WO2004110116A1

WO2004110116A1 - Production method for feedthrough electrode-carrying substrate

Info

Publication number: WO2004110116A1
Application number: PCT/JP2004/007354
Authority: WO
Inventors: Yasuhito Takeuchi; Satoshi Yamaguchi
Original assignee: Hitachi Metals, Ltd.
Priority date: 2003-06-03
Filing date: 2004-05-28
Publication date: 2004-12-16

Abstract

A feedthrough electrode-carrying substrate used for a substrate for a giant magneto-resistance effect element or the like. Thermosetting conductive paste is filled into through-holes formed in an insulating substrate of glass, ceramics, etc. by screen printing or the like, and the filled conductive paste is heated and cured to produce a feedthrough electrode-carrying substrate. Conductive paste is filled in so as to protrude from the opposite ends of through-holes, and the protruded portions of conductive paste are removed by working after heat-cured. Since zones having a low conductive powder density are formed in the vicinities of the protruded portions of cured conductive paste and the ends of through-holes, opposite end surfaces of the insulating substrate including protruded conductive paste portions are worked to remove the zones and hence obtain a good-conduction feedthrough electrode. In addition, properly-shaped through-holes can prevent a feedthrough electrode from loosening.

Description

Specification

Method for manufacturing substrate with through electrodes

Technical field

The present invention relates to a method for manufacturing a substrate with a through electrode, which can stably obtain an electrode having excellent electrical conduction.

Background art

[0002] When a lead wire is taken out from a sensor chip manufactured by a wafer process on an insulating substrate, a metal wire is attached to an electrode terminal of the sensor chip by ultrasonic bonding, or a flexible cable having a pattern formed is used. Soldering is commonly used. If a through-electrode can be formed on the wiring board, the sensor terminals can be formed on the insulating substrate by connecting the electrode terminals on the back side of one sensor chip to the through-electrode. It is not necessary to form a pad, and the sensor chip size can be reduced. In addition, there is no wire / flexible cable wiring on the front side of one sensor chip, and the sensor chip surface can be brought closer to the target of sensing, so that the sensitivity of the sensor can be improved. Furthermore, if the sensing target is a flat surface, the sensor can be slid. By using the wafer process, it is possible to reduce the size and size of the sensor pattern by photolithography technology, and to reduce costs by manufacturing sensor chips all together. A substrate with a through electrode is a very useful substrate for manufacturing a sensor chip because of the advantages described above.

[0003] In order to create a substrate having a through electrode attached to an insulating substrate, a through hole is formed in the insulating substrate, and the through hole is filled with a conductive paste and cured to form a substrate with a through electrode. . An insulator such as ceramics, glass, or resin is used as the insulating base material. Also, a conductive paste that is cured at a temperature equal to or lower than the heat resistant temperature of the insulating base material is used. By using screen printing technology to fill the conductive paste, the paste can be simultaneously filled into many through holes formed in the insulating base material. By forming fine through-holes with high precision, it is possible to manufacture substrates with through electrodes in which fine electrodes are arranged with high precision. it can. In order to form an electrode in the through-hole, it is not desirable because the insulating base material may be cracked by the force S that can insert the plastically deformed metal into the through-hole and the force when the metal is inserted. Les ,. In addition, the force S that can fill the through hole with metal by plating, the seed layer for plating must be formed in advance because the base material is insulating, and the process becomes complicated, which is not desirable. ,. It is generally employed to form an electrode by filling a conductive paste into an insulating base material having through holes formed therein.

[0004] The conductive paste is composed of conductive powder particles called a filler and a liquid binder. Select a binder with appropriate components to control the curing temperature of the conductive paste. The conductive paste used to form electrodes for multilayer ceramic electronic components uses glass as a binder, and therefore requires firing at a temperature of around 900 ° C for curing. However, a thermosetting conductive paste using a thermosetting resin such as epoxy as a binder can be cured at a temperature of about 200 ° C. If a thermosetting conductive paste is used, the conductive paste can be cured even with a simple device such as an electric oven, and an insulating base material made of a material having a low heat-resistant temperature can be used.

[0005] A peeling plate such as a doctor blade is usually used for filling a conductive paste into a through hole formed in an insulating base material. The conductive paste applied to the surface of the base material is filled into the through-hole while being scraped off with a doctor blade, so part of the conductive paste near the tip of the through-hole is removed, and the conductive paste filled in the through-hole is recessed at the tip. May occur. Japanese Patent Application Laid-Open Publication No. 2001-160684 discloses a technique in which a roller is rolled on an insulating base material to fill the through-hole with pressure while applying a conductive paste. According to the technology disclosed in the Japanese Patent, since the conductive paste can be filled into the through-hole while reducing the pressure, the occurrence of a depression on the conductive paste filled in the through-hole can be prevented. be able to.

[0006] However, it is required that the through electrodes provided on the insulating substrate have good conductivity and no conduction failure. Since the penetrating electrode is made by heating and curing a conductive paste obtained by mixing a conductive filler powder and a binder resin, the conduction of the penetrating electrode sometimes becomes poor during the heating and curing. Even if the technology disclosed in the above-mentioned Japanese Patent Publication is used, in order to eliminate the conduction failure of the through electrode, an extremely large pressure is applied to the conductive paste when filling the through-hole with the conductive paste. In addition to this, it was necessary to squeeze excess binder resin and discharge it out of the through-hole. Disclosure of the invention

[0007] In view of the above problems, the present invention does not require a special device for forcibly discharging excess binder resin to the surface of the insulating base material. To provide a method of manufacturing a substrate with a through-electrode that can stably manufacture a substrate having a through-electrode with good electrical conductivity even when using a technique of filling a conductive paste into a through-hole by using And

[0008] In the method for manufacturing a substrate with a through electrode according to the present invention, a through hole is formed in an insulating base material, a thermosetting conductive paste is filled in the through hole, and a height of 50 / m from both ends of the through hole. — 200 μm, preferably 70 βm—100 μm height, formed with thermosetting conductive paste, heat-cured thermosetting conductive paste, including protrusion of thermosetting conductive paste First, the process power is removed from both surfaces of the insulating base material to remove 3 / im—50 μm on one side from the surface of the insulating base material. The through hole preferably has a diameter of 30 _β m—800 μm.

[0009] Ceramics, glass, resin, or a composite material thereof can be used as an insulating substrate used for manufacturing a substrate with a through electrode. Preferably, the insulating substrate is 300 μm 2 mm thick. For substrates with a thickness of less than 300 x m, cracking or chipping occurs during handling during processing or chip mounting after processing, and it is difficult to obtain a substrate with a through-electrode that is immediately strong. For a substrate with a through electrode thicker than 2 mm, it is difficult to uniformly fill the conductive paste in the through hole.

[0010] The thermosetting conductive paste used in the production method of the present invention is preferably composed of 8593% by mass of the filler powder and the balance substantially of the thermosetting binder resin. The thermosetting binder resin preferably contains a liquid epoxy resin having two or more epoxy groups as a main component. The filler powder is preferably made of conductive powder particles having an average particle size of 1.O xm or more and 20 zm or less. The average particle diameter of the filler particles is preferably 1.0 / im—8.0 / im for spherical particles. The average particle diameter of the filler powder is 3.0 / im—20 / im for flake particles. preferable. In addition, the thermosetting conductive paste preferably further contains 0.2% by mass to 3.0% by mass of a curing agent and 1.0% by mass or less of a dispersant. [0011] The through-hole has a height of 1/20 or more of the average particle diameter of the filler powder particles contained in the thermosetting conductive paste to be filled with unevenness of the surface roughness in 30% or more of the inner wall surface of the through-hole. It is preferable that the pitch of the unevenness of the surface roughness is not less than the average particle diameter while having a difference.

[0012] Alternatively, the through-hole may have a local minimum value of the diameter smaller than the diameter of each opening at both ends, and the local minimum value may be larger than eight times the average particle size of the filler particles. preferable. It is further preferred that the minimum value is less than 90% of the diameter of the opening on the smaller side of the opening at both ends. Then, the minimum value is preferably larger than 80 zm.

[0013] Alternatively, the through-hole may be such that the center axes of the openings at both ends thereof are eccentric to each other, and the amount of eccentricity is preferably larger than the difference between the radii of the two openings.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic view for explaining a method for manufacturing a substrate with through electrodes, and FIG. 1 (A) is a perspective view showing an insulating base material used in the manufacturing method of the present invention, and FIG. (B) is a perspective view of the insulating base material with a through hole, FIG. 1 (C) is a cross-sectional view of the insulating base material shown in FIG. 1 (B) along the line 1C-1C, and FIG. 1 (D) is Fig. 1 (C) is a cross-sectional view of the insulating base material in which the conductive paste is filled into the through holes of the insulating base material.The heights H and H 'of the conductive paste projecting from both end surfaces of the base material are shown. FIG. 1E is a cross-sectional view showing the processing amounts W, W from both end surfaces of the insulating base material filled with the conductive paste.

FIG. 2 is a schematic cross-sectional view for explaining a cross section of a conductive paste filled and solidified in a through hole formed in an insulating base material.

FIG. 3 is a schematic cross-sectional view for explaining a state in which a conductive paste filled in a through hole formed in an insulating base material is solidified when heated.

FIG. 4 is an enlarged cross-sectional view of a through hole formed in an insulating base material that can be used in the present invention.

FIG. 5 is an explanatory enlarged sectional view of a wall surface of a through hole.

FIG. 6 is a plan view of a wiring substrate having a GMR element formed on a substrate with through electrodes.

FIG. 7 is a rear view of the wiring board of FIG. 6.

FIG. 8 is a graph showing the relationship between the slack occurrence rate (%) of the through electrode and the ratio (%) of the through hole uneven portion.

FIG. 9 is an enlarged cross-sectional view of another through hole formed in an insulating base material that can be used in the present invention. is there.

FIG. 10 is an enlarged cross-sectional view of still another through-hole formed in an insulating substrate that can be used in the present invention.

Explanation of reference numerals

[0015] 10 Insulating base material

12 Through hole

30 Thermosetting conductive paste

32 Projection

100 PCB with through electrodes

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] A method for manufacturing a substrate with through electrodes according to the present invention will be described in detail with reference to the drawings.

In the method for manufacturing a substrate with a through electrode according to the present invention, an insulating substrate 10 shown in a perspective view in FIG. 1A is used. As the base material 10, ceramics, glass, resin, or a composite material thereof can be used. The substrate 10 preferably has a thickness of 300 zm-2 mm.

When the base material 10 is as thin as 100 μm or 200 μm, the through electrode formed by filling the through-hole formed in the base material 10 with the conductive paste does not cause a conduction failure, but 300 zm Since a thinner substrate has too low mechanical strength and may break during handling, it is desirable to use a substrate 10 having a thickness of 300 zm or more. If the thickness of the base material 10 is more than 2 mm, as will be described in the later examples, even if the present invention is applied, conduction failure may occur in the through-electrode. It is desirable that:

[0019] The insulating base material is preferably ceramics, glass, resin, or a composite material of these materials, which has a proven track record for use in electronic components and is easy to mold and has the required strength. From the viewpoint of maintaining the electrical insulation between the electrodes and preventing the occurrence of a short circuit between the electrodes due to the migration of the electorifice, it is desirable that the volume resistivity indicating the insulating property of the insulating base material is ¹⁰¹ QΩcm or more. Since the curing temperature of the conductive paste is around 200 ° C, it is more desirable for the insulating base material to have a softening temperature of 250 ° C or higher, preferably 300 ° C or higher. Specific examples of ceramics include anoremina, zirconia, silica, BaTiO, CaTiO, Ni

3 3

Zn fluoride or the like can be used. For glass, soda glass, borosilicate glass, lead glass , Quartz glass, crystallized glass and the like can be used. As the resin, polyimide, polycarbonate, polyethersulfone (PES), polysulfone, or the like can be used, and as the composite material, ceramic glass composite material, glass epoxy, or the like can be used.

As shown in FIG. 1 (B) and FIG. 1 (C), a through hole 12 is formed in the insulating base material 10. The through hole 12 of the insulating substrate 10 can be formed by a laser, shot blast, punch, drill, etching, embedding, or the like, which is desired to be easily and accurately formed industrially. In particular, shot blasting and etching are desirable because a large number of through holes can be simultaneously formed in the insulating base material. The diameter of the through-hole is desirably 30 zm or more and 800 zm or less. It is difficult to uniformly fill the conductive paste, which is difficult to form easily and stably, with a through hole having a diameter of less than 0 x m. A through-hole having a diameter larger than 800 zm is not desirable because it has problems such as leakage of the conductive paste between the time of filling the conductive paste and the time of curing. The through hole is not limited to a circle, but may be a square, an ellipse, or an indefinite shape. These diameters are defined by the diagonal line for a rectangle, the major axis for an ellipse, and the average length of the shortest and longest diagonal lines for irregular shapes.

[0021] The thermosetting conductive paste 30 is filled in the through holes 12 shown in FIGS. 1 (B) and 1 (C) as shown in the cross-sectional view of FIG. A protruding portion is formed from a thermosetting conductive paste 30 from the opening. Then, the thermosetting conductive paste 30 filled in the through holes 12 is cured by heating.

[0022] In order to fill the through-holes 12 formed in the insulating base material 10 with the thermosetting conductive paste 30, a method of injecting the conductive paste into each hole, or a method of applying pressure to the conductive paste applied on the insulating base material, is used. And a method of extruding the conductive paste from all the through holes 12 of the insulating base material, or a screen printing method. If screen printing is used, it is possible to simultaneously fill the conductive paste 30 into all of the many through holes arranged and formed in the insulating base material 10 in a precise pattern. In addition, unnecessary conductive paste can be prevented from adhering to the surface of the insulating base material. This eliminates the need for a step of removing the adhered substance in a later step and saves the conductive paste, which is economical. Furthermore, if the screen printing method is used, it becomes easy to control the height of the protrusion of the conductive paste, which is important in the present invention. In the screen printing method, the protrusion height of the conductive paste is set on the filling amount of the conductive paste and the back surface of the insulating base material. Precise control can be achieved by spacing with the stopper sheet to be set.

It is desirable that the protrusion height H of the protrusion 32 when the thermosetting conductive paste 30 is filled in the through-hole 12 provided in the insulating base material 10 be not less than 50 × m and not more than 200 × m. If the protruding height of the conductive paste is less than 50 μm, a region having a low filler powder concentration cannot be completely removed by processing, and an electrode with poor conduction may be generated in the substrate 100 with through electrodes. Further, if the protruding height H of the protruding portion 32 of the conductive paste 30 is larger than 200 μm, the amount of the conductive paste to be removed by the processing increases, and the processing time which is economical is long. In order to more reliably remove the region where the filler powder concentration is low and use the conductive paste more economically, the protrusion height H of the conductive paste protrusion 32 should be 70 am or more and 100 μm or less. desirable.

[0024] The thermosetting conductive paste 30 used in the present invention preferably contains 85% to 93% by mass of the filler powder and the balance substantially of the thermosetting conductive binder resin. The conductive paste may further include a curing agent and a dispersant. The binder resin contains as a main component a liquid epoxy resin having two or more epoxy groups, and the filler powder preferably contains conductive powder particles having an average particle size of 1.0 μm or more and 20 μm or less as the main component. New

[0025] If a liquid epoxy resin is used as a binder resin containing a liquid epoxy resin having two or more epoxy groups as a main component, a conductive paste can be formed even at a low temperature of around 200 ° C by selecting an appropriate curing agent. It can be cured. If the curing temperature is low, a simple device such as an electric oven can be used. Further, even a material having a low heat resistance temperature can be used as an insulating substrate. Liquid epoxy resins having two or more epoxy groups include bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, amine type epoxy resin, naphthalene skeleton epoxy resin, and dimer acid. It is possible to use dinole esterified epoxy resins, etc., alone or as a mixture. In particular, glycidinole ester epoxy resins have low viscosity and have flexibility after curing. By mixing and using these resins, it is possible to increase the reliability of the conductive paste against thermal cycling. Reliable for thermal cycling In the case of a low conductive paste, the contact state between the filler powder particles changes due to expansion and contraction due to heat, and the electric resistance may change.

[0026] The curing agent added to the binder resin, when mixed with the epoxy resin, can be stored at room temperature for a long time without changing its properties, and has a property of rapidly curing when heated to a predetermined temperature or more. It is desirable to have. Examples of the curing agent include amine-based curing agents such as dicyandiamide-carboxylic acid hydrazide, and imidazole-based curing agents such as 2-ethyl-4-methylimidazole, phthalic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, and the like. Acid anhydride-based curing agents such as methylnadic anhydride, and aromatic amine-based (amine adduct) curing agents such as diaminodiphenylmethane and diaminodiphenylsulfonic acid lj, 3_ (3,4-dichlorophenol) Urea-based curing agents such as 1,1-dimethylurea, cationic catalyst-based curing agents, phenol-based curing agents and the like can be used. The amount of the curing agent added is preferably 0.2% by mass to 3.0% by mass relative to the conductive paste. If the curing agent is added in excess of 3.0% by mass, the viscosity of the conductive paste increases, making it difficult to fill the through-hole. If the amount is less than 0.2% by mass, the resin may not be cured.

[0027] The dispersant is preferably added because it has the effect of lowering the viscosity of the conductive paste and assisting the filling of the through-hole. Examples of the dispersing agent include higher fatty acid ethylene oxide, propylene oxide addition esterified product, ester compound of sorbitan and fatty acid, polyhydric alcohol ethylene oxide such as sorbitan, propylene oxide addition ether compound, alkyl benzene ethylene oxide, and the like. Nonionic dispersants such as propylene oxide adducts, alkali salts of alkyl benzene sulfonic acid, alkali salts of higher alcohol sulfates, phosphoric acid ester compounds, higher fatty acids, ethylene oxides of higher fatty acids, and petroleum products with propylene oxide Anionic dispersants such as sulfate alkali salts, and cationic dispersants such as quaternary ammonium salt types can be used. The amount of the dispersant added is desirably 1.0% by mass or less relative to the conductive paste. If the dispersant is added in excess of 1.0% by mass, the viscosity of the conductive paste is too low, which is not desirable.

[0028] As the filler powder, conductive powder particles of noble metal, base metal, carbon and the like can be used. In order to obtain a through electrode having a small electric resistance and good electric conduction, it is desirable to use a filler powder material having a small electric resistance. Filler powder with low electric resistance The material may be used lead volume resistivity of not more than 20 X 10- ⁶ Ω cm, platinum, tungsten, nickel, tin, zinc, metals such as iron material whose main component. For more electrical resistance electrical continuity smaller obtain good penetration electrodes are gold volume resistivity 5. or less OX 10_ ⁶ Q cm, silver, copper, a metal such as aluminum material whose main component It is more desirable to use. In order to prevent the surface oxidation of the filler powder particles, base metal powder particles coated with a noble metal can be used. For example, filler powder particles in which the surface of copper powder particles that are easily oxidized are coated with silver are desirable because they exhibit the same electrical resistance as silver powder particles and are economical.

[0029] The shape of the filler powder particles should be spherical, elliptical, hexahedral or octahedral or more polyhedral, plate-like, flake-like, needle-like, amorphous, or a combination thereof. Is possible. It is also possible to use not a single particle but a particle obtained by combining a plurality of particles. Spherical or flake-shaped particles can be produced by an industrially easy method such as an atomizing method or a reducing method, and thus have a more desirable shape as filler powder particles.

[0030] The average particle diameter of the filler powder particles is: 1. O / im-20 / im is preferred. If the particle shape is spherical, it is 1.0 μm or more and 8.0 μm or less. Is preferably not less than 3.0 μm and not more than 20 μm. Here, the particle size of the filler powder particles was measured by observing a small amount of filler powder particles adhered to the conductive adhesive tape with a scanning electron microscope. The longest diameter of each particle measured from the observation image is defined as the particle diameter, and the average value of the particle diameters of all the particles included in an arbitrary observation field is defined as the average particle diameter. A filler powder having an average particle size smaller than the above range has a large specific surface area with respect to the volume, so that the particles are easily oxidized, which is not desirable. In addition, since the number of contacts between particles increases, the contact resistance tends to increase. On the other hand, a filler powder having an average particle diameter larger than the above range is not desirable because conversely, the number of contact points between the particles is reduced and the electric resistance is increased, and the reliability with respect to the thermal cycle after the conductive paste is cured is lowered. The flake-like filler powder tends to have a higher viscosity at the same mixed weight than the spherical filler powder, so that screen printing becomes difficult. Therefore, it is necessary to change the conditions of screen printing. Spherical filler powder particles, flaked filler powder particles, and filler powder particles of other shapes may be mixed and used. By mixing, excellent adhesion between the flake filler powder particles with low contact resistance and the insulating substrate It is possible to make use of the advantages of the spherical filler powder particles.

[0031] The mixing amount of the filler powder with respect to the conductive paste is desirably 85% by mass or more and 93% by mass or less with respect to the conductive paste. If the mixing amount of the filler powder is less than 85% by mass, the number of contacts between the filler powder particles after curing of the conductive paste decreases and the electric resistance increases, and the reliability with respect to the thermal cycle after curing of the conductive paste decreases. Desirable les ,. If the mixing amount of the filler powder is more than 93% by mass, the viscosity of the conductive paste becomes high, which makes it difficult to fill the through-holes. In order to obtain an electrode with high reliability in thermal cycles as soon as it is filled into the through-holes, it is more preferable that the mixing amount of the filler powder with respect to the conductive paste is 90% by mass to 92% by mass.

[0032] As shown in FIG. 1 (E), the protrusions 32 of the thermosetting conductive paste 30 protruding from both end surfaces of the insulating base material 10 are applied from both end surfaces of the insulating base material 10. Then, 3 μτη−50 μm is removed from one side of the surface of the insulating base material 10 to obtain the substrate 100 having the through electrodes 30a.

[0033] In the processing of the insulating base material 10, it is desirable to process it into a smooth surface by grinding or lapping. By smoothing the surface of the substrate 100 with through electrodes, it is possible to form a fine wiring pattern with high accuracy by photolithography. It is desirable that the processing amount W, W 'of one side of the insulating base material be 3 μm or more and 50 μm or less. If the processing amount is less than 3 μm, it will be difficult to process the entire surface of the insulating base material on average, and there will be portions that cannot be completely removed by processing in the region with low filler powder concentration. There is a possibility that through electrodes with poor conduction may occur. If the processing amount exceeds 50 μΐη, not only is the processing time prolonged, but also a thick insulating base material must be used, which increases the manufacturing cost and is not preferable.

When observing the inside of the thermosetting conductive paste 30 filled in the through holes 12 of the insulating base material 10, as shown in FIG. In addition, regions 36 having a lower filler powder concentration than the surface layer 34 and the inside 38 of the cured conductive paste 30 are formed on both end surfaces of the substrate 10. In this region 36, since the filler powder concentration is low, the contact area between the filler powder particles is small and the electric resistance is large. In the present invention, both sides of the insulating base material 10 including the protrusions 32 of the thermosetting conductive paste 30 are included. Since surface force processing is performed to remove 3 μm – 50 μm on one side from the surface, as shown in Fig. 2 (B), it is possible to remove the area 36 where the filler powder concentration is low. Therefore, the through-electrode 30a of the through-electrode-attached substrate 100 obtained by the present invention has less conduction failure.

[0035] It is considered that the region 36 with a low filler powder concentration is formed near the surface layer 34 of the cured conductive paste 30 due to the following reasons.

[0036] The binder resin of the conductive paste 30 has a large coefficient of thermal expansion and a high fluidity as compared with the filler powder particles, and thus easily oozes from the inside of the conductive paste to the outside during thermosetting. In addition, the filler powder particles agglomerate with each other at the time of thermal curing, and the exudation of the binder resin is easily promoted. Furthermore, when the thickness of the insulating base material 10 is increased, the heating of each portion of the filled conductive base 30 becomes uneven, and as soon as the surface layer 34 of the conductive paste 30 is hardened first. It is presumed that a region 36 having a low filler powder concentration is formed due to the above reasons.

The uncured conductive paste 30 filled in the through holes 12 of the insulating base material 10 shown in FIG. 3A starts to be cured by being exposed to the heat of an electric oven. First, the surface layer 34 shown in Fig. 3 (B) is rapidly cured by the direct heat radiation 42 from the electric oven, which transfers heat to the inside of the conductive paste 30 because the insulating base material 10 is thick. Thus, an initial hardened layer is formed. It is considered that when the surface layer 34 is cured, the binder resin does not exude due to thermal expansion, and is cured while maintaining the ratio of the filler powder and the binder resin substantially at the time of filling. As the heating of the insulating base material 10 progresses, heat is transmitted to the conductive paste 30 through the side wall of the through-hole as indicated by the solid arrow 44, and the inside of the paste starts to cure. However, since the inside of the conductive paste 30 is hardened gently by heat conduction, the binder resin expanded by heat is hardened while seeping out with the surface layer 34, and as shown in FIG. It is considered that a region 36 having a low powder concentration is formed. In the region 36 where the filler powder concentration is low, the contact between the filler powder particles is small, so that the current path becomes narrow and the electric resistance rises. In the present invention, since the protrusions 32 of the conductive paste 30 and 3 μm to 50 μm are removed from the surface of the substrate 10, the region 36 having a low filler powder concentration is removed.

Example 1

[0038] Using a polyimide insulating base material and a glass-epoxy resin insulating base material, A through-hole was formed in the substrate, and a conductive paste was filled in the through-hole and cured to produce a substrate with a through-electrode. The polyimide substrate was a 100 mm square, 1.5 mm thick and 3. Omm thick. The glass-epoxy resin substrate was a square of 120 mm square and had a thickness of 2. Omm and 2.4 mm. Two types of through holes with a diameter of 200 zm and a diameter of 400 zm were formed with a micro drilling machine using an NC drill. These through holes were formed at equal intervals of 2 mm pitch. In each condition, as many substrates as possible were formed so that through electrodes could be formed in 1000 through holes, and a substrate with through electrodes was manufactured. The conductive paste was a 1: 1 (mass ratio) mixture of bisphenol A type epoxy resin (Epicoat 828 Yuka Shell Epoxy) and alicyclic epoxy resin (ST-1000 manufactured by Toto Kasei) as binder resins. An amine-adduct-based curing agent (MY-24, manufactured by Ajinomoto Co.) was used as a curing agent, and a phosphate ester (anionic surfactant "Blysurf" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a dispersing agent. The curing agent and the dispersant were added in an amount of 0.2% by mass and 0.2% by mass, respectively, based on the conductive paste. Spherical silver particles having an average particle size of 2.1 / m were used as the filler powder, and 90.5% by mass of the conductive paste was added. These binder resin and filler powder were stirred and kneaded while defoaming with a three-roll mill. The viscosity of the kneaded conductive paste was 130 0 to 1400 Pa's (at a rotation speed of 0.5 RPS) as measured by an E-type viscometer at room temperature. The through-hole was filled with a conductive paste using a screen printer so that the protrusion heights H and H ′ of the protrusions 32 shown in FIG. 1 (D) were both 100 μm. The conductive paste was cured by heating in an electric oven at 200 ° C for 60 minutes. Then, to obtain a processed amount W, lapping process to a substrate with through electrodes 100 on both sides of the insulating base 10 as W ^f are both 20 mu m shown in FIG. 1 (E).

The resistance between both ends was measured for 1000 through electrodes manufactured under each condition. The resistance evaluation results are shown in Table 1 together with the manufacturing conditions (base material, base material thickness, through-hole diameter). 3. The through electrode substrate with through electrodes using the Om m thick polyimide substrate 2. 4 mm thick glass one epoxy resin substrate of greater than 2 X 10- ⁴ Ω cm in terms of volume resistivity Penetrating electrodes indicating resistance contained more than 70% of all penetrating electrodes. In addition, most of them were penetrating electrodes with no electrical conduction and could not be used as penetrating electrodes. This is probably because the insulating base material was thick and the conductive paste could not be uniformly filled in the through holes. On a substrate with a through electrode with a thickness of 2 mm or less, all the through electrodes In terms of volume resistivity shows the resistivity of below 2 X 10- ⁴ Ω cm, was because it was confirmed that good penetration electrodes of electrical conduction are formed as the evaluation of "good".

[0040] [Table 1]

¾ 2

[0041] Using an insulating base material made of sintered alumina ceramics having a purity of 96% and an alkali-free glass (# 1737 made by Koingen Co., Ltd.) insulating base material, conductive paste protruding into the through-holes The substrates with penetrating electrodes were manufactured by changing the protruding height H of the part and the processing amount W of the substrate, and the penetrating electrodes of those substrates were evaluated. The alumina substrate was a 75 mm diameter disk with a thickness of 1. Omm, and the alkali-free glass substrate was a 150 mm diameter disk with a thickness of 0.7 mm. Circular through holes with a diameter of 150 μm were formed on the alumina substrate with a carbon dioxide laser beam machine, and circular holes with a diameter of 200 m were formed on the non-alkali glass substrate with a resist mask and shot blasting. The through-holes were formed at equal intervals of 2 mm pitch, and as many substrates as possible could be formed in each of the 1000 through-holes for each condition, and a substrate with through-electrodes was manufactured. The same conductive paste as in Example 1 was used. The through-hole was filled with the conductive paste by using a screen printing machine while changing the protrusion height H as shown in Table 2. The protrusion height H 'of the conductive paste on the back side of the insulating base material was adjusted to 100 µm by adjusting the spacer of the screen printing machine. The conductive paste was heated and cured at 200 ° C. for 60 minutes using an electric oven, and then wrapped by changing the surface processing amount W of the insulating base material to obtain a substrate with through electrodes. At this time, insulation The amount of processing W 'on the back side of the substrate was set to 20 μΐη.

[0042] The resistance between both ends was measured for 1000 through electrodes under each condition. Table 2 shows the resistance evaluation results along with the manufacturing conditions (base material, protrusion height H, base material processing amount W). When the conductive base one strike of the projection height H is less than 50 mu m and, when the substrate processing amount W is less than 3 mu m is greater resistance than 2 X 10- ⁴ Ω cm in terms of the body volume resistivity Since the penetrating electrode showing 50% of the total penetrating electrodes was hot, it was evaluated as “impossible”. This is considered to be because the protruding height H of the conductive paste or the amount W of the base material was small, so that the region 36 having a low filler powder concentration remained inside the through electrode, and the resistance of the through electrode was increased. 50 and more protruding height H zm, 3 in the substrate with through electrodes combines both xm more Motozaika卩Eryou W, all the through electrodes in terms of volume resistivity 2 X 10- ⁴ Ω It showed a resistance of not more than cm, and it was confirmed that a through electrode having good electrical conduction was formed.

[Table 2]

Sample Substrate material Substrate thickness Through hole diameter Projection height Substrate processing amount Resistance evaluation

T (mm) Η () W (μ ιη) result

1 Alumina 1.0 0 5 0 3 8 1 0 Not possible

2 5 0 1 0 Good

3 8 1 1 0 Good

4 1 0 3 1 0 Good

5 7 3 2 .8 Not possible

6 7 1 5 Good

7 7 5 1 5 Good

8 6 8 2 5 Good

9 No power 0.7 .2 0 0 4 7 1 5 Not possible

1 0 Glass 6 1 1 5 Good

1 1 8 5 1 5 Good

1 2 1 0 5 2 5 Good

1 3 8 1 2 Not possible

1 4 8 2 3 Good

1 5 8 5 1 5 Good

1 6 8 1 2 5 Good

Three

Using an insulating substrate made of sintered alumina ceramic with a purity of 96% and a polyimide insulating substrate, the method of forming the through hole was changed to change the diameter of the through hole, and a substrate with a through electrode was manufactured. The through electrodes were evaluated. The alumina substrate was a 75 mm disk with a thickness of 0.6 mni, and the polyimide substrate was a 100 mm square square with a thickness of 1.5 mm. For the formation of through holes in the insulating base material, a carbon dioxide gas / one-piece processing machine was used for the alumina base material, and a punching machine using a punch was used for the polyimide base material. The through-holes were formed at equal intervals of 2 mm pitch, and as many substrates as possible were formed for each of the 1000 through-holes in each condition so that through-electrodes could be formed, and a substrate with through-electrodes was manufactured. The same conductive paste as in Example 1 was used. Through hole Use a screen printer to fill the strike, and project the filled conductive paste. Filling was performed so that both heights H and H 'were 100 μ μη. After the conductive paste is cured by heating by using an electric oven at 200 ° C 60 min, surface treatment amount W of the insulating base, W 'force S Rappuka卩E surface together so that the 20 _beta m Thus, a substrate with a through electrode was obtained.

The resistance between both ends was measured for 1000 through electrodes under each condition. Table 3 shows the resistance evaluation results together with the manufacturing conditions (base material, through-hole diameter). In the substrate having an alumina base material having a through hole diameter, than 2 X 10- ⁴ Ω cm in terms of volume resistivity of the through electrode shown a large listening resistance was 70% or more of all the through electrodes . Most of them were electrodes with no electrical conduction and could not be used as penetrating electrodes. This is presumably because the diameter of the through-hole was too small to fill the conductive paste uniformly. In addition, in the case of a substrate using a polyimide substrate having a through hole with a diameter of 900 zm, there was a through hole from which the paste dripped immediately after filling, and the conductive paste could not be stably filled. 30 mu in a substrate with through electrodes having a through-hole was 800 mu m to less diameter than m, all the through-electrode shown the conversion to the resistance of the following 2 X 10- ⁴ Ω cm volume resistivity, electrical Since it was confirmed that a through electrode having good conduction was formed, the evaluation was "good".

[Table 3]

Example 4

[0047] Using a non-alkali glass (# 1737 manufactured by Kojung) insulating base material, a through-hole is opened, and the material of the filler powder contained in the conductive paste filled in the through-hole and the shape and its flatness A substrate with a through electrode was manufactured by changing the uniform particle size, and the through electrode of the substrate was evaluated. The insulating base material was a 150 mm diameter disk with a thickness of 0.7 mm. After forming a resist mask on a glass substrate, shot blasting was applied to form a circular through hole having a diameter of 200 μηη. The through-holes were formed at equal intervals of 2 mm pitch, and as many substrates as possible were formed for each of the 1000 through-holes in each condition, and a substrate with a through-electrode was produced. The conductive paste is a mixture of bisphenol F-type epoxy resin (Epicoat 807 Yuka Shell Epoxy Co.) and epoxy resin obtained by esterifying dimer acid with darcidinole (epoxy equivalent: 400-50 Og / eq) as binder resin. The mixing ratio was adjusted such that the final viscosity of the conductive paste was 12OO-13OOPa-s (0.5¾O. 5RPS) at room temperature as evaluated by an E-type viscometer. Dicyandiamide (DICY7 Yuka Shell Epoxy Co., Ltd.) was used as a curing agent, and an anionic surfactant (manufactured by Daiichigo Daiichi Kogyo Co., Ltd.) was used as a dispersant. The hardener and the dispersant were added in an amount of 1.0% by mass and 0.3% by mass, respectively, relative to the conductive paste. Filler powders having different average particle diameters shown in Table 4 were used, and 90.5% by mass was added to the conductive paste. These binder resin and filler powder were stirred and kneaded while defoaming with a three-roll mill. The conductive paste was filled into the through holes using a screen printer so that the heights H and H 'of the filled conductive paste protrusions were both 100 μΐη. The conductive paste was cured by heating at 200 ° C. for 60 minutes using an electric oven. Both surfaces of the insulating substrate were wrapped so that the weights W and ′ of the insulating substrate were both 20 μm, to obtain a substrate with through electrodes.

The resistance between both ends was measured for 1000 through electrodes under each condition. The results of the resistance evaluation are shown in Table 4 together with the manufacturing conditions (filament powder type, average particle size) and the results of the heat cycle test described below. Average particle sizes of 1. 0 xm and less than flake off Ira one powder of spherical filler powder 3. When it is less than O zm, indicating the conversion to be large resistance Ri by 20 X 10_ ⁴ Q cm in volume resistivity The penetrating electrodes accounted for more than 70% of all penetrating electrodes. For these samples, the resistance evaluation result is “impossible”. This is considered to be due to the fact that the filler powder particles were small and the surface of the particles was covered with resin, resulting in less contact between the particles. In other specimen, all the through electrodes showed the conversion to the resistance of the following 2 X 10- ⁴ Ω cm volume resistivity, the electrical conduction are formed good through electrode was confirmed. These samples Indicates that the resistance evaluation result is “good”.

[Table 4]

[0050] In evaluation on the substrate with through electrodes volume resistivity is equal to or less than 2 X 10- ⁴ Q cm, between -55 ° C and 125 ° C held to between those temperatures, respectively 30 minutes A heat cycle test in which heating and cooling were repeated 1000 times was performed. 8. For the spherical filler powder having an average particle size larger than O zm and the flaked filler powder having an average particle size larger than 20 μm, the resistance increase by the heat cycle test was 3% or more. In such a large filler powder particle, the contact between particles is reduced, so that the reliability of the through electrode with respect to the thermal cycle is reduced. Average particle diameter 1.O xm or more 8. Spherical filler powder with O m or less and average particle diameter 3.0 With flake-like filler powder with β m or more and 20 μm or less, electrical conductivity is good at all electrodes. The resistance change in the heat cycle test was as good as 1% or less. As described above, the evaluation was “good”.

[0051] As described in Examples 1 to 4, the conductive paste is filled into the through holes so that the protruding height H from the surface of the insulating base material is 50 µm or more and 200 µm or less. Obtain an insulating base material with a thermosetting conductive paste, and grind or wrap the insulating base material with a thickness of 3 μm or more and 50 μm or less on one side to a thickness of 300 μm or more and 2 mm or less. When a substrate with a through-electrode was manufactured, the electrical conduction of all the through-electrodes was improved, and a change in resistance in a thermal cycle test was small. A substrate with a through electrode manufactured using the manufacturing conditions of the present invention and further changing the manufacturing conditions will be described below.

Example 5

[0052] Here, a substrate with through electrodes was manufactured using sintered alumina ceramics having a purity of 96% as an insulating base material. The insulating base material had a volume resistivity of 1 ^{× 10ΜΩ} << η and a disk having a diameter of 75 mm and a thickness of 1.0 mm. Circular through holes with a diameter of 150 / im were formed at equal intervals of 2 mm using a carbon dioxide laser processing machine. We used as many substrates as we could form through electrodes in 3000 through holes. The same conductive paste as in Example 1 was used. The conductive paste was filled into the through holes using a screen printer so that the conductive paste protrusion height H and H 'force S were both 100 µm. The conductive paste is cured by heating in an electric oven at 200 ° C for 60 minutes, and then the surface of the insulating substrate is lapped so that the processing amounts W and ^Wr are both 20 μm. A substrate with a through electrode having a thickness of 0.96 mm was obtained.

[0053] When measuring the resistance across the 3000 through-electrodes are converted to resistance of less 2 X 10- ⁴ Ω cm all the through electrodes on the body volume resistivity, electrical conduction is good penetration It was confirmed that the electrodes were formed.

Example 6

Here, a substrate with a through-electrode was manufactured using an alkali-free glass (# 1737 made by KINGING Co., Ltd.) insulating base material. The insulating base material had a volume resistivity of 3 × 10 ¹³ Q cm and was a 150 mm diameter disk with a thickness of 0.7 mm. After forming a photoresist mask on a glass substrate, shot blasting was applied to form through holes with a diameter of 200 μ μη at equal intervals of 2 mm pitch. As many substrates as possible were used to form through electrodes in 3000 through holes. The conductive paste is a bisphenol A-type epoxy resin (Epicoat 828 Yuka Shenore) as a binder resin. Epoxy) and an amine type epoxy resin (ELN-125, manufactured by Sumitomo Chemical Co., Ltd.) in a ratio of 1: 1 (mass ratio) are used, and an amine adduct-based curing agent (PN-23 Ajinomoto) is used as a curing agent. Polyoxyethylene sorbitan fatty acid ester (Nonionic surfactant "Solgen" TW Daiichi Kogyo Seiyaku Co., Ltd.) was used as a dispersant. The curing agent and the dispersant were added in an amount of 0.3% by mass and 0.2% by mass, respectively, in comparison with the conductive paste. As the filler powder, a powder obtained by coating silver on spherical copper particles having an average particle diameter of 4.9 μm prepared by a reduction method was used, and 91.0% by mass was added to the conductive paste. These binder resin and filler powder were stirred and kneaded while defoaming with three rolls. The viscosity of the mixed conductive paste was 1200 to 1300 Pa's (rotation speed: 0.5 RPS) as measured by an E-type viscometer at room temperature. The conductive paste was filled into the through holes using a screen printer so that the protrusion heights 導電 and Η ′ of the conductive paste protrusion were both 100 zm. The conductive paste is cured by heating it at 180 ° C for 60 minutes using an electric oven, and then lapping the surface of the insulating base material so that both processing amounts W and become 20 / im. A substrate with a through electrode having a thickness of 0.66 mm was obtained.

[0055] When measuring the resistance across the 3000 through-electrodes are converted to resistance of less 2 X 10- ⁴ Ω cm all the through electrodes on the body volume resistivity, electrical conduction is good penetration It was confirmed that the electrodes were formed.

Example 7

[0056] A substrate with a through electrode was manufactured using polyimide as an insulating base material. The insulating base material had a volume resistivity of l × 10 ¹⁶ Q cm, a square of 100 mm square and a thickness of 0.5 mm. Elliptical through holes with a short diameter of 130 µm and a long diameter of 180 µm were formed at equal intervals of 2 mm using a punching machine. We used as many substrates as we could form through electrodes in 3000 through holes. The conductive paste is composed of a bisphenol F-type epoxy resin (Epicoat 807 Yuka Shell Epoxy) and an epoxy resin obtained by glycidyl esterification of dimer acid (epoxy equivalent: 400-500 g / eq) as binder resin. : 3 (mass ratio), dicyandiamide (DICY7 manufactured by Yuka Shell Epoxy Co., Ltd.) as a curing agent, and an anionic surfactant (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as a dispersant. The curing agent and the dispersant were added in an amount of 1.0% by mass and 0.3% by mass, respectively, relative to the conductive paste. Filler powder Flake-shaped silver particles having an average particle diameter of 10.5 / m were used, and added in an amount of 90.3% by mass relative to the conductive paste. These binder resin and filler powder were stirred and kneaded while defoaming with three rolls. The viscosity of the kneaded conductive paste was 1300 to 1400 Pa's (rotation speed 0.5 RPS) as measured by an E-type viscometer at room temperature. The through-hole was filled with the conductive paste by using a screen printing machine so that the protruding portions Η and Η ′ of the filled conductive paste became 100 zm. The conductive paste is cured by heating in an electric oven at 200 ° C for 60 minutes, and then wrapping both surfaces of the insulating base material so that the processing amounts W and W 'are both 20 am. A substrate with a through electrode having a square and a thickness of 0.46 mm was obtained.

[0057] When measuring the resistance across the 3000 through-electrodes are converted to resistance of less 2 X 10- ⁴ Ω cm all the through electrodes on the body volume resistivity, electrical conduction is good penetration It was confirmed that the electrodes were formed.

Example 8

A substrate with a through electrode was manufactured using a glass-epoxy resin insulating base material. The insulation substrate has a volume resistivity of 200 _beta m to Aramido nonwoven epoxy sheet having a thickness in those piled six in 2 X 10 ^1Q Q cm, and a thickness of 1. 2 mm in square 120mm square. Circular through-holes with a diameter of 250 μm were formed at equal intervals of 2 mm pitch using a micro-drilling machine using an NC drill nozzle. As many base materials as possible were used to form through electrodes in 3000 through holes. The conductive paste used was a bisphenol A type epoxy resin (Epicoat 828 Yuka Shell Epoxy Co.) and an epoxy resin obtained by darcidyl esterifying dimer acid (epoxy equivalent: 400 500 g / eq) as binder resin. (Mass ratio), phthalic anhydride as a curing agent, and phosphoric acid ester (anionic surfactant "Blysurf" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a dispersant were used. The hardener and the dispersant were added in an amount of 2.8% by mass and 0.2% by mass, respectively, relative to the conductive paste. The filler powder used was a powder obtained by mixing spherical silver particles having an average particle diameter of 1 and flake silver particles having an average particle diameter of 11.2 μm in a ratio of 4: 6, and 89.7% by mass relative to the conductive paste. Was added. These binder resin and filler powder were stirred and kneaded while defoaming with three rolls. The viscosity of the kneaded conductive paste is 1200-1300 Pa's (rotational speed 0.5 RPS) as measured by an E-type viscometer at room temperature. Was. The through-hole was filled with the conductive paste using a screen printer so that the protruding portions Η and Η ′ of the protruding portion of the filled conductive paste were both 100 / m. The conductive paste is cured by heating in an electric oven at 200 ° C for 60 minutes, and then wrapping both surfaces of the insulating substrate so that the processing amounts W and W 'are both 30 xm. A substrate with a through electrode having a thickness of 1.14 mm was obtained.

[0059] When measuring the resistance across the 3000 through-electrodes are converted to resistance of less 2 X 10- ⁴ Ω cm all the through electrodes on the body volume resistivity, electrical conduction is good penetration It was confirmed that the electrodes were formed.

Example 9

[0060] Using a non-alkali glass (# 1737 made by Kohjung) insulating base material (a disk with a diameter of 150 mm and a thickness of 0.7 mm), a resist mask having holes with a diameter of 200 ± 10 μm was used as a glass insulating material. A hole was formed on the base material, and a hole reaching the opposite surface of the glass insulating base material by shot blasting was formed as a through hole. Shot blasting uses # 400- # 800 powder of silicon carbide or alumina, and by adjusting the injection pressure of the powder, the through-hole walls with different surface states were formed. The wall surface of the formed through hole had a height difference hO. 09-0.55 / im and a pitch of p4.0. The surface unevenness of the wall surface of the through hole was measured using a three-dimensional surface structure analysis microscope by cutting the glass insulating substrate along the center axis of the through hole. FIG. 4 is an enlarged sectional view of the through hole 12 formed in the glass insulating substrate 10. 3 shows a resist mask 90 having a through hole 91 on a glass insulating substrate 10 and a surface unevenness of a through hole wall surface 14 formed in the insulating substrate 10.

When a part of the through-hole wall surface 14 is shown in an enlarged manner, as shown in FIG. 5, the through-hole wall surface has a height difference (a difference in height between a peak and a valley) h, There is unevenness consisting of pitch p. The average particle size (average diameter) d of the spherical copper powder particles 31 which are the filler powder contained in the conductive paste is also shown in FIG.

[0062] Spherical copper powder particles (diameter distribution is about 0. 5 _beta m-about 13 mu m, an average diameter of about 4.2, 5.

The same conductive paste used in Example 4, which was kneaded with epoxy resin so that the three types of 1, 7.5 μΐη) was about 91% by mass, was used for the glass insulation with different surface irregularities on the wall surfaces of the through holes. The conductive paste was filled into the through holes by imprinting on the base material. Heat it at 200 ° C for 30 minutes After hardening the conductive paste, both sides of the base are polished by about 20 μΐη, including the hardened conductive paste projections that protrude about 100 μm from both ends of the glass insulating base material. A substrate with electrodes was manufactured.

Using the substrate 100 with the through-electrode thus manufactured, as shown in the plan view of FIG. 6 and the rear view of FIG. 7, a GMR element (giant magnetoresistive element) 50 On the other surface of the substrate, lead terminals 54 were formed so as to electrically connect to the through electrodes 30a, respectively, and then cut into the size of the GMR element 50 to obtain a glass wiring substrate. The average diameter d of the powder particles of the filler shown in Table 5, the height difference h of the unevenness of the through-hole wall surface, and the pitch p were changed. The frequency of occurrence of loosening of the penetrating electrode (including dropout during the process) in Table 2 is also shown in the same table.

[Table 5]

[0065] In Table 5, a sample in which at least one penetrating electrode slackened (dropped) occurred was judged as "impossible". Since each substrate has four through electrodes, the probability of failure of the substrate Is four times the rate of loosening. It is confirmed that a penetrating electrode with slack has a high electric resistance, which causes a problem in the characteristics of the GMR element and an unstable state in which the electric resistance value changes with each measurement. Not done. In Table 5, Samples C, D, H, and L with a slack occurrence rate of 0% that were judged as “good” had irregularities in the surface roughness of the through-hole wall surface with the average diameter d of the filler powder particles 31. The height h was 1Z20 or more, and the pitch p was equal to or more than the average diameter d of the filler powder particles 31. As a result, the filler powder particles 31 contained in the through-electrode are caught on the wall surface by the unevenness of the through-hole wall surface, and the solidified paste is fixed in the through-hole. It is considered to have been prevented.

Example 10

[0066] Using a non-alkali glass (# 1737 made by Kojung) insulating base material (a disk with a diameter of 150 mm and a thickness of 0.7 mm), a resist mask with a hole with a diameter of 200 ± 10 μm was used as a glass insulating material. It was formed on a substrate. Then, a through hole reaching the lower end surface of the glass insulating base material is formed by wet etching with a hydrofluoric acid chemical solution, and then a shot blast is performed at a certain angle with respect to the hole, so that a portion of the through hole wall surface is formed. An uneven portion was formed on the substrate. The height difference h of the formed concavo-convex part is 0.25-0.31 111, and the pitch is 6.1-9.8 μm. — Changed to 50%. The formed concavo-convex portion has a height difference h of 1Z20 or more of the average diameter d of the filler powder particles, and the pitch p thereof is equal to or more than the average diameter d. The ratio of 0% means that the shot blast is not performed only by wet etching. Example 4 in which spherical copper powder particles (diameter distribution was about 0.5 μm, about 10 μm, average diameter was about 5.1 μm) were kneaded with epoxy resin in the through-holes so as to be about 91% by mass. The same conductive paste as that used in (1) was imprinted on a glass insulating substrate, and the through-hole was filled with the conductive paste. Heat the paste at 200 ° C for 30 minutes to cure the paste, and then extend from both ends of the base, including the cured conductive paste protrusions that protrude about 100 xm from both ends of the glass insulating base. A substrate with a through electrode was manufactured by polishing 20 _βm .

[0067] Using the substrate 100 with the through-electrode thus manufactured, as shown in the plan view of FIG. 6 and the rear view of FIG. After forming the lead terminals 54 so as to electrically connect to the through electrodes 30a, the GMR element The glass wiring board was cut into a size of 50. The state of loosening of the penetrating electrode 30a that occurred during the process of forming the GMR element 50 on the substrate 100 was examined. 4 shows a graph showing the relationship between The substrate without shot blasting (roughness ratio 0%) had a slack occurrence rate of 68%, and at the unevenness ratio 18%, the slack occurrence rate was almost zero. If the unevenness ratio is 20% or more, the penetrating electrode will not fall out or move through the through-hole unless a direct force is applied to the penetrating electrode.However, considering the margin, the unevenness ratio should be 30% or more. It turns out to be good. Example 11

[0068] Using a non-alkali glass (# 1737 manufactured by Kojung) insulating base material (a disk with a diameter of 150mm and a thickness of 0.7mm), a through hole having a shape different from that of Examples 9 and 10 was provided. A substrate with a through electrode was fabricated. As shown by the two-dot chain line in Fig. 9, a resist mask 90 having a through hole 91 with a diameter of 200 ± 10 / m is placed on the glass insulating base material 10 and approximately 600 μm is shot blasted. A hole having a depth of m was formed, and by drilling the hole, the remaining portion was chipped to form the through hole 12. 8000 through holes were simultaneously formed on a glass insulating substrate. The opening diameter dl of the through hole 12 on one end surface 16 of the insulating base material 10 is 250 ± 40 Atm, the other side 18 has a small opening diameter, the side opening diameter d2 is 140 ± 40 ^ 111, and the minimum part 19 Had a diameter d3 of 80 120 xm. In all the through holes 12, the opening diameter d2 on the smaller side was larger than the diameter d3 of the minimum portion 19.

[0069] About 91% by mass of spherical copper powder particles (having a diameter distribution of about 1 µm to about 10 µm and an average diameter of about 7 µm) were used in Example 4 in which kneaded with an epoxy resin. The same conductive paste as that which was used was imprinted on a glass substrate, and the through-hole was filled with a conductive paste. Heat the paste at 200 ° C for about 30 minutes to cure the paste, and then from both surfaces of the base, including the cured conductive paste protrusions that protrude about 100 μm from both ends of the glass base. Polishing was performed at 20 zm to produce a substrate with through electrodes.

[0070] Using a glass substrate 100 having a diameter of 150 mm and having 8000 through electrodes formed in this way, as shown in the plan view of FIG. 6 and the rear view of FIG. The GMR element 50 was formed on the other surface of the substrate such that the lead terminals 54 were formed so as to have electrical connection to the through electrodes 30a, respectively, and then cut into the size of the GMR element 50 to obtain a glass wiring substrate. The handling during the forming process did not cause the penetration electrode 30a to fall off. In addition, in a conduction test of the through electrodes performed after this processing step, no conduction failure was observed.

[0071] Here, the minimum diameter d3 of the penetrating electrode is larger than eight times the average diameter of the copper powder particles contained in the penetrating electrode, that is, the average diameter of the filler particles, specifically 80 120 zm. This means that 95 to 227 powder particles exist in the minimum diameter, and the cross section of the other part of the through electrode has an area approximately equal to or larger than the area of the minimum diameter. Therefore, more filler powder particles are present. Also, it is probable that because the difference in diameter between the opening of the through hole and the minimum portion was not so large, the difference in shrinkage during heating and curing of the conductive paste was so large that there was no cutting due to shrinkage of the through electrode. For these reasons, it is considered that continuity was good in the energization test.

In this example, the diameter d3 of the minimum portion of the through hole was 80 120 μm, and the diameter d2 of the inlet on the small side was 140 ± 40 μm. It was less than 90% of the diameter d2. Since the difference between the inlet opening diameter d2 of the side and the diameter d3 of the extremely small part is large, the conductive paste is heated to about 200 ° C and cured. It was possible to prevent the through electrode from falling off or loosening. Example 12

FIG. 10 shows an enlarged cross-sectional view of a base material having a through hole having a different shape. The through hole 12 is formed with two holes 12 ′ and 12 ″ formed from each end face of the glass insulating base material 10, and the holes 12 ′ and 12 連 communicate inside the through hole 12. The center axes of the inlet openings on each end face are eccentric to each other, and in the example shown in this figure, the inlet opening diameter d4 of the large hole 12 'is about 300 xm and the small hole is The 12 mm inlet opening diameter d5 is about 150 zm, and their eccentricity is 100 μm, so the eccentricity is larger than the difference between their radii. In the through electrode of this embodiment, holes need to be formed from both end surfaces of the base material.

Industrial applicability

A through hole formed in an insulating base material is filled with a thermosetting conductive paste, and the surface of the substrate is processed after the thermosetting by an easy method that does not require a special device. A method for manufacturing a substrate with a through electrode, which can stably obtain a pole, can be provided.

Claims

The scope of the claims

[1] Open a through hole in the insulating substrate,

Filling the through hole with a thermosetting conductive paste, forming protrusions having a height of 50 μm and 200 μm from both ends of the through hole with the thermosetting conductive paste,

Heat-curing the thermosetting conductive paste,

Processing from both surfaces of the insulating base material including the protrusions of the thermosetting conductive paste to remove 3 / i m-50 μm on one side from the surface of the insulating base material

A method for manufacturing a substrate with through electrodes, comprising the steps of:

[2] The method for producing a substrate with a through electrode according to claim 1, wherein the insulating base material has a thickness of 300 µm-2 mm.

[3] The method for producing a substrate with a penetrating electrode according to claim 2, wherein the through hole formed in the insulating base material has a diameter of 30 µm to 800 µm.

[4] The method for producing a substrate with a through electrode according to any one of [13] to [13], wherein the height of the protrusion formed of the thermosetting conductive paste is 70 μm to 100 μm.

[5] The thermosetting conductive paste contains 85% to 93% by mass of a conductive filler powder having an average particle size of 1.0 μm to 20 _βm , and the balance is substantially a thermosetting binder resin. 3. The method for manufacturing a substrate with through electrodes as described in 3.

[6] The substrate with a through electrode according to claim 3, wherein the thermosetting conductive paste further contains 0.2% by mass to 3.0% by mass of a curing agent and 1.0% by mass or less of a dispersant. Production method.

7. The method for producing a substrate with through electrodes according to claim 5, wherein the conductive filler powder is spherical particles having an average particle diameter of 1.0 am 8.0 μm.

[8] The conductive filler powder is a flaky particle having an average particle size of 3.0 μm 20 μm.

5. The method for manufacturing a substrate with a through electrode according to 5.

9. The method for producing a substrate with a through electrode according to claim 5, wherein the thermosetting binder resin contains a liquid epoxy resin having two or more epoxy groups as a main component.

[10] The through-hole formed in the insulating base material has an average particle diameter of 1% or more of the filler powder particles contained in the thermosetting conductive paste to be filled with irregularities of the surface roughness in 30% or more of the inner wall surface of the through-hole. / 20 or more, and the pitch of the surface roughness is more than the average particle size 2. The method for producing a substrate with a through electrode according to claim 1, wherein:

[11] The through-hole formed in the insulating base material has a minimum value at the middle of both ends smaller than the diameter of each opening at both ends, and the minimum value is included in the thermosetting conductive paste to be filled. 2. The method for producing a substrate with through electrodes according to claim 1, wherein the average particle diameter of the filler powder particles is larger than eight times.

12. The method for producing a substrate with a through electrode according to claim 11, wherein the minimum value of the diameter of the through-hole is less than 90% of the opening diameter on the smaller side of the opening at both ends.

13. The method according to claim 12, wherein the minimum value of the diameter of the through hole is larger than 80 μm.

[14] The through-hole formed in the insulating base material may be such that the center axes of the openings at both ends thereof are eccentric to each other, and the amount of eccentricity is larger than the difference between the radii of both openings. The method for manufacturing a substrate with a through electrode described above.