and may also include devices that simply transmit electrical signals. The electronic device may also have an element region. The element region is a region in which various element component circuits and the like for functioning as electronic elements are formed. The element region may include, for example, a region in which a memory circuit such as a flash memory, a logic circuit such as a microprocessor and an FPGA (field-programmable gate array), or a region in which a communication module such as a wireless tag and wiring are formed. In addition to the above, a MEMS (Micro Electro Mechanical Systems) may also be formed in the element region. Examples of MEMS include sensors, actuators, and antennas. Examples of sensors include various sensors for acceleration, sound, light, and the like. As described above, the element region has an element component circuit and the like formed therein, and electrodes (not shown) are provided to electrically connect the semiconductor chip to the outside. The element region has an electrode region in which electrodes are formed. The electrodes in the element region are, for example, Cu posts. The electrode region basically refers to a region that includes all the formed electrodes. However, if the electrodes are provided discretely, the region in which each electrode is provided is also referred to as the electrode region. The form of the structure is not particularly limited, and may be an individualized structure such as a semiconductor chip, a form such as a semiconductor wafer, or a form of a wiring layer. Furthermore, the structure may have a configuration including a printed wiring board, a heat sink, and the like in addition to the electronic device.

[0101] In addition to the above, the electronic devices include, for example, logic LSIs (Large Scale Integration) (e.g., ASICs (Application Specific Integrated Circuits), FPGAs (Field Programmable Gate Arrays), ASSPs (Application Specific Standard Products), etc.), microprocessors (e.g., CPUs, GPUs, etc.), memories (e.g., DRAMs (Dynamic Random Access Memory), HMCs (Hybrid Memory Cubes), MRAMs (Magnetic RAMs), PCMs (Phase-Change Memory), ReRAMs (Resistive RAMs), FeRAMs (Ferroelectric RAMs), flash memories (NAND (Not AND) flash), etc.), LEDs (Light Emitting Diodes) (e.g., microflash in mobile terminals, in-vehicle devices, projector light sources, LCD backlights, general lighting, etc.), power devices, analog ICs (Integrated Circuits), (e.g., DC (Direct Current)-DC (Direct Current) Current converters, insulated gate bipolar transistors (IGBT), etc.), MEMS (Micro Electro Mechanical Systems) (e.g., acceleration sensors, pressure sensors, vibrators, gyro sensors, etc.), wireless (e.g., GPS (Global Positioning System), FM (Frequency Modulation), NFC (Near Field Communication), RFEM (RF Expansion Module), MMIC (Monolithic Microwave Integrated Circuit), WLAN (Wireless Local Area Network), etc.), discrete elements, BSI (Back Side Illumination), CIS (Contact Image Sensor), camera modules, CMOS (Complementary Metal OxideExamples include semiconductors, passive devices, SAW (Surface Acoustic Wave) filters, RF (Radio Frequency) filters, RFIPDs (Radio Frequency Integrated Passive Devices), and BB (Broadband). An electronic device is, for example, a self-contained entity that performs a specific function such as a circuit or a sensor by itself. The electronic device is not particularly limited to the above.

[0102] [Organic layer] The organic layer may have the following composition: The composition of the organic layer will be described below: For example, the organic layer contains a polymer material and may also contain an antioxidant material. Specific examples of the resin material constituting the organic layer include thermoplastic resins such as ethylene copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin resins, acrylic resins, acrylonitrile resins, and cellulose resins. Polyacrylonitrile can also be used as the resin material constituting the organic layer 20.

[0103] <Polymer materials> The polymer material contained in the organic layer is not particularly limited, but is preferably a thermosetting resin, because it can efficiently fill the gap between the structure and the electrodes of an electronic device such as a semiconductor chip, thereby improving the adhesion between the structure and the electronic device such as a semiconductor chip. Specific examples of thermosetting resins include epoxy resins, phenolic resins, polyimide resins, polyester resins, polyurethane resins, bismaleimide resins, melamine resins, and isocyanate resins. Among these, it is preferable to use polyimide resin and / or epoxy resin because they have improved insulation reliability and excellent chemical resistance.

[0104] <Antioxidant materials> Specific examples of antioxidants contained in the organic layer include 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 5-methyl-1,2,3,4-tetrazole, 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-succinic acid, 1,2,3-triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 4-carboxy-1H-1,2,3-triazole, 4,5-dicarboxy-1H-1,2,3-triazole, 1H-1,2,3-triazole-4-acetic acid, 4-carboxy-5-carboxymethyl-1H-1,2,3-triazole, 1,2, 4-triazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3-carboxy-1,2,4-triazole, 3,5-dicarboxy-1,2,4-triazole, 1,2,4-triazole-3-acetic acid, 1H-benzotriazole, 1H-benzotriazole-5-carboxylic acid, benzofuroxan, 2,1,3-benzothiazole, o-phenylenediamine, m-phenylenediamine, catechol, o-aminophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, melamine, and derivatives thereof. Of these, benzotriazole and its derivatives are preferred. Benzotriazole derivatives include substituted benzotriazoles having a hydroxyl group, an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.), an amino group, a nitro group, an alkyl group (e.g., a methyl group, an ethyl group, a butyl group, etc.), a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) on the benzene ring of benzotriazole. Further examples include naphthalenetriazole, naphthalenebistriazole, and similarly substituted naphthalenetriazoles and substituted naphthalenebistriazoles.

[0105] Other examples of antioxidant materials contained in the organic layer include general antioxidants such as higher fatty acids, higher fatty acid copper salts, phenolic compounds, alkanolamines, hydroquinones, copper chelating agents, organic amines, and organic ammonium salts.

[0106] The content of the antioxidant material in the organic layer is not particularly limited, but from the viewpoint of anticorrosion effect, it is preferably 0.0001 mass % or more, more preferably 0.001 mass % or more, based on the total mass of the organic layer, and from the viewpoint of obtaining an appropriate electrical resistance in the present bonding process, it is preferably 5.0 mass % or less, more preferably 2.5 mass % or less.

[0107] <Migration prevention material> The organic layer preferably contains a migration prevention material, because this further improves insulation reliability by trapping metal ions, halogen ions, and metal ions derived from the semiconductor chip and semiconductor wafer that may be contained in the organic layer.

[0108] As the migration prevention material, for example, an ion exchanger, specifically a mixture of a cation exchanger and an anion exchanger, or a cation exchanger alone can be used. The cation exchanger and the anion exchanger can be appropriately selected from, for example, inorganic ion exchangers and organic ion exchangers, respectively, which will be described later.

[0109] (inorganic ion exchanger) Examples of inorganic ion exchangers include hydrous metal oxides, such as hydrous zirconium oxide. Known types of metals include, in addition to zirconium, iron, aluminum, tin, titanium, antimony, magnesium, beryllium, indium, chromium, and bismuth. Among these, the zirconium-based ones contain cations such as Cu. 2+ , Al 3+ In addition, the iron-based materials have the ability to exchange Ag. + , Cu 2+Similarly, tin-, titanium-, and antimony-based compounds are cation exchangers. On the other hand, bismuth-based compounds have anions such as Cl - It has the ability to be exchanged. Zirconium-based materials also exhibit anion exchange capacity depending on the manufacturing conditions, as do aluminum-based and tin-based materials. Other known inorganic ion exchangers include acid salts of polyvalent metals such as zirconium phosphate, heteropolyacid salts such as ammonium molybdophosphate, and synthetic compounds such as insoluble ferrocyanides. Some of these inorganic ion exchangers are already commercially available, for example, various grades of IXE, a trade name of Toagosei Co., Ltd., are known. In addition to synthetic products, powders of inorganic ion exchangers such as natural zeolite or montmorillonite can also be used.

[0110] (organic ion exchanger) The organic ion exchanger includes crosslinked polystyrene having sulfonic acid groups as a cation exchanger, and also includes those having carboxylic acid groups, phosphonic acid groups or phosphinic acid groups. Examples of anion exchangers include cross-linked polystyrene having quaternary ammonium groups, quaternary phosphonium groups, or tertiary sulfonium groups.

[0111] These inorganic and organic ion exchangers may be appropriately selected taking into consideration the types of cations and anions to be trapped and the exchange capacity for those ions. Of course, inorganic and organic ion exchangers may be used in combination. Since the manufacturing process of electronic devices includes a heating process, inorganic ion exchangers are preferred.

[0112] The mixing ratio of the ion exchanger to the polymer material is, for example, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2.5% by mass or less, from the viewpoint of mechanical strength. Furthermore, from the viewpoint of suppressing migration when a semiconductor chip or semiconductor wafer is bonded to a structure, the mixing ratio of the ion exchanger is preferably 0.01% by mass or more.

[0113] <Inorganic fillers> The organic layer preferably contains an inorganic filler. The inorganic filler is not particularly limited and can be appropriately selected from known inorganic fillers, and examples thereof include kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, fumed silica, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, aluminum nitride, zirconium oxide, yttrium oxide, silicon carbide, and silicon nitride.

[0114] It is preferable that the average particle size of the inorganic filler is larger than the spacing between the conductors, because this prevents the inorganic filler from entering between the conductors and improves the reliability of electrical continuity. The average particle size of the inorganic filler is preferably 30 nm to 10 μm, and more preferably 80 nm to 1 μm. Here, the average particle size is the primary particle size measured with a laser diffraction scattering particle size measuring device (Microtrac MT3300 manufactured by Nikkiso Co., Ltd.).

[0115] <Curing agent> The organic layer may contain a hardener. When a curing agent is contained, it is more preferable to use a curing agent that is liquid at room temperature rather than a curing agent that is solid at room temperature, in order to prevent poor bonding with the surface shape of the semiconductor chip or semiconductor wafer to be connected. Here, "solid at room temperature" means that the substance is solid at 25°C, for example, a substance whose melting point is higher than 25°C.

[0116] Specific examples of the curing agent include aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives such as 4-methylimidazole, dicyandiamide, tetramethylguanidine, thiourea adduct amine, carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, carboxylic acid hydrazides, carboxylic acid amides, polyphenol compounds, novolac resins, and polymercaptans, and any curing agent that is liquid at 25° C. can be appropriately selected and used from these curing agents. The curing agents may be used alone or in combination of two or more.

[0117] The organic layer may contain various additives such as dispersants, buffers, viscosity adjusters, etc., which are commonly added to resin insulating films in semiconductor packages, within the range that does not impair the properties of the organic layer.

[0118] As the organic layer, in addition to those mentioned above, for example, one containing a main composition including an acrylic polymer, an acrylic monomer, and a maleimide compound shown below can be used.

[0119] <Acrylic polymer> The acrylic polymer is a polymer containing a structural unit derived from a (meth)acrylate component, and is preferably one that does not make the organic layer too tacky and is unlikely to impair workability during the semiconductor mounting process. Examples of the (meth)acrylate component that can be used include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, butoxyethyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and lauryl (meth)acrylate.

[0120] The acrylic polymer may further contain, in addition to the (meth)acrylate component, a structural unit corresponding to another monomer component copolymerizable with the (meth)acrylate component. Examples of the other monomer component include a carboxyl group-containing monomer (e.g., (meth)acrylic acid), an epoxy group-containing monomer (e.g., glycidyl (meth)acrylate), and a nitrile group-containing monomer (e.g., acrylonitrile).

[0121] For example, the acrylic polymer may contain structural units corresponding to butyl acrylate, methyl acrylate, acrylic acid, glycidyl methacrylate, and acrylonitrile.

[0122] Acrylic polymers can be obtained by polymerizing the above-mentioned (meth)acrylate components and other monomer components. Polymerization methods include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. Types of polymerization reactions for acrylic polymers include, for example, radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, living cationic polymerization, living anionic polymerization, and coordination polymerization.

[0123] The weight average molecular weight (Mw) of the acrylic polymer is not particularly limited, but can be, for example, within the range of 100,000 or more and 1,200,000 or less, or can also be within the range of 500,000 or more and 1,000,000 or less.

[0124] The acrylic polymer, acrylic monomer, and maleimide compound in the organic layer are referred to as the main composition. The acrylic polymer is contained in an amount of 10 to 60 parts by weight, preferably 10 to 45 parts by weight, and more preferably 15 to 40 parts by weight, per 100 parts by weight of the main composition. If the acrylic polymer content is less than 10 parts by weight, it tends to be difficult to eliminate voids. If the acrylic polymer content exceeds 60 parts by weight, it tends to be difficult to achieve low-pressure mounting, and connectivity tends to deteriorate.

[0125] The acrylic polymer may be contained in the main composition either as a single acrylic polymer or as a combination of two or more acrylic polymers. When two or more acrylic polymers are used in combination, the total content of the acrylic polymers in the organic layer is preferably within the above-mentioned range.

[0126] <Acrylic monomer> The acrylic monomer may be a monofunctional (meth)acrylate or a bifunctional or higher functional (meth)acrylate. Examples of the acrylic monomer include isocyanuric acid EO-modified diacrylate (manufactured by Toagosei Co., Ltd.), isocyanuric acid EO-modified triacrylate (manufactured by Toagosei Co., Ltd.), dipentaerythritol and tetraacrylate (manufactured by Toagosei Co., Ltd.), 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Toagosei Co., Ltd.), 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), and fluorene-based acrylates (for example, product names: OGSOL EA0200, EA0300, manufactured by Osaka Gas Chemicals Co., Ltd.). Among these acrylic monomers, fluorene-based acrylates are preferred in view of heat resistance and the like, as they have high heat resistance.

[0127] The acrylic monomer in the organic layer can be contained in a range of 10 to 60 parts by weight, preferably 10 to 55 parts by weight, and more preferably 10 to 50 parts by weight, per 100 parts by weight of the main composition. If the acrylic monomer content is less than 10 parts by weight, connectivity tends to deteriorate. If the acrylic monomer content exceeds 60 parts by weight, it tends to be difficult to eliminate voids.

[0128] The acrylic monomer may be contained alone or in combination of two or more kinds of acrylic monomers. When two or more kinds of acrylic monomers are used in combination, the total content of the acrylic monomers in the organic layer is preferably within the above-mentioned range.

[0129] <Maleimide compounds> As the maleimide compound, for example, a compound having two or more maleimide groups per molecule can be used, and bismaleimide is preferred. Examples of maleimide compounds include 4-methyl-1,3-phenylene bismaleimide, 4,4-bismaleimide diphenylmethane, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide. Among these, aromatic bismaleimides are preferred, and in particular, considering the workability in the production process of the organic layer, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, which has good solvent solubility and flowability, is preferred.

[0130] The maleimide compound in the organic layer is contained in a range of 20 to 70 parts by mass, preferably 20 to 60 parts by mass, and more preferably 20 to 55 parts by mass, per 100 parts by mass of the main composition. If the maleimide compound content is less than 20 parts by mass, it tends to be difficult to achieve low-pressure mounting, and connectivity tends to deteriorate. On the other hand, if the maleimide compound content exceeds 70 parts by mass, it tends to be difficult to achieve low-pressure mounting and void-free mounting.

[0131] The composition used in the organic layer may further contain other components in addition to the components constituting the main composition described above, depending on the purpose. Examples of other components include a phenol compound and a filler.

[0132] <Phenol compounds> A phenol compound can be used as a curing agent for the maleimide compound described above, but the thermal curing reaction can be initiated without containing phenol. Examples of phenol compounds that can be used include allylated bisphenols, such as 2,2'-diallyl bisphenol A (product name: DABPA), 4,4'-(dimethylmethylene)bis[2-(2-propenyl)phenol], 4,4'-methylenebis[2-(2-propenyl)phenol], and 4,4'-(dimethylmethylene)bis[2-(2-propenyl)-6-methylphenol]. Among these, 2,2'-diallyl bisphenol A is preferred.

[0133] When a phenolic compound is contained, the content of the phenolic compound can be, for example, 15 parts by mass or less per 100 parts by mass of the total of the acrylic polymer, the acrylic monomer, the maleimide compound, and the phenolic compound. The phenolic compound may be contained alone, or two or more types of phenolic compounds may be contained in combination. When two or more types of phenolic compounds are used in combination, the total content of the phenolic compounds in the organic layer is preferably within the above-mentioned range.

[0134] <Filler> The filler may be an inorganic filler, an organic filler, conductive particles, etc. In particular, from the viewpoint of reducing the linear expansion coefficient and improving reliability, it is preferable to use an inorganic filler (for example, silica filler).

[0135] When a filler is used, the content of the filler can be, for example, 30 parts by mass or less per 100 parts by mass of the total of the acrylic polymer, the acrylic monomer, the maleimide compound, and the filler. The filler may be a single type of filler, or two or more types of fillers may be used in combination. When two or more types of fillers are used in combination, the total content of the fillers in the organic layer is preferably within the above-mentioned range.

[0136] The present invention is basically configured as described above. The anisotropically conductive member, the method for manufacturing an anisotropically conductive member, the structure, and the method for manufacturing a structure of the present invention have been described in detail above, but the present invention is not limited to the above-mentioned embodiments, and various improvements and modifications may be made without departing from the spirit and scope of the present invention. [Example]

[0137] The features of the present invention will be explained in more detail below with reference to examples. The materials, reagents, amounts and proportions of substances, and procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples. In this example, structures of Examples 1 to 11 and a structure of Comparative Example 1 were produced. Conduction reliability was evaluated for the structures of Examples 1 to 11 and the structure of Comparative Example 1. The evaluation results of conduction reliability are shown in Table 2 below. First, the evaluation of conduction reliability will be described.

[0138] (Evaluation of conduction reliability) <Electronic devices used in the evaluation of conduction reliability> The electronic device used in the evaluation of the conduction reliability will be described. A copper film was formed by sputtering on the surface of a silicon wafer with a thermal oxide layer (SiO2) on all surfaces to the thickness of each electrode. Then, a photoresist (AZ P4903: manufactured by Merck) was applied to the surface of the copper film to a thickness of 10 μm to form a resist film. After contact exposure using a mask, the resist film was developed to form an etching mask pattern for the copper film. The copper film was then etched away using nitric acid to form a copper pattern, which was then washed and used. The developer used was AZ400K manufactured by Merck.

[0139] For the evaluation of the electrical continuity reliability, a lower chip and an upper chip were used as electronic devices. Three types of upper chips were used: a first test chip, a second test chip, and a third test chip. The lower chip has the configuration shown in FIG. 29, and has a first electrode portion 61, a second electrode portion 62, and a third electrode portion 63 formed on a surface 60a. The first electrode section 61 has a wiring group 61a in which linearly extending wirings 61c are arranged in parallel, and electrodes 61b are spaced apart from each other and arranged in two rows on both sides of the wiring group 61a in the arrangement direction of the wirings 61c. Terminals 61d are provided on every other wiring 61c in the arrangement direction of the wiring group 61a. The electrodes 61b are 10 μm square and 500 nm high. The second electrode section 62 has a wiring group 62a in which linearly extending wirings 62c are arranged in parallel, and electrodes 62b are spaced apart from each other and arranged in two rows on both sides of the wiring group 62a in the arrangement direction of the wirings 62c. Terminals 62d are provided on every other wiring 62c in the arrangement direction of the wiring group 62a. The electrodes 62b are 20 μm square and 500 nm high. The third electrode section 63 has a wiring group 63a in which linearly extending wirings 63c are arranged in parallel, and electrodes 63b are spaced apart from each other and arranged in a row on both sides of the wiring group 63a in the arrangement direction of the wirings 63c. The ends of the wiring group 63a in the extension direction of the wirings 63c also serve as terminals. The electrode 63b is 80 μm square and 500 nm high.

[0140] A first test chip 64 is connected to the first connection region 60b of the first electrode portion 61 via each structure 70 (see FIG. 33). A second test chip 65 is connected to the second connection region 60c of the second electrode portion 62 via each structure 70 (see FIG. 33). A third test chip 66 is connected to the third connection region 60d of the third electrode portion 63 via each structure 70 (see FIG. 33). 30 has a wiring portion 64b corresponding to the wiring group 61a, and has electrodes 64c corresponding to the electrodes 61b on both sides of the wiring portion 64b in the arrangement direction. The electrode 64c has an electrode size of 10 μm square and an electrode height of 300 nm. 31 has a wiring portion 65b corresponding to the wiring group 62a, and has electrodes 65c corresponding to the electrodes 62b on both sides of the wiring portion 65b in the arrangement direction. The electrode 65c has an electrode size of 20 μm square and an electrode height of 500 nm. 32 has a wiring portion 66b corresponding to the wiring group 63a, and has electrodes 66c corresponding to the electrodes 63b on both sides of the wiring portion 66b in the arrangement direction. The electrode 66c has an electrode size of 80 μm square and an electrode height of 1000 nm (1 μm).

[0141] 33, each structure 70 was placed on the surface 60a of the lower chip 60. The lower chip 60 was placed on the base layer on the other surface of the anodic oxide film of the anisotropic conductive layer, which will be described later. Next, the first test chip 64, the second test chip 65, and the third test chip 66 were placed in each structure 70 at a position corresponding to the first connection region 60b of the first electrode portion 61 of the lower chip 60, at a position corresponding to the second connection region 60c of the second electrode portion 62, and at a position corresponding to the third connection region 60d of the third electrode portion 63. The third test chip 66, with an electrode height of 1000 nm (1 μm), was placed in a location where the organic layer was thick, and the first test chip 64, with an electrode height of 300 nm, and the second test chip 65, with an electrode height of 500 nm, were placed in locations where the organic layer was thin. Next, alignment was adjusted using a flip chip bonder, and the lower chip 60 was temporarily bonded to the first test chip 64, the second test chip 65, and the third test chip 66, and then the final bonding was performed using a wafer bonder.

[0142] In order to maintain a constant pressure during the actual bonding, a carbon sheet was placed on top of the stack of the temporarily bonded lower chip 60, structure 70, first test chip 64, second test chip 65, and third test chip 66, and then a silicon chip of the same size as the lower chip 60 was placed on top of that and pressure was applied. During bonding, the stack was placed inside the chamber, and the chamber was evacuated under a pressure of approximately 5 N to prevent the upper and lower chips from shifting. The chamber was then filled with nitrogen gas containing 5% hydrogen in several stages, heated to 150°C, and held there for 30 minutes. The temperature was then raised to 220°C, and the stack was pressurized to a pressure of 50 MPa per electrode and held there for 30 minutes. The load was then removed, the stack was allowed to cool naturally under vacuum, and the bonded stack was then removed into the atmosphere. This bonding resulted in a bond 68 between the lower chip 60 and the first test chip 64, second test chip 65, and third test chip 66 via the structure 70, as shown in Figure 33. As described above, the third test chip 66 with an electrode height of 1000 nm (1 μm) was placed where the organic layer was thick, and the first test chip 64 with an electrode height of 300 nm and the second test chip 65 with an electrode height of 500 nm were placed where the organic layer was thin, but if the organic layer thickness was uniform, they would all be placed where the thickness was the same.

[0143] <Conductivity reliability evaluation method> After bonding, each wiring group in the laminate was a daisy chain for two joints. Resistance R was measured by applying a probe to the ends of exposed terminals 61d, 62d and wiring 63c in lower chip 60, and conductivity was evaluated according to the following criteria. Evaluation criteria AR≦1Ω B 1Ω <R<10Ω C 10Ω≦R<1kΩ D 1kΩ≦R

[0144] Examples 1 to 11 and Comparative Example 1 will be described below. Example 1 The structure of the first embodiment will be described. [Structure] <<Anisotropic conductive materials>> <Preparation of aluminum substrate> A molten metal was prepared using an aluminum alloy containing 0.06 mass% Si, 0.30 mass% Fe, 0.005 mass% Cu, 0.001 mass% Mn, 0.001 mass% Mg, 0.001 mass% Zn, 0.001 mass% Ti, and the remainder being Al and unavoidable impurities. After molten metal treatment and filtration, an ingot measuring 500 mm in thickness and 1200 mm in width was produced using a DC (Direct Chill) casting method. Next, the surface was scraped off to an average thickness of 10 mm using a facing mill, and then the material was soaked at 550°C for approximately 5 hours. When the temperature dropped to 400°C, it was rolled into a 2.7 mm thick plate using a hot rolling mill. Further, the sheet was heat-treated at 500°C using a continuous annealing machine, and then cold-rolled to a thickness of 1.0 mm to obtain an aluminum substrate of JIS 1050 material. This aluminum substrate was cut to a width of 1030 mm and then subjected to the following treatments.

[0145] <Electrolytic polishing treatment> The above aluminum substrate was subjected to electrolytic polishing treatment using an electrolytic polishing solution having the following composition under conditions of a voltage of 25 V, a solution temperature of 65° C., and a solution flow rate of 3.0 m / min. The cathode was a carbon electrode, and the power supply was GP0110-30R (manufactured by Takasago Manufacturing Co., Ltd.) The flow rate of the electrolyte was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).

[0146] (Electrolytic polishing liquid composition) 85% by weight phosphoric acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.) 660 mL ·Pure water 160mL ·Sulfuric acid 150mL 30mL of ethylene glycol

[0147] <Anodizing process> Next, the aluminum substrate after the electrolytic polishing treatment was subjected to anodizing treatment by a self-ordering method in accordance with the procedure described in JP-A-2007-204802. The aluminum substrate after electrolytic polishing was subjected to a pre-anodizing treatment for 5 hours using an electrolytic solution of 0.50 mol / L oxalic acid under conditions of a voltage of 40 V, a solution temperature of 16°C, and a solution flow rate of 3.0 m / min. Thereafter, the aluminum substrate after the pre-anodizing treatment was subjected to a film removal treatment by immersing it in a mixed aqueous solution of 0.2 mol / L chromic anhydride and 0.6 mol / L phosphoric acid (liquid temperature: 50° C.) for 12 hours. Thereafter, the plate was subjected to re-anodization treatment for 3 hours and 45 minutes in an electrolyte solution of 0.3 mol / L oxalic acid under conditions of a voltage of 40 V, a liquid temperature of 15°C, and a liquid flow rate of 3.0 m / min, to obtain an anodized film with a thickness of 40 μm. In both the pre-anodizing and re-anodizing treatments, a stainless steel cathode was used, and a GP0110-30R power supply (manufactured by Takasago Machinery Co., Ltd.) was used. The cooling device was a NeoCool BD36 (manufactured by Yamato Scientific Co., Ltd.), and the stirring and heating device was a Pair Stirrer PS-100 (manufactured by EYELA Tokyo Rikakikai Co., Ltd.). The flow rate of the electrolyte was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).

[0148] <Barrier layer removal process> Next, after the anodizing treatment step, an etching treatment was performed by immersing the substrate in an alkaline aqueous solution of sodium hydroxide (50 g / l) with zinc oxide dissolved to a concentration of 2000 ppm at 30°C for 150 seconds, thereby removing the barrier layer at the bottom of the micropores of the anodized film and simultaneously depositing zinc on the surface of the exposed aluminum substrate. The average thickness of the anodic oxide film after the barrier layer removal step was 40 μm.

[0149] <Metal filling process> Next, electrolytic plating was carried out using the aluminum substrate as the cathode and platinum as the anode. Specifically, an anisotropic conductive layer in which copper was filled into the micropores was produced by constant-current electrolysis using a copper plating solution with the composition shown below. Here, constant-current electrolysis was performed using a plating device manufactured by Yamamoto Plating Tester Co., Ltd. and a power supply (HZ-3000) manufactured by Hokuto Denko Corporation. After confirming the deposition potential by performing cyclic voltammetry in the plating solution, the process was carried out under the conditions shown below. (Copper plating solution composition and conditions) ·Copper sulfate 100g / L ·Sulfuric acid 50g / L Hydrochloric acid 15g / L ·Temperature 25℃ ·Current density 10A / dm 2

[0150] The surface of the anodized film after filling the micropores with metal was observed using a scanning electron microscope to determine whether 1,000 micropores were sealed with metal. The sealing rate (number of sealed micropores / 1,000) was calculated to be 98%. In addition, after filling the micropores with metal, the anodic oxide film was cut in the thickness direction using a focused ion beam (FIB), and the cross section was photographed using a scanning electron microscope (magnification 50,000x) to examine the inside of the micropores.It was found that the inside of the sealed micropores was completely filled with metal.

[0151] <Substrate removal process> Next, the aluminum substrate was dissolved and removed by immersion in a mixed solution of copper chloride / hydrochloric acid, to produce an anisotropic conductive layer having an average thickness of 40 μm. The average diameter of the conductors in the fabricated anisotropic conductive layer was 60 nm, the spacing between adjacent protrusions was 40 nm, and the density of the conductors was 57.7 million / mm 2 It was.

[0152] <Protrusion process> After the substrate removal process, the anisotropic conductive layer was immersed in a potassium hydroxide (KOH) aqueous solution (concentration: 0.01 mol / L), and the immersion time was adjusted so that the height of the protrusions was 300 nm, selectively dissolving the surface of the aluminum anodized film.The layer was then washed with water and dried to leave a copper cylinder, i.e., a protruding conductor. Similarly, on the back surface of the aluminum anodized film, copper cylinders, i.e., conductors, were protruded so that the average protrusion length ha of the conductor protrusions 14a (see Figure 1) and the average length hb of the conductor protrusions 14b (see Figure 1) were 300 nm.

[0153] The average diameter of the conductors was measured by photographing the surface of the anodized film from directly above at a magnification of 100 to 10,000 times using a scanning electron microscope. At least 20 conductors with a ring-shaped periphery were extracted from the photographed image, and their diameters were measured to determine the opening diameter. The average value of these opening diameters was calculated as the average diameter of the conductors. The average diameter of the conductors was the average diameter of the protrusions. The average protrusion lengths ha and hb (see Figure 1) of the conductor protrusions 14a are calculated as the average values ​​obtained by cutting the anodized oxide film in the thickness direction Dt (see Figure 1) using a focused ion beam (FIB), taking surface photographs of the cross section (magnification 50,000 times) using a scanning electron microscope, and measuring 10 points.

[0154] <Organic Layer Formation Process> A base layer with a thickness of 600 nm was formed on one side of the anodized film of the anisotropic conductive layer by spin coating using Composition 1. Next, the base layer was subjected to pattern etching to partially change its thickness. This resulted in an organic layer with a 100 nm difference between the recessed portions 20c and the protruding portions 20d. The pattern etching treatment involved pattern exposure using a KrF excimer laser (wavelength 248 nm), followed by development treatment. In this way, recesses and protrusions were formed in the base layer to obtain an organic layer.

[0155] (Composition 1) Composition 1 has the composition shown in Table 1 below and is the composition of "Example 1" described in JP 2009-9860 A. Each of the compositions 1 shown in Table 1 below was dissolved in a solvent to prepare a solution with a solids concentration of 6% by mass, which was then filtered through a polyethylene filter with a pore size of 0.1 μm to prepare a solution. This solution was used in the spin coating method described above.

[0156] [Table 1]

[0157] [Resin 1] The synthesis of Resin 1 will be described. Under a nitrogen stream, 18.1 g of a propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) (2 / 8: mass ratio) mixed solvent was placed in a three-neck flask and heated to 80°C. A solution of 4.3 g of methacrylic acid, 35.5 g of 3-hydroxyadamantyl methacrylate, and a 12 mol% (based on the monomers) polymerization initiator V-601 (Wako Pure Chemical Industries, Ltd.) dissolved in 163.0 g of a PGMEA / PGME (2 / 8: mass ratio) mixed solvent was added dropwise over 6 hours. After the addition was completed, the reaction was continued for another 2 hours at 80°C. After allowing the reaction solution to cool, it was added dropwise over 20 minutes to a mixture of 1400 ml of hexane and 600 ml of ethyl acetate. The precipitated powder was collected by filtration and dried, yielding 26.4 g of Resin 1. The weight average molecular weight of the obtained resin 1 was 8900 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.84. The compound having a polymerizable group (CLR-1), initiator (I-4), solvent, and surfactant are shown below.

[0158] [ka]

[0159] [ka]

[0160] 〔solvent〕 A1: Propylene glycol monomethyl ether acetate B1: Propylene glycol monomethyl ether [Surfactant] W-1: Megafac F176 (DIC Corporation) (fluorine-based)

[0161] Composition 1 constituting the organic layer had a contact angle with water of 30°. The organic layer also had a slope length of 20 nm and an index indicating the slope inclination of 0.2. The index indicating the slope inclination is a value defined as (slope length) / (thickness of the second layer). The index indicating the slope inclination indicates the inclination of the sloped portion 20e (see FIG. 6) of the organic layer with respect to the front surface 20a or back surface 12b of the insulating film 12. The smaller the index indicating the slope inclination, the steeper the inclination, and the closer the angle of the sloped portion 20e (see FIG. 6) with respect to the front surface 20a or back surface 12b of the insulating film 12 becomes to 90°. The index indicating the slope inclination was determined as follows. First, after forming the organic layer, the surface was scanned with a digital microscope VHX-7000 (manufactured by Keyence Corporation) to obtain a cross-sectional profile. The slope length and the thickness of the second layer were determined from the step shape of the cross-sectional profile. Next, (slope length) / (second layer thickness) was calculated to obtain an index indicating the slope inclination. The contact angle with water was measured by dropping water onto the surface of the organic layer according to the method of JIS R3257, Testing Method for Wettability of Substrate Glass Surfaces, using a fully automatic contact angle meter DMo-902 (trade name, manufactured by Kyowa Interface Science Co., Ltd.). Furthermore, a base layer having a thickness of 600 nm was formed on the other surface of the anodic oxide film of the anisotropic conductive layer by spin coating using the same material as that on one surface of the anodic oxide film of the anisotropic conductive layer. When forming the base layer by spin coating on the other side of the anodized film of the anisotropic conductive layer as described above, the anisotropic conductive layer was attached to a stage via a porous fluororesin sheet (made of polytetrafluoroethylene) to prevent contamination, and spin coating was performed. The porous fluororesin sheet used was C-Porous (registered trademark) manufactured by Chukoh Chemical Industry Co., Ltd. In addition, the column "film thickness" of "second layer" in Table 2 below indicates the difference between the concave portion 20c and the convex portion 20d, or the film thickness of the second layer.

[0162] Example 2 Example 2 was the same as Example 1 except for the structure of the organic layer. For the organic layer, a base layer with a film thickness of 1000 nm (1 μm) was formed on one side of the anodized film of the anisotropic conductive layer using PAK-02 (product name, Toyo Gosei Co., Ltd.) by spin coating. Next, the base layer was subjected to a nanoimprinting process to partially change its thickness. This resulted in an organic layer with a difference of 200 nm between the recesses 20c and the protrusions 20d. In this way, recesses and protrusions were formed in the base layer to obtain an organic layer. The nanoimprinting process involved placing a nanoimprinting mold on the base layer, pressing it under a pressure of 0.1 MPa, exposing it to UV light, and then releasing it. The nanoimprinting mold had a 100 nm step and a 200 nm step, each with a step area of ​​3 mm. 2 A glass mold was used. The organic layer was made of PAK-02 (product name, Toyo Gosei Co., Ltd.), which had a water contact angle of 40°. The organic layer also had a slope length of 10 nm and an index indicating the slope gradient of 0.05.

[0163] Example 3 Example 3 differs from Example 2 in that a second layer having a thickness of 200 nm was formed by spin coating using Tuftec (registered trademark) H1043 (product name, Asahi Kasei Corporation), but otherwise was the same as Example 2. The organic layer in Example 4 had a two-layer structure, and the second layer, Tuftec (registered trademark) H1043 (product name, Asahi Kasei Corporation), had a water contact angle of 65°. The organic layer also had a slope length of 1000 nm and an index indicating the slope inclination of 5. Example 4 Example 4 differs from Example 2 in that a second layer having a film thickness of 1000 nm was further formed by spin coating, but the rest was the same as Example 2. For the second layer, 100 g of acrylic polymer (Mw=1,000,000), 150 g of acrylic monomer (product name: OGSOL EA0200, manufactured by Osaka Gas Chemicals Co., Ltd.), 80 g of maleimide compound (product name: BMI5100, manufactured by Daiwa Chemical Industry Co., Ltd.), 20 g of bisphenol (product name: DABPA, manufactured by Daiwa Chemical Industry Co., Ltd.), and 100 g of methyl ethyl ketone were weighed and mixed for a period of 12 to 24 hours to obtain a uniformly dissolved and mixed composition. The resulting composition was applied to the first layer using a spin coater with the rotation speed adjusted to achieve the desired film thickness, and then dried in an oven at 80 °C to form the second layer. The drying time was 5 minutes to reduce the residual solvent content in the resulting film to 2% by mass or less. The organic layer of Example 4 had a two-layer structure, and the second layer had a contact angle with water of 30°. The organic layer also had a slope length of 100 nm and an index indicating the slope inclination of 0.1.

[0164] Example 5 In Example 5, a first layer with a thickness of 500 nm was formed on one side of the anodic oxide film of the anisotropic conductive layer by spin coating using Staystik 383 (product number, Alpha Advanced Materials). Next, a film with a thickness of 500 nm was formed on the first layer by spin coating using TPIR (registered trademark)-2000S NL (product name, Tokyo Ohka Kogyo Co., Ltd.). A second layer was then formed by partially varying the film thickness using a nanoimprinting method. This resulted in an organic layer with a 500 nm difference between the recessed portions 20c and the protruding portions 20d. The nanoimprinting process was performed in the same manner as in Example 2, except that the step height of the glass mold was set to 500 nm. The organic layer in Example 5 had a two-layer structure, with the first layer, Staystik 383 (product number, Alpha Advanced Materials), having a water contact angle of 65°, and the second layer, TPIR (registered trademark)-2000S NL (product name, Tokyo Ohka Kogyo Co., Ltd.), having a water contact angle of 60°. The organic layer also had a slope length of 20 nm and an index indicating the slope of the slope of 0.04. As in Example 1, a first layer having a thickness of 500 nm was formed on the other surface of the anodized film of the anisotropic conductive layer by spin coating using the same material as on one surface of the anodized film of the anisotropic conductive layer.

[0165] Example 6 Example 6 differs from Example 5 in that an organic member was formed instead of the second layer, and was otherwise the same as Example 5. In Example 6, droplets of Tuftec (registered trademark) H1043 (product name, Asahi Kasei Corporation) were ejected onto the first layer by an inkjet method while varying the droplet ejection density, and an organic member was formed so that the height after bonding was 100 nm. A material printer DMP-2850 (manufactured by Fujifilm Corporation) was used to eject droplets of Tuftec (registered trademark) H1043 (product name, Asahi Kasei Corporation). The organic layer in Example 6 was a composite layer, and the contact angle with water of Tuftec (registered trademark) H1043 (product name, Asahi Kasei Corporation) was 65°. The organic layer also had a slope length of 1000 nm (1 μm) and an index indicating the slope inclination of 10. Example 7 Example 7 differs from Example 5 in that the second layer was formed using PAK-02 (product name, Toyo Gosei Co., Ltd.) and the difference between the recessed portion 20c and the protruding portion 20d was 500 nm, but otherwise was the same as Example 5. The organic layer of Example 7 had a two-layer structure, and the second layer, PAK-02 (product name, Toyo Gosei Co., Ltd.), had a water contact angle of 40°. The organic layer also had a slope length of 100 nm and an index indicating the slope inclination of 0.2.

[0166] Example 8 Example 8 differs from Example 6 in that the organic component was the same as the second layer in Example 4, and the organic component was formed so that the height after bonding was 1000 nm; otherwise, it was the same as Example 6. The organic layer of Example 8 was a composite layer, and the second layer had a contact angle with water of 30°. The organic layer also had a slope length of 1000 nm and an index of 10 indicating the slope inclination. Example 9 In Example 9, a first layer having a thickness of 500 nm was formed on one surface of the anodized film of the anisotropic conductive layer by spin coating using Staystik 383 (product number, Alpha Advanced Materials). The thickness of the first layer was varied continuously. Next, an organic material was formed on the first layer by ink-jet printing using Staystik 383 (product number, Alpha Advanced Materials), to obtain an organic layer with a difference of 10 μm (10,000 nm) between the recessed portions 20 c and the protruding portions 20 d. The ink-jet printing method in Example 9 was the same as that in Example 6. The organic layer of Example 9 had a two-layer structure, and the second layer, Staystik 383 (product number, Alpha Advanced Materials), had a water contact angle of 65°. The organic layer also had a slope length of 50 nm and an index indicating the slope gradient of 0.005. As in Example 1, a first layer having a thickness of 500 nm was formed on the other surface of the anodized film of the anisotropic conductive layer by spin coating using the same material as on one surface of the anodized film of the anisotropic conductive layer.

[0167] Example 10 Example 10 differs from Example 9 in that the organic member was formed using Tuftec (registered trademark) H1043 (product name, Asahi Kasei Corporation), but otherwise was the same as Example 10. The organic layer of Example 10 was a composite layer, and Tuftec (registered trademark) H1043 (product name, Asahi Kasei Corporation) had a contact angle with water of 65°. The organic layer also had a slope length of 100 nm and an index indicating the slope of 0.01. Example 11 Example 11 differs from Example 9 in that the organic member used was the same as the second layer of Example 4, but the rest was the same as Example 9. The organic layer of Example 11 was a composite layer, and the second layer had a contact angle with water of 30°. The organic layer also had a slope length of 100 nm and an index indicating the slope of 0.01.

[0168] (Comparative Example 1) In Comparative Example 1, Staystik 383 (product number, Alpha Advanced Materials) was used to form organic layers with a thickness of 10 μm (10,000 nm) on both sides of the anodized film of the anisotropic conductive layer by spin coating. The organic layer of Comparative Example 2 had a contact angle with water of 65° and a uniform thickness. Since Comparative Example 1 did not have a second layer, there was no index indicating the inclination of the slope.

[0169] [Table 2]

[0170] As shown in Table 2, Examples 1 to 11 were superior to Comparative Example 1 in terms of electrical connection reliability. In Comparative Example 1, the organic layer had a uniform thickness and the electrical connection reliability was poor. From Examples 1 and 6 and Examples 2 and 3, it was found that the larger the index indicating the inclination of the slope, the more excellent the conduction reliability. From Examples 4 and 5 and Examples 10 and 11, it was found that when the organic layer had a smaller contact angle with water on the surface side, that is, the bonding side, the conduction reliability was better. [Explanation of symbols]

[0171] 10, 10a, 10b, 10c, 10d, 10e, 10f Anisotropic conductive member 11a, 12a, 20a surface 11b, 12b back side 12 insulating film 13 pores 14 Conductors 14a, 14b protrusion 15 Anodic oxide film 16 Anisotropic conductive layer 20 Organic layer 20b part 20c recess 20d convex part 20e Slope 21 First Layer 22 Composite layer 22a Organic materials 23, 24, 25, 26 Second layer 27 Base Layer 27a surface 28 Mold 28a Convex part 29 layers 30 Aluminum substrate 30a surface 31 Barrier Layer 32c bottom 32d surface 35 metal 35a metal layer 35b metal 37 Base Layer 37a surface 37b Slope 40, 50 structures 42, 52 semiconductor memory 44, 54 CPU 44a, 44b, 45a, 46a, 52a, 52b electrode 45, 53 sensors 46 RF Devices 47 Wiring board 53a, 54a, 54b, 54c, 57a, 58a, 58b electrode 56 First Electronic Device 57 Secondary Electronic Device 58 Third Electronic Device 59 Resin layer 60 Lower Chip 60a surface 60b First connection area 60c 2nd connection area 60d Third connection area 61 1st electrode part 61a, 62a, 63a wiring group 61b, 62b, 63b, 64c, 65c, 66c electrode 61c, 62c, 63c wiring 61d, 62d terminals 62 2nd electrode section 63 Third electrode part 64 First test chip 64b, 65b, 66b Wiring section 65 Second test chip 66 Third Test Chip 68 Joint 70 Structure d average diameter Ds stacking direction Dt thickness direction hj average thickness hm average thickness ht Thickness M1 metal p Center distance θ Tilt angle

Claims

1. An anisotropically conductive member having a plurality of conductors that penetrate an insulating film in a thickness direction and are provided in a state of being electrically insulated from one another, and an organic layer that covers at least one surface of the insulating film, the organic layer has a thick portion and a thin portion from the surface of the insulating film when the surface is exposed, The organic layer has a first layer disposed on the insulating film side and organic members disposed in a scattered manner on the first layer.

2. The anisotropically conductive member according to claim 1 , wherein the organic layer has a multi-layer structure.

3. The anisotropically conductive member according to claim 1 , wherein the organic layer has a smaller contact angle on the side opposite to the insulating film than on the side of the insulating film.

4. The anisotropically conductive member according to claim 1 , wherein the organic layer has a smaller contact angle with the organic member than with the first layer.

5. A method for manufacturing an anisotropically conductive member having a plurality of conductors that penetrate an insulating film in a thickness direction and are provided in a state of being electrically insulated from one another, and an organic layer that covers at least one surface of the insulating film, the method comprising: forming the organic layer by varying the amount of a composition for forming the organic layer applied to at least one of the surfaces of the insulating film; The step of forming the organic layer comprises: forming a first layer on the insulating film side; and forming an organic material on the first layer by scattering the organic material thereon.

6. The method for producing an anisotropically conductive member according to claim 5 , wherein the organic layer has a multi-layer structure.

7. The method for manufacturing an anisotropically conductive member according to claim 5 , wherein the organic member has a smaller contact angle than the first layer.

8. the organic layer has layers with different contact angles; The method for manufacturing an anisotropically conductive member according to claim 6 , wherein the step of forming the organic layer includes forming the layer having the small contact angle on the opposite side of the insulating film to form the organic layer having a thickness that varies partially.

9. 6. The method for manufacturing an anisotropically conductive member according to claim 5, wherein the step of forming the organic layer includes a step of forming a first layer of uniform thickness and a step of partially forming a second layer on the surface of the first layer.

10. The method for manufacturing an anisotropically conductive member according to claim 9 , wherein the second layer has a smaller contact angle than the first layer.

11. 11. The method for manufacturing an anisotropically conductive member according to claim 5, wherein the step of forming the organic layer includes a step including at least one of an ink-jet method and a coating method.

12. The method for manufacturing an anisotropically conductive member according to any one of claims 5 to 8, wherein the process for forming the organic layer includes a process for forming a base layer of uniform thickness, and a process for subjecting the base layer to a pattern etching process to change the thickness in parts.

13. A structure in which a plurality of electronic devices are electrically connected to the anisotropically conductive member according to any one of claims 1 to 4, the plurality of electronic devices each have a plurality of electrodes electrically connected to the anisotropically conductive member; The plurality of electronic devices are different from one another in at least one of the height, width, and inter-electrode distance of the electrodes.

14. The structure of claim 13 , wherein the plurality of electronic devices are different from each other in at least one of function and semiconductor type.

15. The structure of claim 13 or 14, wherein the plurality of electronic devices have different thicknesses.

16. A method for manufacturing a structure in which a plurality of electronic devices are electrically connected to the anisotropically conductive member according to any one of claims 1 to 4, comprising the steps of: the plurality of electronic devices each have a plurality of electrodes electrically connected to the anisotropically conductive member; the plurality of electronic devices are different in at least one of the height, width, and inter-electrode distance of the electrodes, and are also different in height; A method for manufacturing a structure, comprising the steps of placing the plurality of electronic devices on the anisotropically conductive member in ascending order of height and bonding the plurality of electronic devices.

17. The method for manufacturing a structure according to claim 16 , wherein the plurality of electronic devices are different from each other in at least one of function and semiconductor type.

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