JP2009244244A - Probe card - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a probe card that has good connection stability between inspection electrodes and electrodes to be inspected even after being exposed to high temperatures due to a burn-in test, and that can prevent displacement in contact between the inspection electrodes and a conductive part and in contact between the conductive part and probe contact needle or the electrodes to be inspected even after repeated use. <P>SOLUTION: The probe card includes an inspection circuit board that has the inspection electrodes formed so as to correspond to the electrodes to be inspected; and an anisotropically conductive member that electrically connects the electrodes to be inspected with the inspection electrodes. The inspection electrodes are provided so that at least chips thereof protrude from a surface of the test circuit board. The anisotropically conductive member has a plurality of conductive paths formed of conductive members that penetrate an insulating base material, which includes an anodic oxide film of an aluminum substrate with micropores, in a thickness direction in a manner such that the conductive paths are insulated from one another. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a probe card used for inspecting electrical characteristics of an object to be inspected such as a semiconductor wafer, and a probe inspection apparatus including the probe card.

In general, in a manufacturing process of a semiconductor integrated circuit device, a semiconductor chip is formed by forming a large number of integrated circuits on a wafer and then cutting the wafer.
Then, in order to inspect the electrical characteristics, this semiconductor chip is a probe test in a wafer state, a state cut into individual semiconductor chips, or a state before being encapsulated in a package and resin-sealed. A burn-in test is being conducted.

For such an inspection, Patent Document 1 describes a probe card used for inspecting the electrical characteristics of an object to be inspected in contact with an electrode to be inspected. A probe contact needle that is in electrical contact with the inspection electrode; a probe contact needle fixing holder that fixes a proximal end portion of the probe contact needle so that the vicinity of the distal end portion of the probe contact needle is exposed from the surface; An inspection circuit board on which an inspection electrode is formed so as to correspond to an inspected electrode of the body, a base end portion of a probe contact needle exposed from the back side of the probe contact needle fixing holder, and an inspection circuit board An anisotropic conductive sheet that electrically connects between the inspection electrodes, and
The anisotropic conductive sheet includes a plurality of connecting conductive portions extending in the thickness direction and spaced apart from each other along the surface direction, and an insulating portion formed between the connecting conductive portions. A probe card comprising an elastic anisotropic conductive film and a frame plate that supports the elastic anisotropic conductive film. A cantilever probe card is disclosed.

Further, in Patent Document 2, “a probe card for inspecting electrical characteristics of an object to be inspected below, which is provided between a circuit board and the circuit board and the object to be inspected,” A contact structure for inspection for energizing between the body and the circuit board,
The inspection contact structure includes a flat substrate and a plurality of elastic conductive parts attached to both upper and lower surfaces of the substrate so as to sandwich the substrate, and an insulating part that connects the conductive parts to each other. And a sheet
The conductive portion is formed to penetrate each sheet and protrude from both upper and lower surfaces of each sheet,
A plurality of energization paths leading from the upper surface to the lower surface are formed on the substrate, and the conductive portions of the sheets on both sides of the substrate are electrically connected to the corresponding energization paths of the substrate,
Each sheet on both sides of the substrate is fixed to the substrate,
The probe card according to claim 1, wherein a sheet on an upper surface side of the substrate is fixed to the circuit substrate. Is disclosed.

JP 2007-225501 A JP 2008-39768 A

Here, in the probe card described in Patent Documents 1 and 2, the conductive part (connecting conductive part) in the sheet (anisotropic conductive sheet) is filled with conductive particles in an insulating elastic polymer substance. For this reason, the conductive portion is electrically conductive when compressed in the vertical direction.
Therefore, as a result of studying the probe cards described in Patent Documents 1 and 2, the inventor of the present invention has a high temperature in a burn-in test because the conductive portion is made of an elastic polymer material as described above. As a result, the conductive portion becomes brittle, and the inspection electrode of the inspection circuit board (hereinafter also simply referred to as “inspection electrode”) and the inspection electrode of the inspection object (hereinafter simply referred to as “inspection electrode”). It was also found that the connection stability with ”might be insufficient. Further, as described above, when the conductive portion is compressed in the vertical direction, it becomes electrically conductive, so that the contact between the inspection electrode and the conductive portion, or the contact between the conductive portion and the probe contact needle or the electrode to be inspected. It has been found that misalignment may occur in these contacts while it is repeated in a compressed state.

On the other hand, since the probe card described in Patent Document 1 has a number average particle diameter of 20 to 80 μm of conductive particles filled in the conductive portion, the pitch of the conductive portions is larger than that. Similarly, for the probe card described in Patent Document 2, the pitch between the conductive portions is about 180 μm.
On the other hand, in recent electronic parts such as semiconductor elements, as the integration is further advanced, the size of electrodes (terminals) becomes smaller, the number of electrodes (terminals) increases, and the distance between terminals also increases. It is getting narrower.
For this reason, it has been found that these probe cards may not be able to sufficiently cope with the evaluation of the electrical characteristics of the electrode to be inspected.

  Therefore, the present invention has good connection stability between the inspection electrode and the electrode to be inspected even after being exposed to a high temperature by the burn-in test, and the inspection electrode and the conductive portion (hereinafter referred to as the present invention) even after repeated use. Is also referred to as a “conduction path”), and a first object is to provide a probe card in which positional displacement is unlikely to occur in contact with a conduction portion and contact between a conduction portion and a probe contact needle or an electrode to be inspected.

  A second object of the present invention is to provide a probe inspection apparatus including a probe card that can sufficiently cope with electronic components such as semiconductor elements even at the present time when the integration is further advanced.

  As a result of earnest research to achieve the first object, the present inventors have insulated a plurality of conductive paths made of conductive members from each other in an insulating base material made of an anodized film of an aluminum substrate having micropores. In this state, the insulating base material is penetrated in the thickness direction, one end of each conductive path protrudes on one surface of the insulating base material, and the other end of each conductive path is the insulating base material. Stability of the connection between the electrode for inspection and the electrode to be inspected even after the probe card using the specific member provided in the protruding state on the other side of the metal as an anisotropic conductive member is exposed to a high temperature by the burn-in test The present invention has been completed by finding that positional deviation is less likely to occur in contact between the inspection electrode and the conducting portion and contact between the conducting portion and the probe contact needle or the electrode to be inspected even after repeated use.

  In addition, as a result of earnest research to achieve the second object, the present inventor appropriately adjusts the regularity and period of micropores existing in the film among the anisotropic conductive members of the specific member described above. As a result, the present invention has been completed by finding that it can sufficiently cope with electronic parts such as semiconductor elements even at the present time when the integration is further advanced.

  That is, the present invention provides the following (1) to (9).

(1) A probe card for inspecting the electrical characteristics of an object to be inspected in contact with the electrode to be inspected,
An inspection circuit board on which inspection electrodes are formed so as to correspond to the electrodes to be inspected;
An anisotropic conductive member that electrically connects the electrode to be inspected and the electrode for inspection,
The inspection electrode is provided with at least a tip portion protruding from the surface of the inspection circuit board,
In the insulating base material, the anisotropic conductive member penetrates the insulating base material in the thickness direction in a state where a plurality of conductive paths made of the conductive member are insulated from each other, and each of the conductive paths A member provided with one end protruding on one surface of the insulating base material and the other end of each conduction path protruding on the other surface of the insulating base material, the insulating base material being a micro A probe card, which is a structure made of an anodized film on an aluminum substrate having pores.

(2) Furthermore, an electrical contact that is in electrical contact with the electrode to be inspected is provided,
The probe card according to (1), wherein the electrode to be inspected and the anisotropic conductive member are connected through the electrical contact.

  (3) The probe card according to (2), wherein the electrical contact is a probe contact needle.

  (4) The probe card according to (3), further including a fixing holder that fixes the probe contact needle so that both tip portions of the probe contact needle protrude from the surface.

(5) The probe card according to any one of (1) to (4), wherein the circuit board for inspection is made of a material having a coefficient of thermal expansion of 2.5 × 10 ⁻⁶ to 10 × 10 ⁻⁶ K ^−1. .

(6) The probe card according to any one of (1) to (5), which is used for the object to be inspected made of a material having a coefficient of thermal expansion of 2.5 × 10 ⁻⁶ to 10 × 10 ⁻⁶ K ^−1. .

(7) The probe card according to any one of (4) to (6), wherein the fixed holder is made of a material having a coefficient of thermal expansion of 2.5 × 10 ⁻⁶ to 10 × 10 ⁻⁶ K ⁻¹ .

(8) before inspecting the electrical characteristics of the object to be inspected, a pretreatment step of bringing the protruding portion of the conduction path in contact with the electrode to be inspected into contact with an alkaline aqueous solution or an acidic aqueous solution;
The method for inspecting a probe card according to (1), further including an inspection step of inspecting the electrical characteristics of the object to be inspected by bringing the protruding portion after the pretreatment step into contact with the electrode to be inspected.

(9) before inspecting the electrical characteristics of the object to be inspected, a pretreatment step of bringing the electrical contact into contact with an alkaline aqueous solution or an acidic aqueous solution;
The probe according to any one of (2) to (7), further comprising an inspection step of inspecting the electrical characteristics of the object to be inspected by bringing the electrical contact after the pretreatment step into contact with the electrode to be inspected. Card inspection method.

  As shown below, according to the present invention, the connection stability between the inspection electrode and the electrode to be inspected is good even after being exposed to a high temperature by the burn-in test, and the inspection electrode and the conduction path are also used after repeated use. It is possible to provide a probe card that is less likely to be misaligned in contact with the contact portion or in contact between the conducting portion and the probe contact needle or the electrode to be inspected.

  In addition, according to the present invention, by appropriately adjusting the period of the micropores (conducting path pitch) and the density of the conducting paths, the present invention is sufficiently applied to electronic components such as semiconductor elements even at the present time when the integration is further advanced. A probe card that can be used can be provided.

  Furthermore, the probe card of the present invention is not only easy to contact even when a probe contact needle is used together with an anisotropic conductive member, but if they are in contact, misalignment occurs. Since it is difficult to join the probe, the probe contact needle can be appropriately replaced according to the type of the object to be inspected and the size of the electrode to be inspected, which is very useful.

  Furthermore, according to the method for inspecting a probe card of the present invention, before inspecting the electrical characteristics of the object to be inspected, the contact part (protruding part of the conduction path, electrical contact) with the electrode to be inspected is treated with an alkaline aqueous solution Since it is brought into contact with the acidic aqueous solution, the deposits, oxide film and the like at the contact site can be removed, and a stable inspection can be performed.

The probe card of the present invention will be described in detail below.
The probe card of the present invention is a probe card for inspecting the electrical characteristics of an object to be inspected in contact with the electrode to be inspected.
An inspection circuit board on which inspection electrodes are formed so as to correspond to the electrodes to be inspected;
An anisotropic conductive member that electrically connects the electrode to be inspected and the electrode for inspection,
The inspection electrode is provided with at least a tip portion protruding from the surface of the inspection circuit board,
In the insulating base material, the anisotropic conductive member penetrates the insulating base material in the thickness direction in a state where a plurality of conductive paths made of the conductive member are insulated from each other, and each of the conductive paths A member provided with one end protruding on one surface of the insulating base material and the other end of each conduction path protruding on the other surface of the insulating base material, the insulating base material being a micro A probe card which is a structure made of an anodized film of an aluminum substrate having pores.
Next, the probe card of the present invention will be described with reference to FIGS.

FIG. 1 is a sectional view showing a schematic configuration of a preferred embodiment of the probe card of the present invention.
As shown in FIG. 1, the probe card 1 of the present invention corresponds to the electrode 3 to be inspected for the purpose of inspecting the electrical characteristics of the object 2 to be inspected by contacting the electrode 3 to be inspected 2. The probe card includes a circuit board for inspection 5 on which an inspection electrode 4 is formed, and an anisotropic conductive member 6 that electrically connects the electrode 3 to be inspected and the electrode 4 for inspection.

  Further, as shown in FIG. 1, the anisotropic conductive member 6 in the probe card 1 of the present invention is insulated in a state where a plurality of conductive paths 8 made of a conductive member are insulated from each other in an insulating base material 7. The conductive substrate 7 penetrates in the thickness direction, and one end of each conduction path 8 protrudes on one surface of the insulating substrate 7, and the other end of each conduction path 8 is on the other surface of the insulating substrate 7. It is a member provided in a protruding state. The inspection circuit board 5 and the anisotropic conductive member 6 will be described in detail below.

[Inspection circuit board]
The inspection circuit board is a circuit board on which inspection electrodes are formed so as to correspond to the electrodes to be inspected.
The circuit board for inspection is a so-called performance board, and a printed wiring board can be used in the same manner as a conventionally known probe card.

In the present invention, the material of the circuit board for inspection is not particularly limited, but is preferably made of a material having a coefficient of thermal expansion of 2.5 to 10 × 10 ⁻⁶ K ⁻¹ , and specific examples thereof include , Silicon substrate (thermal expansion coefficient: 2.6 × 10 ^{−6 to} 3.5 × 10 ⁻⁶ K ⁻¹ ), alumina ceramic substrate (thermal expansion coefficient: 7.5 × 10 ⁻⁶ K ⁻¹ ), silicon carbide (Ceramic) substrates (thermal expansion coefficient: 4.0 × 10 ⁻⁶ K ⁻¹ ) and the like are preferable.
When the coefficient of thermal expansion is within the above range, the displacement between the inspection electrode and the conductive portion is less likely to occur even after repeated use, and as a result, the inspection electrode even after being exposed to a high temperature by a burn-in test. The connection stability between the electrode and the electrode to be inspected becomes better, and the displacement between the conductive portion and the probe contact needle or the electrode to be inspected after repeated use becomes less likely to occur.
Among these, an alumina substrate and a ceramic substrate that are excellent in heat resistance and warpage resistance at high temperatures are preferable.

In the present invention, as shown in FIG. 1, at least the tip of the inspection electrode is provided so as to protrude from the surface of the inspection circuit board.
As described above, by providing the above-described inspection electrode so as to protrude, the inspected electrode of the object to be inspected and the conduction path of the anisotropic conductive member are thermally fused as described in the method of manufacturing the probe card of the present invention described later. It becomes easy to join by wearing or the like.

Here, the method for projecting the inspection electrode is not particularly limited, and can be projected by a known method as described below.
Specifically, for example, as described in pages 151 to 157 of “Introduction to Printed Wiring Board Manufacturing” (8th edition, 2004, Nikkan Kogyo Shimbun), for copper-clad laminate (JIS standard) Then, after the exposure and development, an etching process is performed to form a part of the copper (Cu) wiring as a protruding electrode (protruding portion). The convex electrode is preferably coated with Ni by an electroless plating method or the like, and further coated with Au on the outermost surface to suppress natural oxidation.

  Moreover, as described on pages 158 to 166 of the same document, a method of providing a solder resist layer and forming the protruding portion by solder is also suitably exemplified. In this method, the shape of the solder is determined by the surface tension in the molten state, and becomes almost hemispherical. Therefore, the height of the protruding portion is proportional to the size of the electrode pattern and is generally 1/8 to 1/2 (hemisphere) of the size of the electrode pattern.

Furthermore, the aspect which forms the protrusion part by gold | metal | money (Au) in the Cu electrode part of the printed wiring board produced from the copper clad laminated board is preferable from a viewpoint of press-fit improvement.
The formation of the protruding portion by Au is, for example, a method of patterning a commercially available Au wiring ink (for example, a metal paste for fine wiring (NPG-J) manufactured by Harima Kasei Co., Ltd.) by an inkjet method, or a known forming method ( Examples thereof include JP-A-2-90622, JP-A-2-98139, JP-A-5-175200, and JP-A-2004-289135.

  The height of the projecting portion that can be formed by such a method has a variation of ± 30 μm or less from the viewpoint of easy joining between the electrode to be inspected and the conduction path of the anisotropic conductive member. Preferably, it is ± 10 μm or less, more preferably ± 1 μm or less.

  In the present invention, the inspection circuit board is preferably formed in a substantially disk shape, and its outer peripheral portion is preferably held by a holder (reference numeral 9 in FIG. 1).

The probe card of the present invention having such a circuit board for inspection is preferably used for an object to be inspected made of a material having a coefficient of thermal expansion of 2.5 to 10 × 10 ⁻⁶ K ^−1. For this, a silicon substrate (thermal expansion coefficient: 2.6 × 10 ^{−6 to} 3.5 × 10 ⁻⁶ K ⁻¹ ) or the like can be suitably used.

[Anisotropic conductive member]
2A and 2B are simplified views showing an example of a preferred embodiment of the anisotropic conductive member. FIG. 2A is a plan view, and FIG. 2B is a cross-sectional line IB-IB in FIG. It is sectional drawing seen from.
The anisotropic conductive member 6 includes a plurality of conductive paths 8 made of an insulating base material 7 and a conductive member.
The conduction path 8 has a length in the axial direction that is equal to or greater than the length (thickness) in the thickness direction Z (Z1, Z2) of the insulating base material 7 and penetrates the insulating base material 7 in a state of being insulated from each other. Provided.
The conductive paths 8 are provided with one end of each conductive path 8 protruding from one surface of the insulating base material 7 and the other end of each conductive path 8 protruding from the other surface of the insulating base material 7. It is done. That is, both ends of each conduction path 8 have projections 10 a and 10 b that project from the main surfaces 7 a and 7 b of the insulating substrate 7.
Further, the conductive path 8 has at least a portion in the insulating base material 7 (hereinafter, also referred to as “in-base conductive portion 11”) in the thickness direction Z (Z 1, Z 2) of the insulating base material 7. It is preferably provided so as to be substantially parallel (parallel in FIG. 2). Specifically, the length (length / thickness) of the center line of the conduction path with respect to the thickness of the insulating base material is preferably 1.0 to 1.2, and preferably 1.0 to 1.05. It is more preferable that
Next, materials, dimensions, formation methods, and the like will be described for each of the insulating base material and the conduction path.

<Insulating base material>
The insulating base material constituting the anisotropic conductive member is a structure made of an anodized film of an aluminum substrate having micropores.
By using such a structure, the connection stability between the inspection electrode and the electrode to be inspected is good even after being exposed to a high temperature by the burn-in test, and the inspection electrode and the conductive portion are repeatedly connected even after repeated use. Misalignment is less likely to occur in contact and contact between the conducting portion and the probe contact needle or the electrode to be inspected.
This is because the insulating base material is mainly composed of alumina, which is an inorganic material (thermal expansion coefficient: 4.5 × 10 ⁻⁶ K ⁻¹ ), and thus has excellent heat resistance and is generally used. This is probably because the thermal expansion coefficient is close to the material (ceramic etc.) of the circuit board for inspection.

In the present invention, the degree of ordering defined by the following formula (i) for the micropores is preferably 40% or more, more preferably 70% or more, and even more preferably 80% or more. .
When the degree of ordering is in the above range, the insulating property in the planar direction of the insulating base material can be ensured more reliably particularly with a high frequency signal of 100 kHz or more.

  Ordering degree (%) = B / A × 100 (i)

  In the above formula (i), A represents the total number of micropores in the measurement range. B is centered on the center of gravity of one micropore, and when a circle with the shortest radius inscribed in the edge of another micropore is drawn, the center of gravity of the micropore other than the one micropore is placed inside the circle. This represents the number in the measurement range of the one micropore to be included.

FIG. 3 is an explanatory diagram of a method for calculating the degree of ordering of pores. The above formula (i) will be described more specifically with reference to FIG.
The micropore 101 shown in FIG. 3A is drawn with a circle 103 (inscribed in the micropore 102) having the shortest radius centered on the center of gravity of the micropore 101 and inscribed in the edge of another micropore. In this case, the center of the micropores other than the micropores 101 is included in the circle 103. Therefore, the micropore 101 is included in B.
The micropore 104 shown in FIG. 3B draws a circle 106 having the shortest radius (inscribed in the micropore 105) that is centered on the center of gravity of the micropore 104 and inscribed in the edge of another micropore. In such a case, the center of gravity of the micropores other than the micropores 104 is included inside the circle 106. Therefore, the micropore 104 is not included in B.
Further, the micropore 107 shown in FIG. 3B is centered on the center of gravity of the micropore 107 and has the shortest radius 109 inscribed in the edge of the other micropore (inscribed in the micropore 108). Is drawn, the circle 109 includes seven centroids of micropores other than the micropore 107. Therefore, the micropore 107 is not included in B.

Moreover, it is preferable that the period of the said micropore is 0.1-0.6 micrometer, It is more preferable that it is 0.2-0.6 micrometer, It is still more preferable that it is 0.4-0.6 micrometer.
When the period is in the above range, the connection reliability is improved because it is easy to balance the diameter of each conduction path, which will be described later, and the width between the conduction paths (insulating partition wall thickness), particularly for high-frequency signals of 100 kHz or more. It is excellent in transmission (high-frequency characteristics), and can be sufficiently applied to electronic parts such as semiconductor elements even at the present time when integration is further advanced.
Here, the period refers to the distance between the centers of adjacent micropores.

  Furthermore, from the viewpoint of making the conduction path described later into a straight tube structure, the micropores do not have a branch structure, that is, the number X of micropores per unit area of one surface of the anodized film and the unit of another surface The ratio of the number of micropores Y per area is preferably X / Y = 0.90 to 1.10, more preferably X / Y = 0.95 to 1.05, and X / Y = It is particularly preferably 0.98 to 1.02.

Furthermore, alumina, which is a material of an anodic oxide film of aluminum, has an electrical resistivity of 10 ¹⁴ Ω · like an insulating base material (for example, a thermoplastic elastomer) constituting a conventionally known anisotropic conductive film or the like. It is about cm.

  In the present invention, the thickness of the insulating base (the portion represented by reference numeral 12 in FIG. 2B) is preferably 1-1000 μm, more preferably 5-500 μm. More preferably, it is -300 micrometers. When the thickness of the insulating substrate is within this range, the handleability of the insulating substrate is improved.

  Moreover, in this invention, it is preferable that the width | variety between the said conduction paths in the said insulating base material (part represented by the code | symbol 13 in FIG. 2 (B)) is 10 nm or more, and is 20-400 nm. Is more preferable. When the width between the conductive paths in the insulating substrate is within this range, the insulating substrate sufficiently functions as an insulating partition.

In the present invention, the insulating base material can be produced, for example, by anodizing an aluminum substrate and penetrating micropores generated by the anodization.
Here, the anodizing and penetrating treatment steps will be described in detail in a method for manufacturing an anisotropic conductive member described later.

<Conduction path>
The conduction path constituting the anisotropic conductive member is made of a conductive member.
The conductive member is not particularly limited as long as the electrical resistivity is 10 ³ Ω · cm or less, and specific examples thereof include gold (Au), silver (Ag), copper (Cu), aluminum (Al ), Magnesium (Mg), nickel (Ni), tungsten (W), cobalt (Co), rhodium (Rh), tin oxide doped with indium (ITO), molybdenum (Mo), iron (Fe), Pd Preferred examples include (palladium), beryllium (Be), rhenium (Re), alloys containing these metals as main components, and the like.
Among these, from the viewpoint of electrical conductivity, it is preferably made of any one metal selected from the group consisting of copper, nickel and gold, or an alloy containing these metals as a main component.
Further, from the viewpoint of cost, it is more preferable that only the surfaces of the conductive paths protruding from both surfaces of the insulating base material (hereinafter also referred to as “end faces”) are formed of gold.

By using such a conductive member, the connection stability between the electrode for inspection and the electrode to be inspected is good even after being exposed to a high temperature by the burn-in test, and the electrode for inspection and the conductive portion are connected even after repeated use. And a probe card that is unlikely to be displaced in contact between the contact portion and the conducting portion and the probe contact needle or the electrode to be inspected, and a probe inspection device including the probe card can be provided.
This is because, unlike the conductive parts described in Patent Documents 1 and 2 described above, conduction is possible regardless of compression in the vertical direction, and compression to the anisotropic conductive member in repeated use is reduced. Conceivable.

In the present invention, the conduction path is columnar, and the diameter (portion represented by reference numeral 14 in FIG. 2B) is preferably 5 to 500 nm, more preferably 20 to 400 nm. 260 to 380 nm is more preferable, and 300 to 350 nm is particularly preferable. When the diameter of the conduction path is within this range, a sufficient response can be obtained when a high-frequency electrical signal is passed, and thus the probe card can be used more suitably.
Further, as described above, the length (length / thickness) of the center line of the conduction path with respect to the thickness of the insulating base material is preferably 1.0 to 1.2, and 1.0 to 1. More preferably, it is 05. When the length of the center line of the conduction path with respect to the thickness of the insulating substrate is within this range, it can be evaluated that the conduction path has a straight pipe structure, and a one-to-one response is obtained when an electric signal is passed. Since it can obtain reliably, it can be used more suitably as a probe card.

  Moreover, in this invention, when the both ends of the said conduction path protrude from both surfaces of the said insulating base material, the protruded part (The part represented by code | symbol 10a and 10b in FIG. 2 (B). The height of the “protruding portion” is preferably 10 to 500 nm, and more preferably 10 to 200 nm. When the height of the protruding portion is within this range, the bonding property with the electrode (pad) portion of the electronic component is improved.

In the present invention, the conduction paths exist in a state of being insulated from each other by the insulating base material, and the density is preferably ² million pieces / mm ² or more, and 3 million pieces / mm ^2. The above is particularly preferable.
Since the density of the conductive paths is within this range, it can sufficiently cope with electronic components such as semiconductor elements even at the present time when the high integration is further advanced.

  In the present invention, the center-to-center distance between adjacent conductive paths (the portion represented by reference numeral 15 in FIG. 2; hereinafter also referred to as “pitch”) is 0.1 to 0.6 μm. Is more preferable, it is more preferable that it is 0.2-0.6 micrometer, and it is still more preferable that it is 0.4-0.6 micrometer. When the pitch is within this range, the connection reliability is good because the balance between the conduction path diameter and the width between the conduction paths (insulating partition wall thickness) is easy to achieve, and in particular, transmission with a high-frequency signal of 100 kHz or more (high-frequency characteristics) ) And is capable of sufficiently dealing with electronic parts such as semiconductor elements even at the present time when high integration is further advanced.

Furthermore, in the present invention, the conductive path can be manufactured, for example, by filling a metal, which is a conductive member, into a hole formed by a micropore formed in the insulating base material.
Here, the process of filling the metal will be described in detail in the method for manufacturing the anisotropic conductive member described later.

  As described above, the anisotropic conductive member having such an insulating base and a conduction path has a thickness of the insulating base of 1 to 1000 μm and a diameter of the conduction path of 5. It is preferable that the thickness is ˜500 nm because high conductivity can be confirmed while maintaining high insulation.

[Electrical contact]
The probe card of the present invention preferably includes an electrical contact for connecting the electrode to be inspected and the anisotropic conductive member.

<Probe contact needle>
FIG. 4 is a cross-sectional view showing a schematic configuration of one preferred embodiment of the electrical contact in the probe card of the present invention.
The probe card of the present invention preferably includes a probe contact needle 16 as shown in FIG.

Here, the probe contact needle is not particularly limited as long as it is a material having an electrical resistivity of 10 ³ Ω · cm or less, as in the case of the conduction path. Specific examples thereof include gold (Au) and silver (Ag). , Copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), tungsten (W), cobalt (Co), rhodium (Rh), indium-doped tin oxide (ITO), molybdenum ( Preferred examples include Mo), iron (Fe), Pd (palladium), beryllium (Be), rhenium (Re), and alloys containing these metals as main components.
Above all, from the viewpoint of hardness as an electrical contact, difficulty in natural oxidation, etc., any one metal selected from the group consisting of nickel, tungsten and cobalt, or an alloy containing these metals as a main component Preferably it consists of.

In the present invention, the probe contact needle is not formed of any one metal selected from the group consisting of nickel, tungsten and cobalt, or an alloy containing these metals as a main component. At least the proximal end portion 17 of the probe contact needle is preferably formed of these metals or alloys.
This formation method is not particularly limited, and examples thereof include a formation method using a vacuum apparatus such as a CVD method and a sputtering method, a formation method by electroless plating, and the like.
The probe contact needle may be subjected to a known surface hardening treatment such as DLC coating, ion plating of titanium (Ti), titanium nitride (TiN), etc. from the viewpoint of improving the surface hardness and wear resistance. Good.

As shown in FIG. 4, when the probe contact needle 16 is provided, the base end portion 17 is provided so as to contact the conduction path 8 of the anisotropic conductive member 6, and the tip end portion 18 is provided as a probe. When the card 1 is pressed against the integrated circuit formed on the wafer, the card 1 is provided so as to contact the electrode 3 to be inspected.
Thereby, the electrode 3 to be inspected and the electrode 4 for inspection are electrically connected via the probe contact needle 16 and the conduction path 8 of the anisotropic conductive member 6.
Here, as a method for fixing the probe contact needle 16, for example, a method of fixing to a support ring with an adhesive (see, for example, JP-A-3-139533), a Si wafer is processed by a MEMS method or a VLS method. And a method of creating a probe needle array (see, for example, JP-A-11-190748).

  By having such a probe contact needle, unlike the embodiment shown in FIG. 1, it is possible to inspect the electrical characteristics of an inspected object having a surface structure in which the inspected electrode is located deeper than the surface of the wafer body. it can.

  In the present invention, the probe contact needle is preferably a vertical spring-type contact needle from the viewpoint of easy contact with each electrode to be inspected even when the surface of the wafer body is uneven. .

  In the present invention, the shape of the probe contact needle is not particularly limited, but is preferably a needle shape, and the diameter at the tip thereof is preferably 0.2 to 200 μm, preferably 0.8 to 100 μm. More preferably, it is 1 to 50 μm. When the diameter of the probe contact needle is within this range, a sufficient response can be obtained when an electric signal is flowed, so that it can be more suitably used as a probe card.

Furthermore, in the present invention, the probe contact needle is a surface of the base end portion (referred to as a contact surface with the conduction portion) from the viewpoint of making the displacement of the contact between the conduction portion and the probe contact needle more difficult. The same)) is preferably formed. The depth of such a depression is preferably 10 to 500 nm. For example, by using MEMS (Micro Electro Mechanical Systems) technology, a portion corresponding to the base end portion of the probe contact needle of the probe contact needle mold is used. A depression is provided in advance, and a method of forming a probe contact needle by electroforming, a method of removing a portion that becomes a depression by laser ablation, or the like can be used.
From the same viewpoint, the surface of the proximal end portion of the probe contact needle has an arithmetic average roughness Ra of 0.001 to 0.5 μm, a maximum height Rz of 0.01 to 0.9 μm, and a maximum height. The thickness Rz / arithmetic average roughness Ra is preferably 2 to 15.
As described above, since the columnar diameter of the conducting path is as thin as 5 to 500 nm as described above, when the conducting part comes into contact with the probe contact needle, one end (tip) of the conducting part is the base end of the probe contact needle. It is specified to be caught on the surface of the part.

  As shown in FIG. 4, the probe card of the present invention includes a fixing holder 19 for fixing the probe contact needle 16 so that both end portions (17, 18) of the probe contact needle 16 protrude from the surface. Is more preferable.

Here, the fixed holder is, for example, an epoxy resin (thermal expansion coefficient: 18 × 10 ⁻⁶ K ⁻¹ ) or a glass fiber reinforced epoxy resin (thermal expansion coefficient: 13 × 10 ^{−6 to} 16 × 10 ⁻⁶ K). ^-1 ), glass fiber reinforced phenolic resin (thermal expansion coefficient: 13 × 10 ^{−6 to} 16 × 10 ⁻⁶ K ⁻¹ ), glass fiber reinforced polyimide resin (thermal expansion coefficient: 13 × 10 ^{−6 to} 16 ×) 10 ⁻⁶ K ⁻¹ ), resin such as glass fiber reinforced bismaleimide triazine resin (thermal expansion coefficient: 13 × 10 ^{−6 to} 16 × 10 ⁻⁶ K ⁻¹ ); alumina (thermal expansion coefficient: 4.5 ×) 10 ^{−6 to} 7 × 10 ⁻⁶ K ⁻¹ ), beryllia (thermal expansion coefficient: 7 × 10 ⁻⁶ to 8 × 10 ⁻⁶ K ⁻¹ ), silicon carbide (thermal expansion coefficient: 4.0 × 10 ⁻⁶⁾ Ceramics such as K ^-1 ), aluminum nitride (thermal expansion coefficient: 4.5 × 10 ^-6 K ^-1 ), boron nitride (thermal expansion coefficient: 3 × 10 ^-6 K ^-1 ), etc. It is preferable that it is comprised with the material of these.
Among them, a material having a coefficient of thermal expansion of 2.5 × 10 ⁻⁶ to 10 × 10 ⁻⁶ K ⁻¹ is preferable. Specifically, silicon carbide is an electrode for inspection even after repeated use. This is preferable because positional deviation is less likely to occur in contact with the conductive portion.

  In the probe card of the present invention, it is further preferable that the fixing holder 19 has a function of fixing the anisotropic conductive member 6 to the circuit board 5 for inspection. For example, as shown in FIG. 4, it is preferable to fix to the circuit board 5 for a test | inspection by the fixing member 20 comprised so that it might fasten with the screw etc. which consist of metal materials, such as stainless steel.

Furthermore, in the probe card of the present invention, it is preferable that the surface of the fixed holder 19 (the surface on the anisotropic conductive member 6 side) is covered with the resin material 21.
The resin material is preferably a heat-resistant material, and elastic rubber (for example, fluorine-based FKM, silicon rubber, acrylic rubber, etc.), a thermoplastic polyester elastomer, and the like are preferably exemplified.

Examples of the resin material include a thin film silicone sheet (Sμ-50-50, heat resistant at 200 ° C., manufactured by Sanshin Enterprise), a thermoplastic polyester elastomer (Perprene (registered trademark) C type, heat resistant at 175 ° C .: manufactured by Toyobo Co., Ltd.), under Commercial products such as fill resin (2274B, coefficient of thermal expansion: 7.4 × 10 ⁻⁶ K ⁻¹ , manufactured by Three Bond Co., Ltd.) can be used.

  The coating thickness of the resin material is preferably the same as the protruding height of the proximal end portion 17 of the probe contact needle 16 from the surface of the fixed holder 19, and more preferably 1 μm to 10 mm.

  By using such a resin material, when the fixed holder and the anisotropic conductive material are brought into contact with each other, the pressure is dispersed, preventing cracks in the anisotropic conductive member due to overloading due to excessive tightening. it can. Further, in the burn-in test, it is possible to prevent the parallelism between the anisotropic conductive member and the fixed holder caused by the positional deviation between the anisotropic conductive member and the fixed holder.

  In the present invention, even when such a probe contact needle is provided, the contact between the conduction path and the probe contact needle is easy, and it is difficult to cause a positional shift, so that it is necessary to make a connection. Therefore, the probe contact needle can be appropriately replaced according to the type of the object to be inspected and the size of the electrode to be inspected.

<Bump contact>
FIG. 5 is a sectional view showing a schematic configuration of another preferred embodiment of the electrical contact in the probe card of the present invention.
As shown in FIG. 5, the probe card of the present invention preferably includes a bump contact 21.

Here, the bump-like contact is not particularly limited as long as it has a material with an electric resistivity of 10 ³ Ω · cm or less, as in the case of the conduction path. Specific examples thereof include gold (Au) and silver (Ag). , Copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), tungsten (W), cobalt (Co), rhodium (Rh), indium-doped tin oxide (ITO), molybdenum ( Preferred examples include Mo), iron (Fe), Pd (palladium), beryllium (Be), rhenium (Re), and alloys containing these metals as main components.
Above all, from the viewpoint of hardness as an electrical contact, difficulty in natural oxidation, etc., any one metal selected from the group consisting of nickel, tungsten and cobalt, or an alloy containing these metals as a main component Preferably it consists of.

As shown in FIG. 5, when the bump-shaped contact 22 is provided, the base end portion 23 is provided so as to come into contact with the conduction path 8 of the anisotropic conductive member 6, and the tip end portion 24 is provided on the probe card 1. Is pressed against the integrated circuit formed on the wafer so as to come into contact with the electrode 3 to be inspected.
As a result, the electrode 3 to be inspected and the electrode 4 for inspection are electrically connected via the bump contact 22 and the conduction path 8 of the anisotropic conductive member 6.

  By having such a bump-shaped contact, unlike the embodiment shown in FIG. 1, it is possible to inspect the electrical characteristics of an inspected object having a surface structure in which the inspected electrode is located deeper than the surface of the wafer body. it can.

In the present invention, the bump contact is formed on the back surface of the anisotropic conductive member (the surface on the 7b and 10b side in FIG. 2) by a method such as electroless plating, vapor deposition, or sputtering. After forming a metal (for example, copper) layer, the conductive path of the anisotropic conductive member is formed by a method of patterning by photoetching or laser exposure as described in, for example, Japanese Patent Laid-Open No. 4-126307. A bump-shaped contact (conductive portion) can be formed at a position corresponding to the electrode to be inspected.
In this method, the height of the contact is substantially equal to the thickness of the metal layer formed on the surface, and therefore it can be set to an arbitrary height by controlling the thickness of the metal layer.
In addition, it is preferable to perform this method after the metal filling process and surface smoothing process which will be described later.

In the present invention, the bump contact can also be formed by a trimming process or an electrodeposition process in a protrusion forming process described later.
Further, the bump-shaped contact may be subjected to a known surface hardening treatment such as DLC coating, ion plating of titanium (Ti), titanium nitride (TiN), etc. from the viewpoint of improving the surface hardness and wear resistance. Good.

In the present invention, the shape of the bump contact is not particularly limited, but is preferably columnar or hemispherical, and the diameter is preferably 0.05 to 200 μm, and preferably 0.1 to 100 μm. More preferably, it is 1-50 micrometers. Moreover, it is preferable that the height is 0.05-50 micrometers, it is more preferable that it is 0.1-20 micrometers, and it is still more preferable that it is 1-5 micrometers. Further, the size is preferably about 1/500 to 1/2 of the size of the electrode.
When the diameter, height, and size of the bump-shaped contact are within this range, a sufficient response can be obtained when an electric signal is passed, and therefore, it can be used more suitably as a probe card.

  Below, the manufacturing method of the probe card of this invention which comprises the circuit board for an inspection mentioned above and an anisotropic conductive member is demonstrated in detail.

First, a method for producing the anisotropic conductive member (hereinafter also simply referred to as “anisotropic conductive member manufacturing method”) will be described in detail.
Although the anisotropic conductive member manufacturing method is not particularly limited, an anodizing treatment step for anodizing an aluminum substrate,
After the anodizing treatment step, a penetrating treatment step for obtaining the insulating base material by penetrating holes by the micropores generated by the anodizing,
After the penetrating treatment step, a metal filling step of filling the metal that is a conductive member into the inside of the penetrated hole in the obtained insulating base material and forming the conduction path; and
A method including a projecting portion forming step of obtaining the anisotropic conductive member by causing the end of the formed conductive path to project from the surface of the insulating base material after the metal filling step is preferably exemplified. .
Next, the aluminum substrate used in this anisotropic conductive member manufacturing method and each processing step applied to the aluminum substrate will be described in detail.

[Aluminum substrate]
The aluminum substrate used in the anisotropic conductive member manufacturing method is not particularly limited, and specific examples thereof include a pure aluminum plate; an alloy plate containing aluminum as a main component and containing a small amount of foreign elements; low-purity aluminum (for example, recycled material) ) On which a high-purity aluminum is deposited; a substrate on which the surface of silicon wafer, quartz, glass or the like is coated with high-purity aluminum by a method such as vapor deposition or sputtering; a resin substrate on which aluminum is laminated;

  In the present invention, of the aluminum substrate, the surface on which the anodized film is provided by the anodizing treatment step described later preferably has an aluminum purity of 99.5% by mass or more, and 99.9% by mass or more. Is more preferable, and it is still more preferable that it is 99.99 mass% or more. When the aluminum purity is within the above range, the regularity of the micropore array is sufficient.

  Moreover, in this invention, it is preferable that the surface which performs the anodic oxidation process mentioned later among aluminum substrates performs a degreasing process and a mirror surface finishing process previously.

<Heat treatment>
When heat treatment is performed, it is preferably performed at 200 to 350 ° C. for about 30 seconds to 2 minutes. Thereby, the regularity of the arrangement | sequence of the micropore produced | generated by the anodizing process mentioned later is improved.
The aluminum substrate after the heat treatment is preferably cooled rapidly. As a method of cooling, for example, a method of directly feeding into water or the like can be mentioned.

<Degreasing treatment>
The degreasing treatment uses acid, alkali, organic solvent, etc. to dissolve and remove the organic components such as dust, fat, and resin adhered to the surface of the aluminum substrate, and in each treatment described later due to the organic components. This is done for the purpose of preventing the occurrence of defects.

Specifically, as the degreasing treatment, for example, a method in which an organic solvent such as various alcohols (for example, methanol), various ketones (for example, methyl ethyl ketone), benzine, volatile oil or the like is brought into contact with the aluminum substrate surface at room temperature (organic Solvent method); a method of bringing a liquid containing a surfactant such as soap or neutral detergent into contact with the aluminum substrate surface at a temperature from room temperature to 80 ° C., and then washing with water (surfactant method); concentration of 10 to 200 g A method in which an aqueous solution of sulfuric acid / L is brought into contact with the aluminum substrate surface at a temperature from room temperature to 70 ° C. for 30 to 80 seconds and then washed with water; while contacting about seconds, the aluminum substrate surface and the electrolyte by passing a direct current of a current density of 1 to 10 a / dm ² in the cathode, the , A method of neutralizing by bringing a nitric acid aqueous solution having a concentration of 100 to 500 g / L into contact; while bringing various known anodizing electrolytes into contact with the aluminum substrate surface at room temperature, the aluminum substrate surface is used as a cathode and a current density of 1 to A method in which a 10 A / dm ² direct current is applied or an alternating current is applied for electrolysis; an alkaline aqueous solution having a concentration of 10 to 200 g / L is brought into contact with the aluminum substrate surface at 40 to 50 ° C. for 15 to 60 seconds; A method of neutralizing by bringing a nitric acid aqueous solution having a concentration of 100 to 500 g / L into contact; an emulsion obtained by mixing light oil, kerosene, etc. with a surfactant, water, etc. is brought into contact with the aluminum substrate surface at a temperature from room temperature to 50 ° C. Then, a method of washing with water (emulsification and degreasing method); a mixed solution of sodium carbonate, phosphates, surfactant and the like on the surface of the aluminum substrate at a temperature from room temperature to 50 ° C. Contacting 0-180 seconds, then, a method of washing with water (phosphate method); and the like.

  Among these, the organic solvent method, the surfactant method, the emulsion degreasing method, and the phosphate method are preferable from the viewpoint that the fat content on the aluminum surface can be removed while the aluminum hardly dissolves.

  Moreover, a conventionally well-known degreasing agent can be used for a degreasing process. Specifically, for example, various commercially available degreasing agents can be used by a predetermined method.

<Mirror finish processing>
The mirror finishing process is performed to eliminate unevenness on the surface of the aluminum substrate and improve the uniformity and reproducibility of the particle forming process by an electrodeposition method or the like. Examples of the irregularities on the surface of the aluminum substrate include rolling stripes generated during rolling in the case where the aluminum substrate is manufactured through rolling.
In the present invention, the mirror finish is not particularly limited, and a conventionally known method can be used. Examples thereof include mechanical polishing, chemical polishing, and electrolytic polishing.

  Examples of the mechanical polishing include a method of polishing with various commercially available polishing cloths, a method of combining various commercially available abrasives (for example, diamond, alumina) and a buff. Specifically, when an abrasive is used, a method in which the abrasive used is changed from coarse particles to fine particles over time is preferably exemplified. In this case, the final polishing agent is preferably # 1500. Thereby, the glossiness can be 50% or more (in the case of rolled aluminum, both the rolling direction and the width direction are 50% or more).

As chemical polishing, for example, “Aluminum Handbook”, 6th edition, edited by Japan Aluminum Association, 2001, p. Examples thereof include various methods described in 164 to 165.
Further, the phosphoric acid-nitric acid method, the Alupol I method, the Alupol V method, the Alcoa R5 method, the H ₃ PO ₄ —CH ₃ COOH—Cu method, and the H ₃ PO ₄ —HNO ₃ —CH ₃ COOH method are preferably exemplified. . Among these, the phosphoric acid-nitric acid method, the H ₃ PO ₄ —CH ₃ COOH—Cu method, and the H ₃ PO ₄ —HNO ₃ —CH ₃ COOH method are preferable.
By chemical polishing, the glossiness can be made 70% or more (in the case of rolled aluminum, both the rolling direction and the width direction are 70% or more).

As electrolytic polishing, for example, “Aluminum Handbook”, 6th edition, edited by Japan Aluminum Association, 2001, p. 164-165; various methods described in US Pat. No. 2,708,655; “Practical Surface Technology”, vol. 33, no. 3, 1986, p. The method described in 32-38;
By electropolishing, the gloss can be 70% or more (in the case of rolled aluminum, both the rolling direction and the width direction are 70% or more).

  These methods can be used in appropriate combination. Specifically, for example, a method of performing mechanical polishing in which the abrasive is changed from coarse particles to fine particles with time, and then performing electrolytic polishing is preferable.

By mirror finishing, for example, a surface having an average surface roughness R _{a of} 0.1 μm or less and a glossiness of 50% or more can be obtained. The average surface roughness _Ra is preferably 0.03 μm or less, and more preferably 0.02 μm or less. Further, the glossiness is preferably 70% or more, and more preferably 80% or more.
The glossiness is a regular reflectance obtained in accordance with JIS Z8741-1997 “Method 3 60 ° Specular Gloss” in the direction perpendicular to the rolling direction. Specifically, using a variable angle gloss meter (for example, VG-1D, manufactured by Nippon Denshoku Industries Co., Ltd.), when the regular reflectance is 70% or less, the incident reflection angle is 60 degrees and the regular reflectance is 70%. In the case of exceeding, the incident / reflection angle is 20 degrees.

[Anodizing process]
The anodic oxidation step is a step of forming an oxide film having micropores on the surface of the aluminum substrate by subjecting the aluminum substrate to an anodic oxidation treatment.
For the anodizing treatment in the anisotropic conductive member manufacturing method, a conventionally known method can be used, but the insulating base material is arranged so that the degree of ordering defined by the above formula (i) is 40% or more. Since an anodized film of an aluminum substrate having micropores is preferable, it is preferable to use a self-ordering method or a constant voltage treatment described later.

The self-ordering method is a method for improving the regularity by utilizing the property that the micropores of the anodic oxide film are regularly arranged and removing the factors that disturb the regular arrangement. Specifically, high-purity aluminum is used, and an anodized film is formed at a low speed over a long period of time (for example, several hours to several tens of hours) at a voltage corresponding to the type of the electrolytic solution.
In this method, since the diameter of the micropore (pore diameter) depends on the voltage, a desired pore diameter can be obtained to some extent by controlling the voltage.

In order to form micropores by the self-ordering method, at least an anodic oxidation treatment (A) described later may be performed. ) In this order (self-ordering method I), a method in which an anodic oxidation process (D) and an oxide film dissolution process (E) described later are performed at least once in this order (self-ordering method II), etc. It is preferable to do this.
Next, each process of the self-ordering method I and the self-ordering method II, which are preferred embodiments, will be described in detail.

[Self-ordering method I]
<Anodizing treatment (A)>
The average flow rate of the electrolytic solution in the anodizing treatment (A) is preferably 0.5 to 20.0 m / min, more preferably 1.0 to 15.0 m / min, and 2.0 to 10 More preferably, it is 0.0 m / min. By performing the anodizing treatment (A) at a flow rate in the above range, uniform and high regularity can be obtained.
Moreover, the method of flowing the electrolytic solution under the above-mentioned conditions is not particularly limited, but, for example, a method using a general stirring device such as a stirrer is used. In particular, it is preferable to use a stirrer that can control the stirring speed by digital display because the average flow velocity can be controlled. Examples of such a stirring apparatus include “Magnetic Stirrer HS-50D (manufactured by AS ONE)” and the like.

For the anodizing treatment (A), for example, a method of energizing an aluminum substrate as an anode in a solution having an acid concentration of 1 to 10% by mass can be used.
The solution used for the anodizing treatment (A) is preferably an acid solution, and hydrochloric acid, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid, glycolic acid, tartaric acid, Malic acid, citric acid, and the like are more preferable, and sulfuric acid, phosphoric acid, and oxalic acid are particularly preferable. These acids can be used alone or in combination of two or more.

The conditions for the anodizing treatment (A) vary depending on the electrolyte used, and thus cannot be determined unconditionally. In general, however, the electrolyte concentration is 0.1 to 20% by mass, and the solution temperature is −10 to 30 ° C. , Current density 0.01 to 20 A / dm ² , voltage 3 to 500 V, electrolysis time 0.5 to 30 hours are preferable, electrolyte concentration 0.5 to 15 mass%, liquid temperature −5 to 25 ° C., More preferably, the current density is 0.05 to 15 A / dm ² , the voltage is 5 to 250 V, the electrolysis time is 1 to 25 hours, the electrolyte concentration is 1 to 10% by mass, the solution temperature is 0 to 20 ° C., and the current density is 0.1. More preferably, it is 10A / dm < ² >, voltage 10-200V, and electrolysis time 2-20 hours.

  The treatment time for the anodizing treatment (A) is preferably 0.5 minutes to 16 hours, more preferably 1 minute to 12 hours, and even more preferably 2 minutes to 8 hours.

  The anodizing treatment (A) can be performed by changing the voltage intermittently or continuously in addition to being performed under a constant voltage. In this case, it is preferable to decrease the voltage sequentially. This makes it possible to reduce the resistance of the anodized film, and fine micropores are formed in the anodized film, which is preferable in terms of improving uniformity, particularly when sealing treatment is performed by electrodeposition. .

  In the present invention, the thickness of the anodized film formed by such anodizing treatment (A) is preferably 1-1000 μm, more preferably 5-500 μm, and 10-300 μm. Is more preferable.

In the present invention, the average pore density of micropores in the anodized film formed by such anodizing treatment (A) is preferably 50 to 1500 / μm ² .
The area ratio occupied by the micropores is preferably 20 to 50%.
Here, the area ratio occupied by the micropore is defined by the ratio of the total area of the opening of the micropore to the area of the aluminum surface.

<Film removal treatment (B)>
The film removal process (B) is a process for dissolving and removing the anodized film formed on the surface of the aluminum substrate by the anodizing process (A).
After forming an anodic oxide film on the surface of the aluminum substrate by the anodizing treatment (A), a penetration treatment step described later may be performed immediately. ) And re-anodizing treatment (C) described later are preferably performed in this order, and then a penetration treatment step described later is performed.

  Since the anodized film becomes more regular as it gets closer to the aluminum substrate, the bottom part of the anodized film remaining on the surface of the aluminum substrate is removed once by this film removal treatment (B). Can be exposed to the surface to obtain regular depressions. Therefore, in the film removal treatment (B), aluminum is not dissolved, but only the anodized film made of alumina (aluminum oxide) is dissolved.

  Alumina solution includes chromium compound, nitric acid, phosphoric acid, zirconium compound, titanium compound, lithium salt, cerium salt, magnesium salt, sodium fluorosilicate, zinc fluoride, manganese compound, molybdenum compound, magnesium compound, barium compound and An aqueous solution containing at least one selected from the group consisting of simple halogens is preferred.

Specific examples of the chromium compound include chromium (III) oxide and chromium (VI) anhydride.
Examples of the zirconium-based compound include zircon ammonium fluoride, zirconium fluoride, and zirconium chloride.
Examples of the titanium compound include titanium oxide and titanium sulfide.
Examples of the lithium salt include lithium fluoride and lithium chloride.
Examples of the cerium salt include cerium fluoride and cerium chloride.
Examples of magnesium salts include magnesium sulfide.
Examples of the manganese compound include sodium permanganate and calcium permanganate.
As a molybdenum compound, sodium molybdate is mentioned, for example.
Examples of the magnesium compound include magnesium fluoride pentahydrate.
Examples of barium compounds include barium oxide, barium acetate, barium carbonate, barium chlorate, barium chloride, barium fluoride, barium iodide, barium lactate, barium oxalate, barium perchlorate, barium selenate, selenite. Examples thereof include barium, barium stearate, barium sulfite, barium titanate, barium hydroxide, barium nitrate, and hydrates thereof.
Among the barium compounds, barium oxide, barium acetate, and barium carbonate are preferable, and barium oxide is particularly preferable.
Examples of the halogen alone include chlorine, fluorine, and bromine.

Among them, the alumina solution is preferably an aqueous solution containing an acid. Examples of the acid include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and a mixture of two or more acids may be used.
The acid concentration is preferably 0.01 mol / L or more, more preferably 0.05 mol / L or more, and still more preferably 0.1 mol / L or more. There is no particular upper limit, but generally it is preferably 10 mol / L or less, more preferably 5 mol / L or less. An unnecessarily high concentration is not economical, and if it is higher, the aluminum substrate may be dissolved.

  The alumina solution is preferably −10 ° C. or higher, more preferably −5 ° C. or higher, and still more preferably 0 ° C. or higher. In addition, since the starting point of ordering will be destroyed and disturbed if it processes using the boiling alumina solution, it is preferable to use it without boiling.

  The alumina solution dissolves alumina and does not dissolve aluminum. Here, the alumina solution may not dissolve aluminum substantially or may dissolve it slightly.

  The film removal treatment (B) is performed by bringing the aluminum substrate on which the anodized film is formed into contact with the above-described alumina solution. The method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.

The dipping method is a treatment in which an aluminum substrate on which an anodized film is formed is dipped in the above-described alumina solution. Stirring during the dipping process is preferable because a uniform process is performed.
The time for the dipping treatment is preferably 10 minutes or more, more preferably 1 hour or more, and further preferably 3 hours or more and 5 hours or more.

<Re-anodizing treatment (C)>
After removing the anodic oxide film by the film removal treatment (B) and forming regular depressions on the surface of the aluminum substrate, the anodic oxidation treatment is performed again, so that the degree of ordering of the micropores is higher. A film can be formed.
The anodizing treatment in the re-anodizing treatment (C) can be performed by a conventionally known method, but is preferably performed under the same conditions as the above-described anodizing treatment (A).
Also, a method of repeatedly turning on and off the current intermittently while keeping the DC voltage constant, and a method of repeatedly turning on and off the current while intermittently changing the DC voltage can be suitably used. According to these methods, fine micropores are generated in the anodic oxide film, which is preferable in that uniformity is improved particularly when sealing treatment is performed by electrodeposition.

When the re-anodizing treatment (C) is performed at a low temperature, the arrangement of micropores becomes regular and the pore diameter becomes uniform.
On the other hand, by performing the re-anodizing treatment (C) at a relatively high temperature, the arrangement of the micropores can be disturbed, and the pore diameter variation can be within a predetermined range. Also, the pore diameter variation can be controlled by the processing time.

  In the present invention, the film thickness of the anodized film formed by such re-anodizing treatment (C) is preferably 30 to 1000 μm, and more preferably 50 to 500 μm.

In the present invention, the pore diameter of the micropores of the anodized film formed by such anodizing treatment (C) is preferably 0.01 to 0.5 μm, preferably 0.02 to 0.1 μm. It is more preferable that
The average pore density is preferably 10 million pieces / mm ² or more.

  In the self-ordering method I, instead of the above-described anodizing treatment (A) and film removal treatment (B), for example, a physical method, a particle beam method, a block copolymer method, a resist pattern / exposure / etching method, etc. In addition, a recess serving as a starting point for generating micropores by the re-anodizing treatment (C) described above may be formed.

<Physical method>
For example, a method using an imprint method (a transfer method or a press patterning method in which a substrate or a roll having a protrusion is pressed against an aluminum plate to form a recess) can be used. Specifically, a method of forming a depression by pressing a substrate having a plurality of protrusions on the surface thereof against the aluminum surface can be mentioned. For example, a method described in JP-A-10-121292 can be used.
Another example is a method in which polystyrene spheres are arranged in a dense state on the aluminum surface, SiO ₂ is vapor-deposited thereon, then the polystyrene spheres are removed, and the substrate is etched using the vapor-deposited SiO ₂ as a mask to form depressions. It is done.

<Particle beam method>
The particle beam method is a method in which a hollow is formed by irradiating the aluminum surface with a particle beam. The particle beam method has an advantage that the position of the depression can be freely controlled.
Examples of the particle beam include a charged particle beam, a focused ion beam (FIB), and an electron beam.
As the particle beam method, for example, a method described in JP-A-2001-105400 can be used.

<Block copolymer method>
The block copolymer method is a method in which a block copolymer layer is formed on an aluminum surface, a sea-island structure is formed in the block copolymer layer by thermal annealing, and then an island portion is removed to form a depression.
As a block copolymer method, the method described in Unexamined-Japanese-Patent No. 2003-129288 can be used, for example.

<Resist pattern, exposure, etching method>
In the resist pattern / exposure / etching method, the resist on the surface of the aluminum plate is exposed and developed by photolithography or electron beam lithography to form a resist pattern, which is then etched. In this method, a resist is provided and etched to form a recess penetrating to the aluminum surface.

[Self-ordering method II]
<First step: Anodizing treatment (D)>
For the anodizing treatment (D), a conventionally known electrolytic solution can be used. When the film formation rate A is energized and the film dissolution rate B is non-energized under a direct current constant voltage condition, When the parameter R represented by the general formula (ii) is 160 ≦ R ≦ 200, preferably 170 ≦ R ≦ 190, and particularly preferably 175 ≦ R ≦ 185, the treatment is performed using an electrolytic solution. The regular arrangement can be greatly improved.

  R = A [nm / s] ÷ (B [nm / s] × applied voltage [V]) (ii)

The average flow rate of the electrolytic solution in the anodizing treatment (D) is preferably 0.5 to 20.0 m / min, similarly to the above-described anodizing treatment (A), and is 1.0 to 15.0 m / min. More preferably, it is 2.0 to 10.0 m / min. By performing anodization treatment (D) at a flow rate in the above range, uniform and high regularity can be obtained.
Moreover, the method of flowing the electrolytic solution under the above-mentioned conditions is not particularly limited as in the case of the above-described anodic oxidation treatment (A). For example, a method using a general stirring device such as a stirrer is used. In particular, it is preferable to use a stirrer that can control the stirring speed with a digital display because the average flow rate can be controlled. Examples of such a stirring apparatus include “Magnetic Stirrer HS-50D (manufactured by AS ONE)” and the like.
The viscosity of the anodizing solution is preferably 0.0001 to 100.0 Pa · s, more preferably 0.0005 to 80.0 Pa · s at 25 ° C. under 1 atm. By performing the anodic oxidation treatment (D) with an electrolytic solution having a viscosity in the above range, uniform and high regularity can be obtained.

Although both acidic and alkaline can be used for the electrolytic solution used in the anodizing treatment (D), an acidic electrolytic solution is preferably used from the viewpoint of enhancing the roundness of the holes.
Specifically, hydrochloric acid, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, glycolic acid, tartaric acid, malic acid, citric acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid, as in the above-described anodizing treatment (A) Of these, sulfuric acid, phosphoric acid, and oxalic acid are particularly preferable. These acids can be used singly or in combination of two or more, adjusted to the desired parameters from the calculation formula of the above general formula (ii).

The conditions for the anodizing treatment (D) vary depending on the electrolyte used, and cannot be determined unconditionally. However, as with the above-described anodizing treatment (A), generally, the concentration of the electrolyte is 0.1 to It is preferably 20% by mass, a liquid temperature of −10 to 30 ° C., a current density of 0.01 to 20 A / dm ² , a voltage of 3 to 500 V, an electrolysis time of 0.5 to 30 hours, and an electrolyte concentration of 0.5 to 15 It is more preferable that the mass%, the liquid temperature −5 to 25 ° C., the current density 0.05 to 15 A / dm ² , the voltage 5 to 250 V, the electrolysis time 1 to 25 hours, and the electrolyte concentration 1 to 10 mass%, the liquid More preferably, the temperature is 0 to 20 ° C., the current density is 0.1 to 10 A / dm ² , the voltage is 10 to 200 V, and the electrolysis time is 2 to 20 hours.

  In the present invention, the thickness of the anodized film formed by such anodizing treatment (D) is preferably 0.1 to 300 μm, more preferably 0.5 to 150 μm. More preferably, it is ˜100 μm.

In the present invention, the average pore density of micropores in the anodized film formed by such anodizing treatment (D) is preferably 50 to 1500 / μm ² .
The area ratio occupied by the micropores is preferably 20 to 50%.
Here, the area ratio occupied by the micropore is defined by the ratio of the total area of the opening of the micropore to the area of the aluminum surface.

  By this anodizing treatment (D), an anodized film 34 a having micropores 36 a is formed on the surface of the aluminum substrate 32 as shown in FIG. 6A. A barrier layer 38a is present on the aluminum substrate 32 side of the anodized film 44a.

<Second step: oxide film dissolution treatment (E)>
The oxide film dissolution treatment (E) is a treatment (pore diameter enlargement treatment) for expanding the pore diameter present in the anodized film formed by the anodization treatment (D).

  The oxide film dissolution treatment (E) is performed by bringing the aluminum substrate after the anodization treatment (D) into contact with an acid aqueous solution or an alkali aqueous solution. The method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.

In the oxide film dissolution treatment (E), when an acid aqueous solution is used, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or a mixture thereof. Especially, the aqueous solution which does not contain chromic acid is preferable at the point which is excellent in safety | security. The concentration of the acid aqueous solution is preferably 1 to 10% by mass. The temperature of the acid aqueous solution is preferably 25 to 60 ° C.
On the other hand, when an alkaline aqueous solution is used in the oxide film dissolution treatment (E), it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass. The temperature of the alkaline aqueous solution is preferably 20 to 35 ° C.
Specifically, for example, 50 g / L, 40 ° C. phosphoric acid aqueous solution, 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution or 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution is preferably used. .
The immersion time in the acid aqueous solution or alkali aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and still more preferably 15 to 60 minutes.

  Further, in the oxide film dissolution treatment (E), the amount of enlargement of the pore diameter varies depending on the conditions of the anodization treatment (D), but the enlargement ratio before and after the treatment is preferably 1.05 times to 100 times, and 1.1 times to 75 times is more preferable, and 1.2 times to 50 times is particularly preferable.

  By this oxide film dissolution treatment (E), as shown in FIG. 6B, the surface of the anodic oxide film 34a and the inside of the micropore 36a shown in FIG. 6A (barrier layer 38a and porous layer) The aluminum member having the anodic oxide film 34b having the micropores 36b on the aluminum substrate 32 is obtained. As in FIG. 6A, a barrier layer 38b is present on the aluminum substrate 32 side of the anodized film 34b.

<Third step: Anodizing treatment (D)>
In the self-ordering method II, the anodic oxidation treatment (D) is preferably performed again after the oxide film dissolution treatment (E).

  By the second anodic oxidation process (D), as shown in FIG. 6C, the oxidation reaction of the aluminum substrate 32 shown in FIG. 6B proceeds, and on the aluminum substrate 32, more than the micropores 36b. An aluminum member having an anodic oxide film 34c having deep micropores 36c is obtained. As in FIG. 6A, a barrier layer 38c is present on the aluminum substrate 32 side of the anodized film 34c.

<Fourth step: Oxide film dissolution treatment (E)>
Further, in the self-ordering method II, after the anodic oxidation treatment (D), the oxide film dissolution treatment (E) and the anodic oxidation treatment (D) are performed in this order, the oxide film dissolution treatment (E) is further performed. It is preferable to apply.

By this treatment, since the treatment liquid enters the micropores, all the anodized film formed in the anodizing treatment (D) performed in the third step is dissolved, and the anodizing treatment performed in the third step The pore diameter of the micropore formed in (D) can be increased.
That is, by the oxide film dissolution treatment (E) again, as shown in FIG. 6D, the inside of the micropore 36c on the surface side from the inflection point of the anodic oxide film 34c shown in FIG. The aluminum member which melt | dissolves and has the anodic oxide film 34d which has the straight tubular micropore 36d on the aluminum substrate 32 is obtained. As in FIG. 6A, the barrier layer 38d is present on the aluminum substrate 32 side of the anodized film 34d.

  Here, the amount of expansion of the pore diameter of the micropore varies depending on the processing conditions of the anodizing treatment (D) performed in the third step, but the expansion ratio before and after the treatment is preferably 1.05 times to 100 times. 1 to 75 times is more preferable, and 1.2 to 50 times is particularly preferable.

In the self-ordering method II, the above-described cycle of the anodic oxidation treatment (D) and the oxide film dissolution treatment (E) is performed one or more times. The greater the number of repetitions, the higher the regularity of the pore arrangement described above.
In addition, by completely dissolving the anodized film formed by the last anodizing treatment (D) by the oxide film dissolving treatment (E), the roundness of the micropores viewed from the surface of the film is dramatically improved. The above cycle is preferably repeated twice or more, more preferably 3 times or more, and even more preferably 4 times or more.
In addition, when the above cycle is repeated twice or more, the conditions of each oxide film dissolution treatment and anodization treatment may be the same or different, respectively, and the last treatment is anodization treatment. You can finish it.

[Constant voltage processing]
The constant voltage treatment is a treatment method in which an anodized film is formed at a low speed over a long time (for example, several hours to several tens of hours). In this processing method, since the pore diameter depends on the voltage, it is essential to control the voltage to be constant from the viewpoint of preventing branching of the micropores.

The average flow rate of the electrolytic solution in the anodizing treatment is preferably 0.5 to 20.0 m / min, more preferably 1.0 to 15.0 m / min, and 2.0 to 10.0 m / min. More preferably, it is min. By performing anodizing treatment at a flow rate in the above range, uniform and high regularity can be obtained.
Moreover, the method of flowing the electrolytic solution under the above-mentioned conditions is not particularly limited, but, for example, a method using a general stirring device such as a stirrer is used. In particular, it is preferable to use a stirrer that can control the stirring speed by digital display because the average flow velocity can be controlled. Examples of such a stirring apparatus include “Magnetic Stirrer HS-50D (manufactured by AS ONE)” and the like.

For the anodizing treatment, for example, a method in which an aluminum substrate is used as an anode in a solution having an acid concentration of 1 to 10% by mass can be used.
The solution used for the anodizing treatment is preferably an acid solution, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid, glycolic acid, tartaric acid, malic acid, citric acid. Of these, sulfuric acid, phosphoric acid, and oxalic acid are particularly preferable. These acids can be used alone or in combination of two or more.

The conditions for anodizing treatment vary depending on the electrolyte used, and therefore cannot be determined unconditionally. In general, however, the electrolyte concentration is 0.1 to 20% by mass, the solution temperature is -10 to 30 ° C., and the current density. 0.01 to 20 A / dm ² , voltage 3 to 300 V, electrolysis time 0.5 to 50 hours are preferable, electrolyte concentration 0.5 to 15% by mass, liquid temperature −5 to 25 ° C., current density 0 0.05 to 15 A / dm ² , voltage 5 to 250 V, electrolysis time 1 to 25 hours are more preferable, electrolyte concentration 1 to 10% by mass, solution temperature 0 to 20 ° C., current density 0.1 to 10 A / dm ² , voltage 10-2
More preferably, it is 00V and electrolysis time is 2 to 20 hours.

  The treatment time for the anodizing treatment is preferably 0.5 minutes to 16 hours, more preferably 1 minute to 12 hours, and further preferably 2 minutes to 8 hours.

  In the present invention, the film thickness of the anodized film formed by such anodizing treatment is preferably 1-1000 μm, more preferably 5-500 μm, and even more preferably 10-300 μm. preferable.

In the present invention, the average pore density of micropores in the anodized film formed by such anodizing treatment is preferably 50-1500 / μm ² .
The area ratio occupied by the micropores is preferably 20 to 50%.
Here, the area ratio occupied by the micropore is defined by the ratio of the total area of the opening of the micropore to the area of the aluminum surface.

[Penetration process]
The penetrating treatment step is a step of obtaining the insulating base material by penetrating holes by the micropores generated by the anodizing after the anodizing treatment step.
Specifically, as the penetration treatment step, for example, after the anodization treatment step, an aluminum substrate (portion represented by reference numeral 32 in FIG. 6D) is dissolved, and the bottom of the anodized film is formed. (The part represented by reference numeral 38d in FIG. 6D); a method of cutting the aluminum substrate and the anodized film in the vicinity of the aluminum substrate after the anodizing treatment step; and the like.
Next, the former method which is a preferred embodiment will be described in detail.

<Dissolution of aluminum substrate>
For the dissolution of the aluminum substrate after the anodizing treatment step, a treatment solution in which the anodized film (alumina) is difficult to dissolve and aluminum is easily dissolved is used.
That is, the aluminum dissolution rate is 1 μm / min or more, preferably 3 μm / min or more, more preferably 5 μm / min or more, and the anodic oxide film dissolution rate is 0.1 nm / min or less, preferably 0.05 nm / min or less, more preferably Uses a treatment liquid having a condition of 0.01 nm / min or less.
Specifically, a treatment liquid containing at least one metal compound having a lower ionization tendency than aluminum and having a pH of 4 or less and 8 or more, preferably 3 or less and 9 or more, more preferably 2 or less and 10 or more is used. Immerse treatment.

Such treatment liquid is based on an acid or alkaline aqueous solution, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum, A gold compound (for example, chloroplatinic acid), a fluoride thereof, a chloride thereof, or the like is preferably used.
Among them, an acid aqueous solution base is preferable, and it is preferable to blend a chloride.
In particular, a treatment liquid (hydrochloric acid / mercury chloride) in which mercury chloride is blended with an aqueous hydrochloric acid solution and a treatment liquid (hydrochloric acid / copper chloride) in which copper chloride is blended with an aqueous hydrochloric acid solution are preferable from the viewpoint of treatment latitude.
The composition of such a treatment liquid is not particularly limited, and for example, a bromine / methanol mixture, a bromine / ethanol mixture, aqua regia and the like can be used.

  Moreover, 0.01-10 mol / L is preferable and, as for the acid or alkali concentration of such a processing liquid, 0.05-5 mol / L is more preferable.

  Furthermore, the processing temperature using such a processing liquid is preferably −10 ° C. to 80 ° C., more preferably 0 ° C. to 60 ° C.

  In the present invention, the aluminum substrate is dissolved by bringing the aluminum substrate after the anodizing treatment step into contact with the treatment liquid described above. The method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred. The contact time at this time is preferably 10 seconds to 5 hours, and more preferably 1 minute to 3 hours.

<Removal of the bottom of the anodized film>
The bottom part of the anodized film after the aluminum substrate is dissolved is removed by dipping in an acid aqueous solution or an alkali aqueous solution. By removing the bottom anodic oxide film, the pores by the micropores penetrate.

  The bottom of the anodized film is removed by pre-soaking in a pH buffer solution and filling the hole with the pH buffer solution from the opening side of the micropore, and then on the opposite side of the opening, that is, on the bottom of the anodized film. It is preferably carried out by a method of contacting with an acid aqueous solution or an alkali aqueous solution.

In the case of using an acid aqueous solution, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or a mixture thereof. The concentration of the acid aqueous solution is preferably 1 to 10% by mass. The temperature of the acid aqueous solution is preferably 25 to 40 ° C.
On the other hand, 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% by mass. The temperature of the alkaline aqueous solution is preferably 20 to 35 ° C.

  Specifically, for example, a 50 g / L, 40 ° C. phosphoric acid aqueous solution, a 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution, or a 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution is suitably used. It is done.

The immersion time in the acid aqueous solution or alkali aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and still more preferably 15 to 60 minutes.
Moreover, when immersing in a pH buffer solution beforehand, the buffer solution corresponding to the acid / alkali mentioned above is used appropriately.

  By this penetration process, a structure in which the aluminum substrate 32 and the barrier layer 38d shown in FIG. 6D are eliminated, that is, the insulating base material 40 shown in FIG. 7A is obtained.

  On the other hand, as a method for cutting the latter aluminum substrate and the anodic oxide film in the vicinity of the aluminum substrate, an aluminum substrate (portion represented by reference numeral 32 in FIG. 6D) and the bottom of the anodic oxide film (FIG. 6D). ) Is preferably exemplified by a method in which the portion represented by the reference numeral 38d) is physically removed using a cutting process using a laser or the like or various polishing processes.

[Metal filling process]
The metal filling step is a step of obtaining the anisotropic conductive member by filling a metal which is a conductive member into the inside of the penetrated hole in the obtained insulating base material after the penetrating treatment step. is there.

Here, the metal to be filled constitutes the conduction path of the anisotropic conductive member, and as described in the anisotropic conductive member, gold (Au), silver (Ag), copper (Cu), Aluminum (Al), magnesium (Mg), nickel (Ni), tungsten (W), cobalt (Co), rhodium (Rh), tin oxide doped with indium (ITO), and these metals as main components An alloy etc. are illustrated suitably.
Among these, from the viewpoint of electrical conductivity and ease of filling, it is preferably made of any one metal selected from the group consisting of copper, nickel and gold, or an alloy containing these metals as a main component.

In the anisotropic conductive member manufacturing method, an electrolytic plating method or an electroless plating method can be used as a metal filling method.
Here, in the conventionally known electroplating method used for coloring or the like, it is difficult to selectively deposit (grow) a metal in a hole at a high aspect. This is presumably because the deposited metal is consumed in the holes and the plating does not grow even if electrolysis is performed for a certain time or longer.

Therefore, in the anisotropic conductive member manufacturing method, when the metal is filled by the electrolytic plating method, the potential scanning method (potential scanning electrolysis) in which the potential is scanned at a constant speed as time passes, and the electrolysis is performed so that the current value is always constant. Electroplating by a constant current method (constant potential electrolysis) is preferable.
Here, during the electrolysis, a pause time can be appropriately provided. In this case, the pause time is preferably several seconds to 10 seconds or more and 10 minutes or less, and 30 to 60 seconds or more and 10 minutes or less. Preferably there is. Thus, by appropriately providing the downtime, hydrogen gas generated in the through hole is sufficiently degassed, and the electrochemical reaction in the through hole can be smoothly advanced. In particular, a resting time of 10 minutes or less is preferable because damage (for example, chemical dissolution) applied to the anodized film constituting the insulating base material is small.
It is also desirable to apply ultrasonic waves in order to promote the degassing of the hydrogen gas generated in the through hole and the stirring of the electrolytic solution.
Furthermore, the electrolysis voltage is usually −20 V or less, preferably −5 V or less, but it is preferable to perform potential scanning electrolysis with 0 V as the starting potential. In addition, when performing potential scanning electrolysis, what can use cyclic voltammetry together is desirable, and potentiostat apparatuses, such as Solartron, BAS, Hokuto Denko, and IVIUM, can be used. On the other hand, in the case of galvanostatic electrolysis, the current density is preferably 0.1~5A / dm ^2, and more preferably 0.5~3A / dm ^2.

A conventionally known plating solution can be used as the plating solution.
Specifically, when copper is precipitated, an aqueous copper sulfate solution is generally used. The concentration of copper sulfate is preferably 1 to 600 g / L, and more preferably a saturated solution. Moreover, precipitation can be promoted by adding hydrochloric acid to the electrolytic solution. In this case, the hydrochloric acid concentration is preferably 10 to 20 g / L.
When gold is deposited, it is desirable to perform plating by direct current electrolysis using a sulfuric acid solution of tetrachlorogold.

On the other hand, in the electroless plating method, since it takes a long time to completely fill the hole made of micropores with a high aspect ratio, in the anisotropic conductive member manufacturing method, it is desirable to fill the metal by the electrolytic plating method. .
In addition, as the conditions of the electroless plating method, for example, the method described in JP-A-3-266306, specifically, the insulating base material obtained by the penetration process step is cyanated at 60 ° C. A method of immersing in a gold plating bath and depositing metal on the wall surface inside the through hole is mentioned.

  In addition, as another method for filling the metal, for example, the method described in JP-A-4-170036, specifically, the insulating group obtained by the penetration treatment step on the electrode for electrodeposition is used. There is a method in which a material is installed and electrodeposition is performed using the electrode for electrodeposition as a cathode (see FIG. 1 (d) of the publication).

  By this metal filling step, the anisotropic conductive member precursor 41 shown in FIG. 7B is obtained.

[Surface smoothing]
In the anisotropic conductive member manufacturing method, it is preferable to include a surface smoothing process for smoothing the front and back surfaces of the anisotropic conductive member by mechanical polishing, particularly chemical mechanical polishing after the metal filling process.
By performing chemical mechanical polishing (CMP) treatment, the surface and back surface of the insulating base material (that is, anisotropic conductive member) after the metal is filled are smoothed and excessively attached to the surface. The metal can be removed.
For the CMP treatment, CMP slurry such as PANANERLITE-7000 manufactured by Fujimi Incorporated, GPX HSC800 manufactured by Hitachi Chemical Co., Ltd., CL-1000 manufactured by Asahi Glass (Seimi Chemical Co., Ltd.), or the like can be used.

[Protrusion formation process]
In the projecting portion forming step, after the metal filling step (the surface smoothing step when the CMP treatment is performed, the same applies in the following step), the end portion of the conductive path formed is insulative. In this step, the anisotropic conductive member is obtained by projecting from the surface of the substrate.
Specifically, the end of the conduction path can be projected from the surface of the insulating substrate by performing the following trimming process and / or electrodeposition treatment, but the pitch and diameter of the conduction path Depending on the case, solder may be formed on the end of the conduction path by coating.

<Trimming>
The trimming process is a process in which only the insulating base material on the surface of the anisotropic conductive member is partially removed after the metal filling process to project the conduction path.
Here, the trimming process can be performed under the same processing conditions as the oxide film dissolution process (E) described above as long as the metal constituting the conduction path is not dissolved. In particular, it is preferable to use phosphoric acid that can easily control the dissolution rate.
By this trimming process, an anisotropic conductive member 42 shown in FIG. 7C is obtained.

<Electrodeposition treatment>
In the anisotropic conductive member manufacturing method, the same or different conductive metal is further deposited only on the surface of the conduction path 8 shown in FIG. 7B instead of or after the trimming process. Electrodeposition treatment may be performed (FIG. 7D).
In the present invention, the electrodeposition process is a process including an electroless plating process using a difference in electronegativity of different metals.
Here, the electroless plating treatment is a step of immersing in an electroless plating treatment solution (for example, a solution obtained by appropriately mixing a noble metal-containing treatment solution having a pH of 1 to 9 and a reducing agent treatment solution having a pH of 6 to 13). is there.
By this electrodeposition process, an anisotropic conductive member 42 shown in FIG. 7D is obtained.

In the present invention, as will be described below, the contact surface on the inspection electrode side of the conduction path and the contact surface on the electrode to be inspected (electrical contact if having an electrical contact) side can be formed of different materials. For the reason, an electrodeposition process is preferable as the protrusion forming step.
Specifically, when forming the protruding portion of the conduction path by the electrodeposition process, the protruding portion on the side to be joined to the inspection electrode side is a noble metal, for example, gold (Au) or the like from the viewpoint of ease of bonding. It is preferable to deposit copper (Cu) and an alloy mainly composed of these metals.
Moreover, as a protrusion part on the side which contacts a non-inspection electrode (in the case of having an electrical contact), a hard metal such as nickel (Ni) or tungsten is used from the viewpoint of durability against repeated contact. It is preferable to deposit (W) or cobalt (Co) or an alloy mainly composed of these metals.

In the present invention, the contact surface on the side of the electrode to be inspected (electrical contact in the case of having an electrical contact) in consideration of the joining of the circuit board for inspection and the anisotropic conductive member, which will be described later. Preferably, the protrusion is formed after such joining.
Specifically, when the bonding of the circuit board for inspection and the anisotropic conductive member is a mode using a pressure head described later, the conduction path (protrusion) on the inspection electrode side is connected to the pressure head. From the viewpoint of protection, it is preferable not to perform the trimming process and the electrodeposition process on the contact surface on the electrode to be inspected (or the electrical contact in the case of having an electrical contact) until after the joining.

  Furthermore, in the present invention, from the viewpoint of protecting the conduction path (protruding portion) on the side of the electrode to be inspected from the pressure head, the electrode to be inspected of the above-described conduction path even after the trimming process and the electrodeposition process are performed. (Electrical contact if it has an electrical contact) The contact surface on the side is an easily peelable resin layer (eg, Teflon (registered trademark), polyimide, laminate layer, etc.), and the conductive path (protrusion) on the electrode to be inspected An embodiment in which the height is approximately the same as the height of is also preferable.

[Surface curing treatment]
In the anisotropic conductive member manufacturing method, ion plating such as DLC coating, titanium (Ti), and titanium nitride (TiN) is used from the viewpoint of improving the hardness and wear resistance of the surface of the protrusion formed by the protrusion formation step. A known surface hardening treatment such as ting can be performed.

[Protective film formation treatment]
On the other hand, in the anisotropic conductive member manufacturing method, since the insulating base material formed of alumina changes its pore diameter over time due to hydration with moisture in the air, it is protected before the metal filling step. It is preferable to perform a film forming process.

  Examples of the protective film include an inorganic protective film containing Zr element and / or Si element, or an organic protective film containing a water-insoluble polymer.

  The method for forming the protective film containing the Zr element is not particularly limited, but, for example, a method in which the protective film is directly immersed in an aqueous solution in which a zirconium compound is dissolved is generally used. Further, from the viewpoint of the robustness and stability of the protective film, it is preferable to use an aqueous solution in which a phosphorus compound is dissolved together.

Here, specific examples of the zirconium compound include zirconium, zirconium fluoride, sodium fluoride zirconate, calcium fluoride zirconate, zirconium chloride, zirconium oxychloride, zirconium oxynitrate, zirconium sulfate, zirconium ethoxide. , Zirconium propoxide, zirconium butoxide, zirconium acetylacetonate, tetrachlorobis (tetrahydrofuran) zirconium, bis (methylcyclopentadienyl) zirconium dichloride, dicyclopentadienylzirconium dichloride, ethylenebis (indenyl) zirconium (IV) dichloride Among them, sodium zirconate fluoride is preferable.
Moreover, as a density | concentration of the zirconium compound in aqueous solution, 0.01-10 wt% is preferable from a viewpoint of the uniformity of a protective film thickness, and 0.05-5 wt% is more preferable.

Examples of the phosphorus compound include phosphoric acid, sodium phosphate, calcium phosphate, sodium hydrogen phosphate, and calcium hydrogen phosphate. Among them, sodium hydrogen phosphate is preferable.
Moreover, as a density | concentration of the phosphorus compound in aqueous solution, 0.1-20 wt% is preferable from a viewpoint of the uniformity of a protective film thickness, and 0.5-10 wt% is more preferable.

  Moreover, as processing temperature, 0-120 degreeC is preferable and 20-100 degreeC is more preferable.

On the other hand, the method for forming the protective film containing Si element is not particularly limited. For example, a method in which the protective film is directly immersed in an aqueous solution in which an alkali metal silicate is dissolved is generally used.
The aqueous solution of alkali metal silicate has a ratio of silicon oxide SiO ₂ and alkali metal oxide M ₂ O which is a component of silicate (generally expressed as a molar ratio of [SiO ₂ ] / [M ₂ O]). The protective film thickness can be adjusted by the concentration.
Here, as M, sodium and potassium are particularly preferably used.
The molar ratio of [SiO ₂ ] / [M ₂ O] is preferably 0.1 to 5.0, and more preferably 0.5 to 3.0.
Furthermore, the content of SiO ₂ is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass.

As the organic protective film, a method in which only the solvent is volatilized by heat treatment after being directly immersed in an organic solvent in which a water-insoluble polymer is dissolved is preferable.
Examples of the water-insoluble polymer include polyvinylidene chloride, poly (meth) acrylonitrile, polysulfone, polyvinyl chloride, polyethylene, polycarbonate, polystyrene, polyamide, cellophane and the like.
Examples of organic solvents include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane. , Methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene and the like.
As a density | concentration, 0.1-50 wt% is preferable and 1-30 wt% is more preferable.
Moreover, as heating temperature at the time of solvent volatilization, 30-300 degreeC is preferable and 50-200 degreeC is more preferable.

  After the protective film formation treatment, the thickness of the anodized film including the protective film is preferably 0.1 to 1000 μm, and more preferably 1 to 500 μm.

In the anisotropic conductive member manufacturing method, the hardness and heat cycle resistance can be controlled by heat treatment.
For example, heating at 100 ° C. or higher is preferable, 200 ° C. or higher is more preferable, and 400 ° C. or higher is particularly preferable. The heating time is preferably 10 seconds to 24 hours, more preferably 1 minute to 12 hours, and particularly preferably 30 minutes to 8 hours. Hardness is improved by such heat treatment, and expansion and contraction are suppressed even during a heat cycle of heating and cooling in a semiconductor manufacturing process or the like.

Next, a method for manufacturing the probe card of the present invention using the anisotropic conductive member obtained by such a manufacturing method will be described in detail.
The probe card of the present invention joins the inspection circuit board and the anisotropic conductive member, that is, joins the inspection electrode of the inspection circuit board and the conduction path of the anisotropic conductive member. Can be manufactured.
When the probe card of the present invention includes the probe contact needle as an electrical contact, for example, after joining the inspection circuit board and the anisotropic conductive member, the anisotropic conductive member It can manufacture by contacting a conduction path and the probe contact needle.
Below, the method of this joining and contact is demonstrated concretely.

[Join]
As a method for joining the circuit board for inspection and the anisotropic conductive member, the following thermocompression bonding method, ultrasonic connection method, and the like are preferably exemplified.

<Thermo-compression bonding>
Thermocompression bonding uses diffusion bonding of metals between the inspection electrode of the inspection circuit board and the conduction path of the anisotropic conductive member, and applies a predetermined pressure at a temperature below the melting point of the metal. It is a method of joining.
The temperature is not particularly limited because it varies depending on the metal used for the inspection electrode and the conduction path, but is preferably 150 ° C. or higher, and more preferably 180 to 300 ° C.
Similarly, the pressure is not particularly limited because it varies depending on the metal used for the inspection electrode and the conduction path, but it is preferably 0.2 to 1.0 MPa, and 0.4 to 0.8 MPa. Is more preferable.
For thermocompression bonding, a commercially available thermocompression bonding apparatus (MODEL6000, manufactured by Hisol Co., Ltd.) or the like can be used.

FIG. 8 is a schematic diagram illustrating a preferred embodiment of a method for joining the circuit board for inspection and the anisotropic conductive member by thermocompression bonding.
In the present invention, the inspection circuit board and the anisotropic conductive member are joined by using a predetermined pressure head 45 to connect the anisotropic conductive member 6 to the inspection circuit board as shown in FIG. The aspect which presses on a heating condition on the surface in which the test | inspection electrode 4 of 5 was provided is preferable.
Here, it is preferable that the pressure head 45 uses a head 45a whose back surface (the surface in contact with the anisotropic conductive member 6) is a mold frame or a head 45b whose mesh frame is used. .

<Ultrasonic bonding>
In ultrasonic bonding, the inspection electrode of the circuit board for inspection and the conduction path of the anisotropically conductive member are subjected to ultrasonic vibration using a pressure head, and a predetermined load is applied as appropriate. It is a method to do.
The amplitude is preferably in the range of 2 to 10 μm and 10 to 20% of the bonding electrode area.
Similarly, the load is preferably set to 0.1 to 10 g per electrode and 100 g to 11 kg / mm ² per unit area of the bonded electrode.
For ultrasonic bonding, a commercially available ultrasonic bonding apparatus (FC2000, manufactured by Toray Industries, Inc.) can be used.

[contact]
The contact between the conduction path of the anisotropic conductive member and the probe contact needle does not easily disengage the conduction path and the probe contact needle unless the fixing holder for fixing the probe contact needle is provided. However, when the fixed holder is provided, the conduction path, the probe contact needle, and the probe contact needle are sandwiched between the fixed folder and the inspection substrate as shown in FIG. Is preferably brought into contact so as to be removable.

In the above-described inspection method using the probe card of the present invention, before inspecting the electrical characteristics of the object to be inspected, the contact portion with the electrode to be inspected (the protruding portion of the conduction path, the electrical contact) is subjected to an alkaline aqueous solution. Or it is preferable to make it contact with acidic aqueous solution.
Specifically, the inspection method of the present invention includes a pretreatment step in which a protruding portion of the conduction path on the side in contact with the electrode to be inspected is brought into contact with an alkaline aqueous solution or an acidic aqueous solution, and the protruding portion after the pretreatment step. And an inspection step of inspecting the electrical characteristics of the object to be inspected by bringing it into contact with the electrode to be inspected.
Further, when the probe card of the present invention has the above-described electrical contact, the inspection method of the present invention contacts the electrical contact with an alkaline aqueous solution or an acidic aqueous solution before inspecting the electrical characteristics of the object to be inspected. It is preferable that the method includes a pretreatment step to be performed and an inspection step in which the electrical contact after the pretreatment step is brought into contact with the electrode to be inspected to inspect the electrical characteristics of the object to be inspected.

Here, examples of the alkaline aqueous solution or acidic aqueous solution in contact with the contact portion (protruding portion of the conduction path, electrical contact) with the electrode to be inspected include the solutions exemplified in the above-described trimming treatment and oxide film dissolution treatment.
Specifically, as the alkaline aqueous solution, for example, a 1 to 35% by mass sodium hydroxide aqueous solution, a 1 to 35% by mass potassium hydroxide aqueous solution, and an ammonium persulfate aqueous solution are preferably used. Further, the pH of the aqueous solution is preferably 12 or more, and more preferably 13 or more.
On the other hand, as the acidic aqueous solution, specifically, for example, 0.01 to 0.05 mass% hydrogen peroxide solution, 5 to 30 mass% sulfuric acid aqueous solution, and 1 to 10 mass% phosphoric acid aqueous solution are preferable. Used.
In this invention, these aqueous solutions may contain about 5-20 mass% of alcohols, such as methanol and isopropanol, and may contain the degreasing agent for aqueous solutions. Moreover, about 0.5-5 mass% of chlorides, such as zinc chloride, may be contained.

  In the present invention, there are no particular limitations on the treatment conditions and treatment method for bringing the contact portion (the protruding portion of the conduction path, the electrical contact) with the electrode to be inspected into contact with an alkaline aqueous solution or an acidic aqueous solution.

The treatment temperature varies greatly depending on the type of solution, but is preferably about 30 to 85 ° C.
In addition, the treatment time varies greatly depending on the type of the solution, but is preferably about 1 to 600 seconds, and more preferably 30 to 300 seconds.

On the other hand, as a treatment method, it is preferable to use an absorbent body impregnated with an alkaline aqueous solution or an acidic aqueous solution from the viewpoint of contact efficiency.
Such an absorbent body is not particularly limited as long as it is a member that can be impregnated with a liquid, and examples thereof include a chemical absorbent, a gel substance, a glass fiber filter, a nonwoven fabric, and a sponge.
Specifically, for example, a sheet type (P-110) or folded (C-FL550DD) is preferably used among the liquid absorbents manufactured by 3M, as the chemical absorbent.
Specifically, for example, a sheet-like gel such as polyacrylamide gel is suitably used as the gel-like substance. In addition, it is preferable that a gel-like substance contains about 20-30 mass% sodium hydroxide or about 15-25 mass% potassium hydroxide.
As the glass fiber filter, for example, a glass fiber filter treated with an organic binder is preferably used, and specifically, a glass fiber filter treated with an acrylic resin can be used. As the glass fiber filter, commercially available products such as GC-90 and GS-25 manufactured by Advantech Toyo Co., Ltd. can also be used.
Specifically, for example, a polyolefin-based nonwoven fabric can be suitably used as the nonwoven fabric.
Among these absorbers, a chemical solution absorbent, a gel substance, and a glass fiber filter are preferable, and a chemical solution absorbent is particularly preferable.

Moreover, as a processing method, the method of immersing the contact part (the protrusion part of a conduction path, an electrical contact) with a to-be-inspected electrode in the container which accommodated the alkaline aqueous solution or acidic aqueous solution mentioned above may be sufficient.
In this case, although the contact part after immersion may be washed with water, the washing member (for example, the absorbent body described above) that can be impregnated (absorbed with water) with the alkaline aqueous solution or the acidic aqueous solution described above, In particular, it can be cleaned using a material impregnated with pure water.

In the inspection method of the present invention, it is preferable to perform a polishing treatment as necessary before contacting the contact portion with the electrode to be inspected, particularly the protruding portion of the conduction path with the alkaline aqueous solution or the acidic aqueous solution.
As the polishing treatment, the same treatment as the surface smoothing treatment described above can be performed.
Even if the protruding portion of the conduction path is lost due to wear or the like by performing contact with an alkaline aqueous solution or an acidic aqueous solution after performing such a polishing treatment, the above-described surface smoothing treatment and trimming treatment are performed. The same effect, that is, the protruding portion of the conduction path can be reproduced.

By inspecting the electrical characteristics of the object to be inspected by the inspection method according to such an embodiment, the contact portion (the protruding portion of the conduction path, the electrical contact) with the electrode to be inspected is brought into contact with the alkaline aqueous solution or the acidic aqueous solution. The deposits, oxide film, and the like at the contact portion can be removed, and a stable inspection can be performed.
In addition, since the contact portion with the electrode to be inspected can be maintained in an electrically active state by the inspection method according to such an aspect, the electrical characteristics can be inspected even in a usage aspect where the pressure load is low. it can.

The present invention can also provide a probe inspection apparatus including the above-described probe card of the present invention.
FIG. 9 is a schematic diagram showing a schematic configuration of a preferred embodiment of the probe inspection apparatus.
The probe device is not particularly limited as long as it includes the probe card of the present invention instead of the conventionally known probe card. For example, as shown in FIG. 9, the probe device 70 of the present invention is a probe of the present invention. It is preferable that the card 1, the inspected object 2 on which the inspected electrode is installed, the prober 71 for storing the inspected object 2, the interface ring 72 and the tester head 73 connected to the prober 71.

<Manufacture of anisotropic conductive member>
(A) Mirror finish (electropolishing)
A high-purity aluminum substrate (manufactured by Sumitomo Light Metal Co., Ltd., purity 99.99 mass%, thickness 0.4 mm) is cut so that it can be anodized in an area of 10 cm square, using an electropolishing liquid having the following composition, voltage 25 V, liquid The electropolishing treatment was performed under conditions of a temperature of 65 ° C. and a liquid flow rate of 3.0 m / min.
The cathode was a carbon electrode, and GP0110-30R (manufactured by Takasago Seisakusho) was used as the power source. The flow rate of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE).

(Electrolytic polishing liquid composition)
-660 mL of 85% phosphoric acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.)
・ Pure water 160mL
・ Sulfuric acid 150mL
・ Ethylene glycol 30mL

(B) Anodizing treatment process (self-regulating method I)
Next, the aluminum substrate after the electropolishing treatment is subjected to a pre-anodizing treatment for 10 hours with an electrolyte solution of 0.5 mol / L oxalic acid at a voltage of 40 V, a liquid temperature of 15 ° C., and a liquid flow rate of 3.0 m / min. gave.
Thereafter, a film removal treatment was performed in which the aluminum substrate after the pre-anodizing treatment was immersed in a mixed aqueous solution (liquid temperature: 50 ° C.) of 0.2 mol / L chromic anhydride and 0.6 mol / L phosphoric acid for 12 hours.
Then, re-anodizing treatment was performed for 15 hours with an electrolyte solution of 0.5 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.
In both the pre-anodizing treatment and the re-anodizing treatment, the cathode was a stainless electrode, and the power source was GP0110-30R (manufactured by Takasago Seisakusho). Moreover, NeoCool BD36 (made by Yamato Kagaku) was used for the cooling device, and Pear Stirrer PS-100 (made by EYELA) was used for the stirring and heating device. Furthermore, the flow rate of the electrolyte was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE).

(C) Penetration treatment step Next, an aluminum substrate was immersed by using a treatment solution in which 0.1 mol / L copper chloride was blended in a 20% hydrochloric acid aqueous solution at a liquid temperature of 15 ° C until the aluminum was visually removed. In addition, the bottom of the anodized film is removed by immersing in 5% by mass phosphoric acid at 30 ° C. for 30 minutes to form a structure (insulating group) having an anodized film having micropores with an enlarged pore diameter. Material). The thickness of the structure after the penetration treatment was 120 μm.

(D) Heat treatment Next, the structure obtained above was subjected to a heat treatment at a temperature of 400 ° C for 1 hour.

(E) Metal filling treatment step Next, gold was deposited on one surface of the structure after the heat treatment to a thickness of 0.1 μm to form a gold electrode. Electrolytic plating was performed using the gold electrode as a cathode and copper as a positive electrode.
Using a 600 g / L copper sulfate saturated solution as the electrolytic solution in a state kept at 60 ° C., DC electrolysis was performed to produce a structure in which copper formed in the pores made of micropores was filled.
Here, for direct current electrolysis, a plating apparatus manufactured by Yamamoto Sekin Co., Ltd. was used, and a potentiostat / galvanostat (Model 7060) manufactured by AMEL was used. The standard electrode was an Ag / AgCl type.
Electrolysis, Cu: scanning at a scan rate of 1 mV / sec on the negative side from 0V, the quantity of electricity was conducted until 4000C / dm ^2.
When the fracture surface of the structure after the metal filling process was observed with an optical microscope, copper was filled in the micropore in an amount such that the height from the gold electrode side was about 70 μm.

(F) Surface smoothing treatment Subsequently, the surface on the gold electrode side of the structure after the metal filling treatment was polished by 10 μm, and the opposite surface was polished by 60 μm.
Specifically, after lapping polishing with a sheet of silicon carbide (# 1200), the polishing is performed with diamond slurry having a particle size of 2 μm, and further polishing is performed with diamond slurry having a particle size of 0.25 μm. To obtain a mirror state.
When the fracture surface of the structure after the surface smoothing treatment is observed with an optical microscope, the thickness of the conductive path (copper) and the insulating base material (anodized film) is 50 μm. I understood.

(G) Protrusion part formation process Next, the trimming process was performed to the structure after a surface smoothing process for 10 minutes using 40 degreeC 5% phosphoric acid aqueous solution.
Thereafter, the structure was washed with water, and a mixed aqueous solution of 0.9 mol / L nickel sulfate, 0.99 mol / L nickel chloride and 0.5 mol / L boric acid was used, and conditions of 40 ° C., 5 A / dm ² , and an electric charge of ² C. The electrolytic treatment was applied.
The fracture surface of the structure after these treatments was observed with FE-SEM. As a result, nickel with a thickness of 0.1 μm was deposited on the copper, and the projecting portion made of nickel was formed as a conduction path. It was found to be a conductive member.
Furthermore, immersion treatment was performed for 1 minute at a liquidity of 80 ° C. using an electroless rhodium plating solution (RH-1, manufactured by Okuno Pharmaceutical Co., Ltd.). As a result of ESCA analysis after the treatment, it was found that the deposited nickel was covered with rhodium.

  The process from the metal filling process (E) to the protrusion formation process (G) is performed without exposing the plated part to the atmosphere from the start of copper plating to the end of rhodium plating. The process was carried out continuously without opening.

Subsequently, it was washed with water and dried, and then observed with an FE-SEM.
As a result, as shown in Table 1 below, the height of the protruding portion of the conductive path is 0.1 μm, the diameter of the conductive path as the electrode part size is 60 nm, and the thickness of the member is 50 μm. It was confirmed. Moreover, it confirmed that the length (length / thickness) of the centerline of the conduction path with respect to the thickness of a member was 1.01.

The shape of the anisotropically conductive member obtained is shown in Table 1 below.
Here, the degree of ordering is defined by the above formula (i) for the micropores in the field of view of 2 μm × 2 μm by taking a surface photograph (magnification 20000 times) for the obtained anisotropic copper conductive member by FE-SEM. The degree of ordering was measured. The degree of ordering was measured at 10 locations, and the average value was calculated.
Moreover, a period means the distance (pitch) between the centers of a conduction path, surface photographs (magnification 50000 times) were taken with FE-SEM about the obtained anisotropic copper conductive member (film), and 50 points were measured. Average value.
Further, as shown in FIG. 10, the density is 1/2 conductive electrode in the unit cell 51 of the micropore arranged so that the degree of ordering defined by the above formula (i) is 50% or more. Assuming that there is a part 52, the following formula was used for calculation. Here, in the following formula, Pp represents a period.

Density (pieces / μm ² ) = (1/2 piece) / {Pp (μm) × Pp (μm) × √3 × (1/2)}

(Examples 1-12)
The anisotropically conductive member obtained above and the circuit board for inspection shown in Table 2 below were used at a temperature of 300 ° C. and a pressure of 0.6 MPa using a thermocompression bonding apparatus (MODEL6000, manufactured by Hisol). Was added and thermocompression bonded.
Next, probe contact needles (number: 50, area: 10 cm, adjacent tip portion pitch: 2 mm, base end surface, fixed to the anisotropic conductive member by the fixing holder shown in Table 2 below A probe card was prepared by bringing a size (500 μmφ) into contact.

(Comparative Examples 1-4)
A commercially available anisotropically conductive member (anisol AC-4000, manufactured by Hitachi Chemical Co., Ltd.) and a circuit board for inspection shown in Table 2 below are used 180 using a thermocompression bonding apparatus (MODEL6000, manufactured by Hisol Co.). At a temperature of 0 ° C., a pressure of 0.4 MPa was applied for thermocompression bonding.
Next, probe contact needles (number: 50, area: 10 cm, adjacent tip portion pitch: 2 mm, base end surface, fixed to the anisotropic conductive member by the fixing holder shown in Table 2 below A probe card was prepared by bringing a size (500 μmφ) into contact.

FIG. 11 is a schematic cross-sectional view for explaining the contact (joining) state of the inspection electrode, the anisotropic conductive member, and the probe contact needle of the probe card used in the examples and comparative examples.
As shown in FIG. 11, in the example and the comparative example, 50 probe contact needles 16 fixed by a fixing holder 19 whose one side is connected to the circuit board for inspection 5 by a fixing member 20 are arranged at equal intervals, and the outermost side. The one arranged so that the distance between the probe contact needles provided on the head was 10 cm.

<Conductivity>
Each manufactured probe card was examined for conductivity before examining the electrical characteristics of the object to be inspected.
Specifically, the tip of the contact needle of each probe card produced is contacted with a gold ribbon (AU-170324, size: 0.10 mm × 2.0 mm × 500 mm, purity: 99.95%, manufactured by Niraco). The conductivity test was conducted.
In the measurement of electrical conductivity, the electrical resistance measured by the 4-terminal method was measured with a milliohm meter, and converted into a specific resistance from the size of the gold ribbon and the distance (10 cm) between the probe contact needles provided on the outermost side.
Here, according to page 597 of the “Electrical and Electronic Materials Handbook” (first edition, 1987, Asakura Shoten), the specific resistance (ρ) of gold is as follows.
ρ = 2.21 × 10 ⁻⁸ [Ω · m] (20 ° C.)
ρ = 3.57 × 10 ⁻⁸ [Ω · m] (150 ° C.)
Therefore, when the specific resistance value is 1 to 5 times the reference value, it is evaluated as ◯, and when the specific resistance value is more than 5 times and less than 10 times from the reference value, it is evaluated as △ and more than 10 times from the reference value. What was was evaluated as x. The results are shown in Table 2 below.

<Position>
About each produced probe card, position shift (between AB of Drawing 11) with an inspection electrode and a conduction path of an anisotropic conductive member, and a position of a conduction path of an anisotropic conductive member and a probe contact needle The shift (between B and C in FIG. 11) was examined.
Specifically, each probe card is placed on a hot plate (HTP452AA, manufactured by ASONE), and the contact interval dr [μm] before heating (25 ° C.) and the contact interval dh [μm] before heating (125 ° C.) are measured. The contact deviation amount was calculated from the difference.
Contact displacement [mm] = dh-dr
Here, the contact interval was measured using a digital reading microscope (NRM-D-2XZ, measurement range: X axis 0 to 200 mm, Z axis: 0 to 150 mm, minimum reading value: liquid crystal digital 0.01 mm).

  In Table 2, the materials used for the circuit board for inspection and the fixed holder and the coefficient of thermal expansion are shown in Table 3 below.

The probe card manufactured in Example 1 and Comparative Example 4 was subjected to a heat cycle test (186 cycles at 125 hours) at temperatures of −40 ° C. and 125 ° C.
As a result, for the probe card of Example 1, the increase rate of the specific resistance remained at 10%, whereas for the probe card of Comparative Example 4, the increase rate of the specific resistance was 80%.

  From these results, the insulating base material made of an anodized film of an aluminum substrate having micropores penetrates the insulating base material in the thickness direction in a state where a plurality of conductive paths made of a conductive member are insulated from each other. And a specific member provided in a state in which one end of each conductive path protrudes on one surface of the insulating base material and the other end of each conductive path protrudes on the other surface of the insulating base material. By using an anisotropic conductive member, the connection stability between the inspection electrode and the electrode to be inspected is good even after being exposed to a high temperature by a burn-in test, and the inspection electrode and the conductive portion are not used even after repeated use. It has been found that positional displacement hardly occurs in contact and contact between the conductive portion and the probe contact needle.

About the probe card manufactured in Example 1, the heat cycle test (186 cycles in 125 hours) was performed under the temperature of -40 degreeC and 125 degreeC.
As a result of measuring the resistance value before and after the heat cycle test by the above-described conductivity test, the resistance value after the heat cycle test was 10% larger than the resistance value before the heat cycle test.
Next, the probe contact needle of the probe card after the heat cycle test was placed in a liquid absorbent material (sheet type (P-110) manufactured by 3M Co., Ltd.) impregnated with 0.1N potassium hydroxide aqueous solution at 25 ° C., Contacted for 5 minutes.
As a result of measuring the specific resistance after the contact by the above-described conductivity test, it was found that the increase in the resistance value after the heat cycle test was reduced to 5%, and the electrical activity of the probe contact needle was restored. It was.

  In the present invention, the probe contact needle described above is described as an electrical contact for connecting the electrode to be inspected and the anisotropic conductive member. For example, the semiconductor described in JP-A-2002-257898 is described. When used in the probe pin usage mode in the device inspection probe structure, as the usage mode included in the probe card according to claim 1 of the claims, the anisotropic conductive member includes the electrode to be inspected, the probe pin, It can also be used as a contact between the two.

  Similarly, when the probe contact needle described above is used, for example, in the usage mode of the probe pin in the probe card described in JP-A-11-190748, it is included in the probe card according to claim 1 of the claims. As a usage mode, the anisotropic conductive member can also be used as a connector for contacting a circuit on a contactor and a wiring circuit (FPC) on a substrate.

FIG. 1 is a sectional view showing a schematic configuration of a preferred embodiment of the probe card of the present invention. FIG. 2 is a simplified diagram showing an example of a preferred embodiment of the anisotropic conductive member. FIG. 3 is an explanatory diagram of a method for calculating the degree of ordering of pores. FIG. 4 is a cross-sectional view showing a schematic configuration of one preferred embodiment of the electrical contact in the probe card of the present invention. FIG. 5 is a sectional view showing a schematic configuration of another preferred embodiment of the electrical contact in the probe card of the present invention. FIG. 6 is a schematic end view for explaining an example of the anodizing process in the anisotropic conductive member manufacturing method. FIG. 7 is a schematic end view for explaining an example of a metal filling step and the like in the anisotropic conductive member manufacturing method. FIG. 8 is a schematic diagram illustrating a preferred embodiment of a method for joining the circuit board for inspection and the anisotropic conductive member by thermocompression bonding. FIG. 9 is a schematic diagram showing a schematic configuration of a preferred embodiment of the probe inspection apparatus of the present invention. FIG. 10 is an explanatory diagram for calculating the density of the conductive path of the conductive member. FIG. 11 is a schematic cross-sectional view for explaining the contact (joining) state of the inspection electrode, the anisotropic conductive member, and the probe contact needle of the probe card used in the examples and comparative examples.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Probe card 2 Inspected object 3 Inspected electrode 4 Inspection electrode 5 Inspection circuit board 6 Anisotropic conductive member 7 Insulating base material 8 Conducting path 9 Holder 10a, 10b Protrusion part 11 In-base conductive part 12 Insulation Thickness of base material 13 Width between conductive paths 14 Diameter of conductive paths 15 Distance between centers of conductive paths (pitch)
16 Probe Contact Needle 17 Base End 18 Tip 19 Fixed Holder 20 Fixing Member 21 Resin Material 22 Bump Contact 23 Base End 24 Tip 32 Aluminum Substrate 34a, 34b, 34c, 34d Anodized Films 36a, 36b, 36c, 36d Micropores 38a, 38b, 38c, 38d Barrier layer 40 Insulating substrate 41 Precursor of anisotropic conductive member 42 Anisotropic conductive member 45, 45a, 45b Pressure head 51 Unit cell of micropore 52 Conductive electrode Part 70 Probe device 71 Probe card 72 Interface ring 73 Tester head 101, 102, 104, 105, 107, 108 Micropore 103, 106, 109 yen

Claims (9)

A probe card for inspecting the electrical characteristics of a test object in contact with the test electrode of the test object,
An inspection circuit board on which inspection electrodes are formed so as to correspond to the electrodes to be inspected;
An anisotropic conductive member that electrically connects the electrode to be inspected and the electrode for inspection, and
The inspection electrode is provided with at least a tip portion protruding from the surface of the inspection circuit board,
The anisotropic conductive member penetrates the insulating base material in the thickness direction in a state in which a plurality of conductive paths made of the conductive member are insulated from each other in the insulating base material, and each of the conductive paths A member provided with one end projecting on one surface of the insulating base material and the other end of each conduction path projecting on the other surface of the insulating base material, wherein the insulating base material is micro A probe card, which is a structure made of an anodized film on an aluminum substrate having pores. Furthermore, an electrical contact that makes electrical contact with the electrode to be inspected is provided,
The probe card according to claim 1, wherein the electrode to be inspected and the anisotropic conductive member are connected via the electrical contact.   The probe card according to claim 2, wherein the electrical contact is a probe contact needle.   The probe card according to claim 3, further comprising a fixing holder that fixes the probe contact needle so that both tip portions of the probe contact needle protrude from the surface. The probe card according to claim 1, wherein the inspection circuit board is made of a material having a coefficient of thermal expansion of 2.5 × 10 ⁻⁶ to 10 × 10 ⁻⁶ K ⁻¹ . The probe card according to claim 1, wherein the probe card is used for the object to be inspected made of a material having a thermal expansion coefficient of 2.5 × 10 ⁻⁶ to 10 × 10 ⁻⁶ K ⁻¹ . The probe card according to claim 4, wherein the fixed holder is made of a material having a coefficient of thermal expansion of 2.5 × 10 ⁻⁶ to 10 × 10 ⁻⁶ K ⁻¹ . Before inspecting the electrical characteristics of the object to be inspected, a pretreatment step of contacting the protruding portion of the conduction path on the side in contact with the electrode to be inspected with an alkaline aqueous solution or an acidic aqueous solution;
The probe card inspection method according to claim 1, further comprising: an inspection step of inspecting electrical characteristics of the object to be inspected by bringing the protruding portion after the pretreatment step into contact with the electrode to be inspected. Before inspecting the electrical characteristics of the object to be inspected, a pretreatment step of bringing the electrical contact into contact with an alkaline aqueous solution or an acidic aqueous solution;
The inspection of the probe card according to claim 2, further comprising: an inspection step of inspecting an electrical characteristic of the object to be inspected by bringing the electrical contact after the pretreatment step into contact with the electrode to be inspected. Method.

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