TWI616475B - Resin sheet - Google Patents

Abstract

The present invention is a resin sheet for forming a wiring circuit board connectable to an electrode formed on a semiconductor wafer. The resin sheet is thermally hardened at 180 ° C for 1 hour, and is immersed at 20 ° C to 25 ° C. After 2400 seconds in methyl ethyl ketone at a temperature below 10 ° C, the weight reduction rate was 1.0% by weight or less.

Description

Resin sheet

The present invention relates to a resin sheet.

In recent years, among LSI packaging technologies, CSP (Chip Size / Scale Package) technology has attracted attention. Among this technology, WLP (Wafer Level Package) is one of the representative examples. It is a package in the form of a wafer that does not use a general circuit board, and has attracted attention in terms of miniaturization and high integration. As a manufacturing method of WLP, for example, a method in which a conductor portion of a printed circuit board corresponds to an electrode position of a semiconductor wafer and then the two are connected.

The above-mentioned printed circuit board has poor operability in manufacturing steps such as a chip package due to its flexible properties. Therefore, conventionally, as shown in Patent Documents 1, 2, and the like, the following method has been adopted: First, a flexible printed circuit board is formed on a supporting substrate, and the printed circuit board having an appropriate rigidity is formed. The operability is to perform wafer packaging in an improved state, and the supporting substrate is removed after the rigid body wafer is packaged.

Compared to bare crystals that only expose electrode pads A chip is a semiconductor device that has been packaged on a printed circuit board and the support substrate has been removed. It is a semiconductor device that has a connection with an external conductor (external circuit, etc.) or is packaged as a conductor for easy connection.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-349198

[Patent Document 2] Japanese Patent Laid-Open No. 2001-44589

The above-mentioned wiring circuit board can be used to manufacture conventionally known circuit boards or interposers such as the semi-additive process or the subtractive process for the base material of the base insulating layer formed on the support. Technology to make it happen. However, in such a method, since various solvents are used, the base insulating layer is expected to have high solvent resistance.

In order to solve the foregoing problems, the team of the present invention reviewed the resin sheet used to form the printed circuit board. As a result, it was found that the solvent resistance can be improved by employing the following constitution, and the present invention has been completed.

That is, the resin sheet according to the present invention is used to form A printed circuit board that can be connected to an electrode formed on a semiconductor wafer is characterized in that it is immersed in methyl ethyl ketone at a temperature of 20 ° C. to 25 ° C. for 2400 seconds after being thermally cured at 180 ° C. for one hour. The reduction rate is 1.0% by weight or less.

With the aforementioned configuration, after the resin sheet is thermally cured at 180 ° C for 1 hour, the resin sheet is immersed in methyl ethyl ketone at a temperature of 20 ° C to 25 ° C for 2400 seconds, and the weight reduction rate is 1.0% by weight or less. Since the weight reduction rate after immersion in methyl ethyl ketone at 20 ° C. to 25 ° C. for 2400 seconds is 1.0% by weight or less, it can be called p-methyl ethyl ketone to suppress elution. Therefore, as long as p-methyl ethyl ketone is used as the resin sheet which suppresses elution and has solvent resistance, a highly accurate printed circuit board can be manufactured.

In the aforementioned configuration, it is preferable that, after heat-curing at 180 ° C. for 1 hour, immersion in 0.5% by weight of hydrofluoric acid at a temperature of 20 ° C to 25 ° C for 60 seconds, the weight reduction rate is 1.0% by weight or less. In the production of the above-mentioned printed circuit board, an acid (for example, hydrofluoric acid) may be used. After heat curing, after immersing in 0.5% by weight of hydrofluoric acid at a temperature of 20 ° C to 25 ° C for 60 seconds, when the weight reduction rate is 1.0% by weight or less, it has more acid resistance. As a result, if the resin sheet is used, a printed circuit board with higher accuracy can be manufactured.

In the aforementioned configuration, it is preferable that the weight reduction rate is 1.0 weight after immersed in a 3.0% by weight aqueous solution of tetramethylammonium hydroxide for 20 seconds at a temperature of 20 ° C to 25 ° C for 1 hour after thermal curing at 180 ° C for 1 hour. %the following. In the manufacture of the above-mentioned printed circuit board, an alkali such as hydrogen is used. In the case of tetramethylammonium oxide aqueous solution). After heat curing, after being immersed in a 3.0% by weight aqueous solution of tetramethylammonium hydroxide at a temperature of 20 ° C to 25 ° C for 240 seconds, the weight reduction rate is 1.0% by weight or less, and alkali resistance is further enhanced. As a result, by using the aforementioned resin sheet, a printed circuit board with higher accuracy can be manufactured.

1‧‧‧ support

2‧‧‧ Wiring circuit board

20a‧‧‧Resin sheet (base insulating layer)

20b‧‧‧ Adhesive layer

21‧‧‧Conductor for connection

22‧‧‧Conductor for external connection

23‧‧‧conductor layer

23a‧‧‧ seed film

24‧‧‧ channel

25‧‧‧ channel

211‧‧‧metal film

3‧‧‧ semiconductor wafer

31‧‧‧electrode

4‧‧‧ semiconductor device

5‧‧‧ peeling layer

r1‧‧‧Photoresist

r2‧‧‧Photoresist

[Fig. 1] A cross-sectional simulation view of a resin sheet according to this embodiment.

[FIG. 2] A cross-sectional simulation view for explaining a method for manufacturing a semiconductor device according to this embodiment.

3 is a cross-sectional simulation diagram for explaining a method for manufacturing a semiconductor device according to this embodiment.

[FIG. 4] A cross-sectional simulation view for explaining a method for manufacturing a semiconductor device according to this embodiment.

[FIG. 5] A cross-sectional simulation view for explaining a method for manufacturing a semiconductor device according to this embodiment.

6 is a cross-sectional simulation diagram for explaining a method for manufacturing a semiconductor device according to this embodiment.

FIG. 7 is a cross-sectional simulation view for explaining a method for manufacturing a semiconductor device according to this embodiment.

[FIG. 8] A cross-sectional simulation view for explaining a method for manufacturing a semiconductor device according to this embodiment.

[Fig. 9] Illustrates the manufacture of a semiconductor device according to this embodiment Sectional simulation of the method.

[FIG. 10] A cross-sectional simulation view for explaining a method for manufacturing a semiconductor device according to this embodiment.

[FIG. 11] A cross-sectional simulation view for explaining a method for manufacturing a semiconductor device according to this embodiment.

[FIG. 12] A cross-sectional simulation view for explaining a method for manufacturing a semiconductor device according to this embodiment.

[Best Mode for Implementing Invention]

The embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to these examples. FIG. 1 is a cross-sectional simulation view of a resin sheet according to this embodiment. In this specification, parts that do not need to be explained are omitted in the drawings; for ease of explanation, there are parts that are illustrated by expanding or reducing, etc. However, the so-called "upper" and "lower" used in the present invention are used to indicate upper and lower words, and are only used to describe the positional relationship of the layers, and are not intended to limit the actual vertical posture of the printed circuit board or semiconductor device.

The resin sheet 20a (refer to FIG. 1) is a resin sheet for forming a wiring circuit board which can be connected to electrodes formed on a semiconductor wafer. A method of forming a printed circuit board using the resin sheet 20a or a method of manufacturing a semiconductor device using the printed circuit board will be described in detail using FIGS. 2 to 12 described later.

The resin sheet 20a was thermally cured at 180 ° C for 1 hour, and then After being immersed in methyl ethyl ketone at 20 ° C. to 25 ° C. for 2400 seconds, the weight reduction rate was 1.0% by weight or less. The weight reduction rate after immersion in methyl ethyl ketone is preferably 0.8% by weight or less. The smaller the weight reduction rate after immersion in methyl ethyl ketone, the better, for example, 0% by weight or more and 0.01% by weight or more. Since the weight reduction rate after immersion in methyl ethyl ketone at 20 ° C. to 25 ° C. for 2400 seconds is 1.0% by weight or less, it can be called p-methyl ethyl ketone to suppress elution. Therefore, as long as p-methyl ethyl ketone is used as the resin sheet 20a which suppresses elution and has solvent resistance, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing.

After the resin sheet 20a is thermally hardened at 180 ° C for 1 hour, it is preferably immersed in 0.5% by weight hydrofluoric acid at a temperature of 20 ° C to 25 ° C for 60 seconds. The weight reduction rate is preferably 1.0% by weight or less, and more preferably It is 0.8% by weight or less, and more preferably 0.6% by weight or less. The lower the weight reduction rate after immersion in 0.5% by weight of hydrofluoric acid, the better, for example, 0% by weight or more and 0.01% by weight or more. An acid (for example, hydrofluoric acid) is used in the manufacture of a printed circuit board. After heat curing, after immersing in 0.5% by weight of hydrofluoric acid at a temperature of 20 ° C to 25 ° C for 60 seconds, if the weight reduction rate is 1.0% by weight or less, it has more acid resistance. As a result, a printed circuit board with higher accuracy can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing.

The resin sheet 20a was thermally cured at 180 ° C for 1 hour, and then After 240 seconds of immersion in a 3.0% by weight tetramethylammonium hydroxide aqueous solution at a temperature of 20 ° C to 25 ° C, the weight reduction rate is preferably 1.0% by weight or less, more preferably 0.8% by weight or less, and still more preferably 0.6. % By weight or less. The lower the weight reduction rate after immersion in a 3.0% by weight tetramethylammonium hydroxide aqueous solution, the better, for example, 0% by weight or more and 0.01% by weight or more. An alkali (for example, a tetramethylammonium hydroxide aqueous solution) is used in the manufacture of a printed circuit board. After thermosetting, after being immersed in a 3.0% by weight tetramethylammonium hydroxide aqueous solution at a temperature of 20 ° C to 25 ° C for 240 seconds, if the weight reduction rate is 1.0% by weight or less, it has more alkali resistance. As a result, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing.

The resin sheet 20a was heat-cured at 180 ° C for 1 hour, and then SC-1 (composed of a weight ratio of ammonia water (15% by weight)) was immersed at 20 ° C to 80 ° C: hydrogen peroxide: water = 1: After 100 seconds in 2: 5), the weight reduction rate is preferably 1.0% by weight or less, more preferably 0.8% by weight or less, and still more preferably 0.6% by weight or less. The smaller the weight reduction rate, the better, for example, from 0% by weight to 0.01% by weight. SC-1 may be used in the cleaning step of the printed circuit board. When the aforementioned weight reduction rate is 1.0% by weight or less, it is more resistant to SC-1. As a result, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing.

The resin sheet 20a was thermally hardened at 180 ° C for 1 hour, and then SC-2 (composed of a weight ratio of hydrochloric acid (38% by weight)) was immersed in a temperature ratio of 20 ° C to 80 ° C: hydrogen peroxide: water = 1: 2: 160) After 160 seconds, the weight reduction rate is preferably 1.0% by weight or less, more preferably 0.8% by weight or less, and still more preferably 0.6% by weight or less. The smaller the weight reduction rate, the better, for example, from 0% by weight to 0.01% by weight. SC-2 may be used in the cleaning step of the printed circuit board. When the aforementioned weight reduction rate is 1.0% by weight or less, the SC-2 is more resistant. As a result, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing.

The resin sheet 20a is thermally hardened at 180 ° C for 1 hour, and then immersed in 30% by weight hydrogen peroxide water at a temperature of 20 ° C to 80 ° C for 840 seconds. The weight reduction rate is preferably 1.0% by weight or less, more preferably 0.8% by weight or less, and more preferably 0.6% by weight or less. The smaller the weight reduction rate, the better, for example, from 0% by weight to 0.01% by weight. In the manufacture of printed circuit boards, hydrogen peroxide water is sometimes used. When the aforementioned weight reduction rate is 1.0% by weight or less, it is more resistant to hydrogen peroxide water. As a result, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing.

The resin sheet 20a is thermally hardened at 180 ° C for 1 hour, and then immersed in a degreasing solution (alkaline, water-soluble, non-water-soluble) at a temperature of 20 ° C to 80 ° C. After 300 seconds in a water-soluble solvent, a surfactant, etc.), the weight reduction rate is preferably 1.0% by weight or less, more preferably 0.8% by weight or less, and still more preferably 0.6% by weight or less. The smaller the weight reduction rate, the better, for example, from 0% by weight to 0.01% by weight. In the manufacture of a printed circuit board, a degreasing solution may be used. When the aforementioned weight reduction rate is 1.0% by weight or less, it is more resistant to a solution for degreasing. As a result, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing. Examples of the degreasing solution include Rapid clean P-1000 manufactured by JX Nippon Mining & Metals.

The resin sheet 20a is heat-cured at 180 ° C for 1 hour, and then immersed in a 70% by weight aqueous nitric acid solution at a temperature of 20 ° C to 80 ° C for 30 seconds. The weight reduction rate is preferably 1.0% by weight or less, more preferably 0.8 It is not more than 0.6% by weight, and more preferably not more than 0.6% by weight. The smaller the weight reduction rate, the better, for example, from 0% by weight to 0.01% by weight. In the manufacture of a printed circuit board, a degreasing solution may be used. When the aforementioned weight reduction rate is 1.0% by weight or less, it is more resistant to a solution for degreasing. As a result, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing.

The resin sheet 20a is thermally hardened at 180 ° C for 1 hour, and then immersed in a plating pretreatment liquid (composition: having gold After 30 seconds in an alkaline aqueous solution of a salt), the weight reduction rate is preferably 1.0% by weight or less, more preferably 0.8% by weight or less, and still more preferably 0.6% by weight or less. The smaller the weight reduction rate, the better, for example, from 0% by weight to 0.01% by weight. In the manufacture of a printed circuit board, a zincate solution is sometimes used. When the weight reduction rate is 1.0% by weight or less, the zinc salt solution is more resistant. As a result, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing. Examples of the zincate solution include SUPERZINCATEPROCESS S ZII manufactured by JX Nippon Mining & Metals.

The resin sheet 20a is thermally hardened at 180 ° C for 1 hour, and then immersed in a nickel plating solution (composition: nickel sulfate, sodium hypophosphite, organic acid, etc.) at 20 ° C to 80 ° C for 1800 seconds. The weight reduction rate is preferably 1.0% by weight or less, more preferably 0.8% by weight or less, and still more preferably 0.6% by weight or less. The smaller the weight reduction rate, the better, for example, from 0% by weight to 0.01% by weight. In the manufacture of a printed circuit board, a nickel plating solution may be used. When the weight reduction rate is 1.0% by weight or less, the nickel-plating solution is more resistant. As a result, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing. Examples of the nickel plating solution include KG-535-0: KG-535-1 = 3: 1 manufactured by JX Nippon Mining & Metals.

The resin sheet 20a is thermally hardened at 180 ° C for 1 hour, and then immersed in a gold plating solution (composition: phosphoric acid compound, sulfurous acid compound, amine compound, etc.) at a temperature of 20 ° C to 80 ° C for 1200 seconds. It is preferably 1.0% by weight or less, more preferably 0.8% by weight or less, and still more preferably 0.6% by weight or less. The smaller the weight reduction rate, the better, for example, from 0% by weight to 0.01% by weight. In the manufacture of a printed circuit board, a nickel plating solution may be used. When the weight reduction rate is 1.0% by weight or less, the nickel-plating solution is more resistant. As a result, a highly accurate printed circuit board can be manufactured. The aforementioned weight reduction rate can be reduced by reducing the content of the elastomer, using a resin having a high glass transition temperature, or increasing the crosslinking density after heat curing. Examples of the gold plating solution include CF-500SS manufactured by JX Nippon Mining & Metals.

With respect to the resin sheet 20a, the glass transition temperature after thermal curing at 180 ° C for 1 hour is preferably 100 ° C or higher, more preferably 110 ° C or higher, and even more preferably 120 ° C or higher. By having such a structure, the resin sheet 20a can effectively exhibit characteristics such as solvent resistance, acid resistance, and alkali resistance.

The resin composition forming the resin sheet 20a is not particularly limited as long as it has the characteristics as described above and can be used to form a wiring circuit board that can be connected to electrodes formed on a semiconductor wafer. Examples thereof include epoxy resin compositions containing the following A component to E component. However, the C component is added as required, and may or may not be added.

Component A: epoxy resin

Component B: phenol resin

Component C: Elastomer

Component D: inorganic filler

Component E: Hardening accelerator

(A component)

The epoxy resin (component A) is not particularly limited. For example, a triphenylmethane type epoxy resin, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a modified bisphenol A type epoxy resin, and a bisphenol A ring can be used. Epoxy resin, bisphenol F-type epoxy resin, denatured bisphenol F-type epoxy resin, dicyclopentadiene-type epoxy resin, phenol novolac type epoxy resin, phenoxy resin And other various epoxy resins. These epoxy resins can be used alone or in combination of two or more.

From the viewpoint of ensuring the toughness of the epoxy resin after curing and the reactivity of the epoxy resin, those having an epoxy equivalent weight of 150 to 250, a softening point or melting point of 50 to 130 ° C, and a solid shape at room temperature are preferred. Among them, from the viewpoint of reliability, triphenylmethane type epoxy resin, cresol novolac type epoxy resin, and biphenyl type epoxy resin are preferred.

From the viewpoint of low stress, a modified bisphenol A epoxy resin having a flexible skeleton such as an acetal group or a polyoxyalkylene group; and a modified bisphenol A having an acetal group are preferred. Type epoxy resin, because it is liquid and operates well, it is particularly suitable for use.

The content of the epoxy resin (component A) is preferably set to a range of 1 to 10% by weight based on the entire epoxy resin composition.

(Component B)

The phenol resin (component B) is not particularly limited as long as it is capable of curing between epoxy resin (component A) and epoxy resin (component A). For example, a phenol novolac resin, a phenol aralkyl resin, a biphenylaralkyl resin, a dicyclopentadiene type phenol resin, a cresol novolac resin, a resol resin, and the like can be used. These phenol resins can be used alone or in combination of two or more.

As a phenol resin, from the viewpoint of reactivity with epoxy resin (component A), it is preferable to use a hydroxyl equivalent of 70 to 250 and a softening point of 50 to 110 ° C. Among them, the hardening reactivity is From a high viewpoint, a phenol novolac resin can be suitably used. From the viewpoint of reliability, those having low hygroscopicity such as a phenol aralkyl resin or a biphenyl aralkyl resin can be suitably used.

From the viewpoint of curing reactivity, the blending ratio of the epoxy resin (component A) and the phenol resin (component B) is preferably 1 equivalent to the epoxy group in the epoxy resin (component A). The resin (component B) is blended so that the total amount of hydroxyl groups becomes 0.7 to 1.5 equivalents, and more preferably 0.9 to 1.2 equivalents.

(C component)

Simultaneous use with epoxy resin (component A) and phenol resin (component B) Elastomer (C component) is the one that gives the epoxy resin composition the required flexibility (embedding property) for the adherend, and it is not particularly required as long as it can perform such an action. Define the structure. Various acrylic copolymers such as polyacrylates, styrene acrylate copolymers, butadiene rubber, styrene-butadiene rubber (SBR), ethylene-vinyl acetate copolymer (EVA), Rubber polymers such as pentadiene rubber and acrylonitrile rubber. Among them, since the epoxy resin (component A) is easily dispersed and the reactivity with the epoxy resin (component A) is high, the heat resistance or strength of the obtained resin sheet 20a can be improved from the viewpoint of In other words, an acrylic copolymer is preferably used. These are used singly or in combination of two or more kinds.

The acrylic copolymer can be synthesized by, for example, polymerizing an acrylic monomer with a predetermined mixing ratio by radical polymerization.

As a method of radical polymerization, a solution polymerization method using an organic solvent as a solvent, or a suspension polymerization method in which polymerization is performed while dispersing a raw material monomer in water can be used. As the polymerization initiator used at this time, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2 '-Azobis-4-methoxy-2,4-dimethylvaleronitrile, other azo- or diazo-based polymerization initiators, benzamidine peroxide and methyl ethyl ketone peroxidation And other peroxide-based polymerization initiators. In the case of suspension polymerization, it is preferable to add a dispersant such as polyacrylamide and polyvinyl alcohol.

The content of the elastomer (component C) is preferably 15 to 30% by weight of the entire epoxy resin composition. If the content of the elastomer (C component) is When it is 15% by weight or more, the flexibility and flexibility of the resin sheet 20a are easily obtained. On the other hand, when the above-mentioned content is 30% by weight or less, reduction in strength and heat resistance of the hardened body of the resin sheet 20a can be suppressed.

The weight ratio of the elastomer (C component) to the epoxy resin (A component) (weight of component C / weight of component A) is preferably set in a range of 3 to 4.7. When the weight ratio is 3 or more, it is easy to control the fluidity of the resin sheet 20a, and when it is 4.7 or less, the adhesiveness of the resin sheet 20a can be made good.

(D component)

The inorganic filler (component D) is not particularly limited, and various conventionally known fillers can be used. Examples include quartz glass, talc, silica (fused silica or crystalline silica), alumina, aluminum nitride, and nitrogen. Siliconized powder. These can be used alone or in combination of two or more.

Among these, silica powder is preferably used from the viewpoints of solvent resistance, acid resistance, and alkali resistance, and fused silica powder is preferably used among the silica powders. Examples of the fused silica powder include spherical fused silica powder and crushed fused silica powder. From the viewpoint of fluidity, it is preferable to use spherical fused silica powder. Among these, it is preferable to use the range whose average particle diameter is 0.1-30 micrometers, and it is especially preferable to use the range which is 0.3-15 micrometers.

The average particle diameter can be derived by using a sample arbitrarily drawn from the mother population and measuring it using a laser diffraction scattering type particle size distribution measuring device.

The content of the inorganic filler (component D) is preferably epoxy The entire resin composition is 70 to 95% by weight, more preferably 72 to 93% by weight, and still more preferably 75 to 90% by weight. By setting the content of the inorganic filler (component D) to 70% by weight or more, solvent resistance, acid resistance, and alkali resistance can be improved. On the other hand, by setting the above-mentioned content to 90% by weight, it is possible to suppress deterioration in the flexibility or fluidity of the resin sheet 20a.

(E component)

The hardening accelerator (component E) is not particularly limited as long as it can harden the epoxy resin and the phenol resin, but in terms of hardenability and storage stability, triphenylphosphine or tetraphenyl is suitable. Organophosphorus compounds or imidazole compounds such as perylene tetraphenylborate. These hardening accelerators may be used alone or in combination with other hardening accelerators.

The content of the hardening accelerator (component E) is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total of the epoxy resin (component A) and the phenol resin (component B).

(Other ingredients)

In addition, in addition to the A component to the E component, a flame retardant component may be added to the epoxy resin composition. As the flame retardant composition, various metal hydroxides such as aluminum hydroxide, magnesium hydroxide, iron hydroxide, calcium hydroxide, tin hydroxide, and composite metal hydroxide can be used. From the viewpoint of the point that the flame retardancy can be exhibited in a small amount or the cost, it is preferable to use aluminum hydroxide or magnesium hydroxide, and it is particularly preferable to use aluminum hydroxide.

From the viewpoint of ensuring an appropriate fluidity when heating the epoxy resin composition, the average particle diameter of the metal hydroxide is preferably 1 to 10 μm, and more preferably 2 to 5 μm. When the average particle diameter of the metal hydroxide is less than 1 μm, it becomes difficult to uniformly disperse the epoxy resin composition. At the same time, the fluidity of the epoxy resin composition tends to be insufficient when it is heated. . When the average particle diameter exceeds 10 μm, the surface area per unit addition amount of the metal hydroxide (component E) becomes small, and therefore, the flame retardancy effect tends to decrease.

As the flame retardant component, a phosphazene compound can be used in addition to the above-mentioned metal hydroxide. As the phosphazene compound, commercially available products such as SPR-100, SA-100, SP-100 (the above are Otsuka Chemical Co., Ltd.), FP-100, FP-110 (the above are Fushimi Pharmaceutical Co., Ltd.) )Wait.

From the viewpoint of exhibiting a flame-resistant effect even in a small amount, the phosphazene compound represented by the formula (1) or the formula (2) is preferred, and the content rate of the phosphorus element contained in these phosphazene compounds, It is preferably 12% by weight or more.

(In the formula (1), n is an integer of 3 to 25, R ¹ and R ² may be the same or different, and have a member selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group, and an allyl group. Functional group of the group is a monovalent organic group).

(In formula (2), n and m are each independently an integer of 3 to 25, R ³ and R ⁵ may be the same or different, and have a group selected from alkoxy, phenoxy, amine, hydroxy, and alkoxy A functional group is a monovalent organic group of a propyl group, and R ⁴ is a divalent organic group having a functional group selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group, and an allyl group. base).

From the viewpoints of stability and suppression of void generation, it is preferable to use a cyclic phosphazene oligomer represented by the formula (3).

(In formula (3), n is an integer of 3 to 25, and R ⁶ and R ⁷ are the same or different hydrogen, hydroxyl, alkyl, alkoxy, or glycidyl).

As the cyclic phosphazene oligomer represented by the above formula (3), commercially available products can be obtained, for example, FP-100, FP-110 (the above is Fushimi Pharmaceutical Co., Ltd.) and the like.

The content of the phosphazene compound is preferably the epoxy resin (component A), phenol resin (component B), elastomer (component D), and hardening accelerator (component E) contained in the epoxy resin composition. And 10-30% by weight of the entire organic component of the phosphazene compound (other components). That is, when the content of the phosphazene compound is less than 10% by weight of the entire organic component, it is found that the flame retardancy of the resin sheet 20a tends to decrease. When the content exceeds 30% by weight of the entire organic component, self-adhesion tends to occur on the surface of the resin sheet 20a, and workability tends to decrease.

In addition, by using the metal hydroxide and the phosphazene compound in combination, it is possible to obtain a resin sheet 20a having excellent flame resistance while ensuring the flexibility required for sealing the sheet. By using both in combination, sufficient flame retardance can be obtained when only a metal hydroxide is used, and sufficient flexibility can be obtained when only a phosphazene compound is used.

When the content of both the metal hydroxide and the phosphazene compound is used in combination, the total amount of the two components is preferably 70 to 90% by weight of the entire epoxy resin composition, and more preferably 75 to 85% by weight. When the total amount is less than 70% by weight, it is difficult to obtain sufficient flame retardancy of the resin sheet 20a, and when it exceeds 90% by weight, self-adhesion tends to occur on the surface of the resin sheet 20a, and workability is found There is a tendency to decrease.

In addition, in addition to the above components, the epoxy resin composition may be appropriately blended with carbon black-based pigments and other additives as required.

(Production method of resin sheet)

A method for producing the resin sheet 20a will be described below. First, an epoxy resin composition is prepared by mixing the above components. The mixing method is not particularly limited as long as the components can be dispersed and mixed uniformly. After that, for example, a varnish in which each component is dissolved or dispersed in an organic solvent is applied to form a sheet. Alternatively, the kneaded product can be prepared by kneading the various blends with a direct kneader or the like, and the kneaded product obtained in this way can also be formed into a sheet shape after extrusion.

As a specific production procedure using a varnish, the varnish is prepared by appropriately mixing the above-mentioned A to E components and other additives required in accordance with a conventional method, and uniformly dissolving or dispersing in an organic solvent. Then, the above-mentioned varnish is applied to a support such as polyester and dried to obtain a resin sheet 20a. If necessary, in order to protect the surface of the resin sheet 20a, a release sheet such as a polyester film may be bonded.

The organic solvent is not particularly limited, and various conventionally known organic solvents such as methyl ethyl ketone, acetone, cyclohexanone, dioxane, diethyl ketone, toluene, and ethyl acetate can be used. These can be used alone or in combination of two or more. In addition, it is generally preferable to use an organic solvent in a range where the solid content concentration of the varnish is 30 to 60% by weight.

The thickness of the sheet after the organic solvent is dried is not particularly limited, However, from the viewpoint of the uniformity of the thickness and the amount of the residual solvent, it is usually preferably set to 5 to 100 μm, and more preferably 20 to 70 μm.

On the other hand, in the case of using kneading, the above-mentioned A to E components and other components of other additives corresponding to the needs are mixed using a known method, and then the kneaded product is prepared by melt kneading. The method of melt-kneading is not particularly limited, but examples thereof include a method of melt-kneading by a known kneader such as a mixing roll, a pressure kneader, and an extruder. As the kneading conditions, the temperature is not particularly limited as long as it is above the softening point of each of the components, for example, 30 to 150 ° C. When considering the thermosetting properties of the epoxy resin, it is preferably 40 to 140 ° C, and more preferably 60. ~ 120 ° C; time is, for example, 1 to 30 minutes, preferably 5 to 15 minutes. Therefore, a kneaded material can be prepared by this.

The obtained kneaded material is formed by extrusion molding to obtain a resin sheet 20a. Specifically, the resin sheet 20a can be formed by extrusion molding without cooling the kneaded material after the melt-kneading and keeping it at a high temperature. The extrusion method is not particularly limited, and examples thereof include a T-die extrusion method, a roll calendering method, a roll kneading method, a coextrusion method, and a calendering method. There is no particular limitation on the extrusion temperature as long as it is above the softening point of each of the above components. When considering the thermosetting and moldability of the epoxy resin, for example, 40 to 150 ° C, preferably 50 to 140 ° C, more It is preferably 70 to 120 ° C. In this way, the resin sheet 20a can be formed.

The resin sheet 20a obtained in this way can be used by laminating it to a desired thickness as required. That is, the resin sheet 20a may be used in a single-layer structure, or may be used as a laminate having a multilayer structure in which two or more layers are laminated.

(Manufacturing method of semiconductor device)

An example of a method for manufacturing a semiconductor device according to this embodiment will be described in detail below with reference to FIGS. 2 to 12. 2 to 12 are cross-sectional simulation diagrams illustrating a method for manufacturing a semiconductor device according to this embodiment.

[Preparation of support with release layer]

First, the support body 1 is prepared (refer to FIG. 2). The support 1 preferably has a certain strength or more.

The support 1 is not particularly limited, but examples include compound wafers such as silicon wafers, SiC wafers, and GaAs wafers, glass wafers, SUS, 6-4Alloy, metal foils such as Ni foil, and Al foil. . When the plan view is a circle, a silicon wafer or a glass wafer is preferred. When the plan view is square, a SUS plate or a glass plate is preferred.

In addition, as the support 1, for example, low-density polyethylene, linear polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer polypropylene, and block copolymer polypropylene may be used. , Polypropylene such as polypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer, ionomer polymer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid Polymers of ester (random, interactive) copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, polyurethanes, polyethylene terephthalate, polyethylene naphthalate, etc. Ester, polycarbonate, polyimide, polyetheretherketone, polyimide, polyetherimide, polyimide, fully aromatic polyimide, polyphenylene sulfide, aromatic polyimide (paper ), Glass, glass Cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, paper, etc.

The support 1 may be used alone or in combination of two or more kinds. The thickness of the support is not particularly limited, but it is usually about 10 μm to 20 mm, for example.

Next, a release layer 5 is formed on the support 1.

The peeling layer 5 is preferably immersed in N-methyl-2-pyrrolidone (NMP) at 50 ° C for 60 seconds and dried at 150 ° C for 30 minutes. The weight reduction rate is preferably 1.0% by weight or more, more preferably It is 1.2% by weight or more, and more preferably 1.3% by weight or more. The larger the weight reduction rate, the better, for example, 50% by weight or less and 30% by weight or less. Since the weight reduction rate after being immersed in N-methyl-2-pyrrolidone (NMP) at 50 ° C for 60 seconds and drying at 150 ° C for 30 minutes was 1% by weight or more, the release layer 5 was eluted to In N-methyl-2-pyrrolidone, this indicates that the weight is sufficiently reduced. As a result, the release layer 5 can be easily peeled by N-methyl-2-pyrrolidone. The aforementioned weight reduction rate of the release layer 5 can be controlled, for example, by the solubility of NMP to the raw material. That is, the more the solubility of NMP as the raw material is selected, the higher the solubility of the release layer obtained after using the raw material for NMP.

The dynamic hardness of the release layer 5 is preferably 10 or less, more preferably 9 or less, and even more preferably 8 or less. The smaller the dynamic hardness, the better, for example, 0.001 or more. When the aforementioned dynamic hardness is 10 or less, the adhesive force of the peeling layer 5 to the adherend can be made sufficient.

The surface hardness of the release layer 5 is preferably 10 GPa or less, and more It is preferably 8 GPa or less, and even more preferably 6 GPa or less. The surface hardness is preferably as small as possible, for example, 0.05 GPa or more. When the aforementioned surface hardness is 10 GPa or less, the adhesion between the peeling layer 5 and the adherend can be controlled.

After peeling the layer 5 and immersing it in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes, the weight reduction rate is preferably less than 1% by weight, more preferably less than 0.9% by weight, and even more preferably less than 0.8% by weight. %. The smaller the weight reduction rate, the better, for example, from 0% by weight to 0.001% by weight. If it is immersed in a 3% tetramethylammonium hydroxide aqueous solution for 5 minutes, and the weight reduction rate is less than 1% by weight, it will be less dissolved in the 3% tetramethylammonium hydroxide aqueous solution, so the solvent resistance can be improved. Resistance (especially solvent resistance to tetramethylammonium hydroxide aqueous solution). The aforementioned weight reduction rate of the release layer 5 can be controlled, for example, by the composition of the diamine used (the solubility of the diamine in the tetramethylammonium hydroxide aqueous solution).

When the peeling layer 5 is adhered to the silicon wafer and peeled off, the increase in the number of particles of 0.2 μm or more on the surface of the silicon wafer is preferably less than 1,000 / 6-inch wafers, preferably less than 900 / 6-inch wafers, and even more preferably less than 800 / 6-inch wafers. When the silicon wafer is adhered and peeled off, the increase in the number of particles of 0.2 μm or more on the silicon wafer surface can be compared with that of less than 1000 / 6-inch wafers before being adhered to the silicon wafer. Suppresses adhesive residue after peeling.

The peeling adhesion force of the peeling layer 5 for a silicon wafer maintained at that temperature for 1 minute at 200 ° C. is preferably 0.25 kg / 5 × 5 mm or more, more preferably 0.30 kg / 5 × 5 mm or more, and more It is preferably 0.50kg / 5 × 5mm or more. The release layer 5 is maintained at a temperature of more than 200 ° C and at a temperature of 500 ° C. The shearing force of the silicon wafer after 3 minutes at any temperature in the temperature range below ℃ is preferably less than 0.25kg / 5 × 5mm, more preferably less than 0.10kg / 5 × 5mm, Still more preferably, it is less than 0.05 kg / 5 × 5 mm. When the shear adhesive force for a silicon wafer maintained at 200 ° C for 1 minute at that temperature is 0.25kg / 5 × 5mm or more, for any temperature in the temperature range maintained above 200 ° C and below 500 ° C When the shear adhesion force of the silicon wafer is kept below 0.25 kg / 5 × 5 mm at the temperature maintained for 3 minutes, the peeling layer 5 exhibiting peelability at a higher temperature can be obtained. The aforementioned shearing force of the release layer can be controlled, for example, by the number of functional groups contained in the release layer.

In addition, the shear adhesive force of the peeling layer on the silicon wafer is less than 0.25kg / 5 × 5mm (preferably less than 0.10kg / 5 × 5mm, more preferably 0.05kg / 5 × 5mm). The temperature is not particularly limited as long as it exceeds 200 ° C. and is in a temperature range of 500 ° C. or lower, but is preferably more than 220 ° C. and 480 ° C., and more preferably more than 240 ° C. and 450 ° C. or lower.

In addition, even if the peeling layer is 200 ° C. or lower, the shear adhesive force on the silicon wafer may be less than 0.25 kg / 5 × 5 mm when the peeling layer is held for a long time. In addition, even if the peeling layer is maintained at a temperature greater than 200 ° C., if the peeling layer is kept for a short period of time, the shear adhesive force to the silicon wafer may not be less than 0.25 kg / 5 × 5 mm.

That is, "for holding the silicon wafer with a shear adhesive force of less than 0.25 kg / 5 x 5 mm at any temperature in a temperature range of more than 200 ° C and less than 500 ° C for 3 minutes at that temperature" was evaluated as high temperature. Peeling Standard, but if it is set to "any temperature in a temperature range greater than 200 ° C and less than 500 ° C", it does not mean that the shear adhesive force on the silicon wafer will immediately become less than 0.25kg / 5 × 5mm. Moreover, it does not mean that it must be set to "any temperature in a temperature range higher than 200 ° C and less than 500 ° C" in order to exhibit the meaning of peelability.

The release layer 5 can be immersed in N-methyl-2-pyrrolidone (NMP) at 50 ° C for 60 seconds and dried at 150 ° C for 30 minutes. The weight reduction rate can be 1.0% by weight or more. The forming material is not particularly limited, and examples thereof include polyimide resin, polysiloxane resin, acrylic resin, fluororesin, epoxy resin, urethane resin, and rubber resin.

The polyfluorene imine resin is generally obtained by subjecting the precursor polyamic acid to fluorination (dehydration condensation). As a method for the polyamidation of polyimide, for example, a conventionally well-known heating method, an azeotropic dehydration method, a chemical method, and the like can be used. Among them, the heating method is preferred. If the heating method is used, in order to prevent the deterioration caused by the oxidation of the polyfluorene resin, it is preferable to perform the heat treatment in an inert environment such as a nitrogen environment or a vacuum.

The polyamic acid can be obtained by filling the acid anhydride and diamine in a substantially equal molar ratio in a suitable solvent.

The polyfluorene imine resin preferably has a constituent unit derived from a diamine having an ether structure. The diamine having an ether structure is a compound having an ether structure and is not particularly limited as long as it is a compound having at least two terminals having an amine structure. Among the aforementioned diamines having an ether structure, A diamine having an ethylene glycol skeleton is preferred. When the aforementioned polyfluorene imine resin has a constituent unit derived from a diamine having an ether structure, particularly a constituent unit derived from a diamine having an ethylene glycol skeleton, if the release layer is heated to a high temperature (for example, 200 ° C) (Above), the shearing force can be reduced. With regard to this phenomenon, the team of the present invention speculated that the high-temperature heating causes the aforementioned ether structure or the aforementioned ethylene glycol skeleton to be detached from the resin constituting the solvent release sheet, and the shear adhesive force is reduced by this detachment.

In the case where the aforementioned ether structure or the aforementioned ethylene glycol skeleton will be detached from the resin constituting the solvent release sheet, for example, by comparing the FT-IR spectrum before and after heating at 300 ° C for about 30 minutes, it can be confirmed that the The reduction of the frequency spectrum from 2800 to 3000 before and after.

Examples of the diamine having an ethylene glycol skeleton include: a diamine having a polypropylene glycol structure and one amine group at each end; a diamine having a polyethylene glycol structure and one amine at each end Diamine; a diamine having a polytetramethylene glycol structure and one amine group at each end. In addition, for example, a diamine having a plurality of such ethylene glycol structures and having one amine group at each end.

The molecular weight of the diamine having an ether structure is preferably in the range of 100 to 5000, and more preferably 150 to 4,800. When the molecular weight of the diamine having an ether structure is in the range of 100 to 5000, a peeling layer 5 having a high adhesive force at a low temperature and exhibiting peelability at a high temperature is easily obtained.

For the formation of the aforementioned polyfluorene imine resin, in addition to the diamine having an ether structure, other diamines having no ether structure may be used in combination. Examples of other diamines having no ether structure include aliphatic diamines and aromatic diamines. By using other diamines without an ether structure in combination, the adhesion to the adherend can be controlled. As a mixing ratio of the diamine having an ether structure and other diamines having no ether structure, Mohr is more preferably 100: 0 to 20:80, and more preferably 99: 1 to 30:70.

Examples of the aliphatic diamine include ethylenediamine, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminodeca Dioxane, 4,9-dioxa-1,12-diaminododecane, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisilazane Alkanes (α, ω-bisaminopropyltetramethyldisilaxane) and the like. The molecular weight of the aforementioned aliphatic diamine is usually 50 to 1,000,000, preferably 100 to 30,000.

Examples of the aromatic diamine include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, and m- Phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3 , 3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 1,4-bis (4-aminophenoxy Phenyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 4,4'-diaminodiphenyl ketone and the like. The molecular weight of the aforementioned aromatic diamine is usually 50 to 1,000, preferably 100 to 500. In this specification, the molecular weight means a value (weight average molecular weight) calculated by polystyrene conversion as measured by GPC (gel permeation chromatography).

Examples of the acid anhydride include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4, 4'-diphenyl ketone Tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylketone tetracarboxylic dianhydride, 4,4'-oxybisphthalic anhydride, 2,2-bis (2,3-di (Carboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-Dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) fluorenyl dianhydride, bis (3,4-dicarboxyphenyl) fluorenyl dianhydride, pyromelic acid Dianhydride, ethylene glycol trimellitic anhydride, etc. These can be used alone or in combination of two or more.

Examples of the solvent for reacting the acid anhydride with the diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, and cyclopentyl. Ketones, etc. These can be used alone or in combination of plural types. In addition, in order to adjust the solubility of the raw materials or the resin, a non-polar solvent such as toluene or xylene may be appropriately mixed and used.

The release layer 5 can be produced by the following method, for example. First, a solution containing the aforementioned polyamic acid is prepared. Next, the aforementioned solution is applied on the substrate so as to have a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions. As the aforementioned substrate, metal foils such as SUS304, 6-4 alloy, aluminum foil, copper foil, Ni foil, etc., or polyethylene terephthalate (PET), polyethylene, polypropylene, or fluorine-based A plastic film or paper coated on the surface of a release agent such as a release agent or a long-chain alkyl acrylate-based release agent. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, gravure coating, and spin coating. The drying conditions are performed, for example, in a range of a drying temperature of 50 to 150 ° C. and a drying time of 3 to 30 minutes. Thereby, the peeling layer 5 which concerns on this embodiment can be obtained.

The support 1 having the release layer 5 can be produced by transferring the release layer 5 to the support 1. The support 1 having the release layer 5 can also be produced by directly applying a solution containing polyamic acid on the support 1 to form a coating film, and drying the coating film under specified conditions.

[Formation of wiring circuit board]

Next, the printed circuit board 2 is formed on the release layer 5 of the support 1. As a method for forming a printed circuit board on a support having a release layer, a conventionally well-known manufacturing technique of a circuit board or an interposer such as a semi-additive method or an erase method can be applied. By forming the printed circuit board on the support, in the manufacturing steps, dimensional stability is good, and the operation of the thin printed circuit board is good. An example of a method for forming a printed circuit board is shown below.

[Formation of base insulating layer]

As shown in FIG. 3, a resin sheet 20 a as a base insulating layer is adhered to the release layer 5 of the support 1. The thickness of the resin sheet 20a is preferably 3 to 50 μm.

Next, an opening h1 is formed at a position where the external connection conductor portion 22 should be formed (see FIG. 4). As a method for forming the opening h1, a conventionally known method can be adopted. For example, by using a photosensitive material for exposure and development, the opening h1 can be formed. The shape of the opening is not particularly limited, but is preferably circular and the diameter can be appropriately set, for example, 5 μm to 500 μm. After that, do heat curing. As the conditions for heat curing, in terms of heating temperature, preferably from 20 ° C to 150 ° C, more preferably from 40 ° C to 120 ° C; heating In terms of time, it is preferably from 0.5 minutes to 60 minutes, and more preferably from 1 minute to 30 minutes.

[Formation of metal film for contacts]

Next, a contact metal film 211 is formed at the opening h1 (see FIG. 5). Since the metal film 211 is formed, better electrical connection can be made and corrosion resistance can be improved. The method of forming the metal film 211 is not particularly limited, but plating is preferred. Examples of the material of the metal film include copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, Individual metals such as tungsten and ruthenium, or alloys formed from two or more of these metals. Among these, as a preferred material, for example, gold, tin, nickel, etc .; as a preferred metal film state, the bottom layer is set to Ni, and the surface layer is set to a two-layer structure of Au.

[Formation of seed film, lower conductive path, and conductor layer]

Next, a conductive layer 23 is formed as needed, and a seed film (metal thin film) 23a (see FIG. 6) is formed so that a metal material can be deposited on the wall surface of the portion to be the conductive path 25 well. The seed film 23a can be formed by, for example, sputtering. As the material of the seed film, for example, a single metal such as copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, ruthenium, or the like may be used. Alloys, etc. The thickness of the conductive layer 23 is not particularly limited, but may be appropriately selected within a range of 1 to 500 nm. The guide path 25 is preferably cylindrical in shape, and the diameter is 5 to 500 μm, and more preferably 5 to 300 μm. Thereafter, a conductor layer 23 and a via 25 having a predetermined wiring pattern are formed. The wiring pattern can be Formed by plating. After that, a part of the seed film of the non-conductive layer 23 is removed.

Next, as shown in FIG. 7, the upper surface of the conductor layer 23 is covered with a plated photoresist r1 (except the portion where the conductive path should be formed), and the lower surface of the support 1 is covered with the entire surface with a photoresist r2. The conductive path 24 is formed by electrolytic plating.

[Formation of Adhesive Layer]

Next, the plating resists r1 and r2 are removed, and the exposed conductive layer 23 and the conductive path 24 are buried to form an adhesive layer 20b containing epoxy and polyimide as main components to make the conductive path. The upper end face of 24 is used as a terminal and exposed on the bonding layer, and the bonding layer is etched with an alkaline solution or the like (see FIG. 8).

[Formation of a metal film to the end surface of the conductor portion for connection]

Next, as shown in FIG. 9, the upper end surface of the conduction path 24 is formed by, for example, electrolytic plating to form the connection conductor portion 21. The connection conductor portion 21 can be formed by, for example, a nickel film, a gold film, or the like. In this way, a printed circuit board can be formed. In the forming step of the printed circuit board, various solvents (especially methyl ethyl ketone) may be used. However, after the resin sheet 20a was thermally hardened at 180 ° C for 1 hour, it was immersed in methyl ethyl ketone at 20 ° C to 25 ° C for 2400 seconds, and the weight reduction rate was 1.0% by weight or less. Therefore, it can be called p-methyl ethyl ketone to suppress dissolution. As a result, if the resin sheet 20a is used, a highly accurate printed circuit board can be manufactured.

In addition, in the resin sheet 20a, after being thermally cured at 180 ° C for 1 hour, the weight reduction rate was 1.0% by weight or less after being immersed in 0.5% by weight of hydrofluoric acid at a temperature of 20 ° C to 25 ° C for 60 seconds. It will become more acid-resistant. At this time, in the aforementioned forming step of the printed circuit board, even if an acid is used, a printed circuit board with higher accuracy can be manufactured.

In addition, in the resin sheet 20a, after being heat-cured at 180 ° C for one hour, the weight reduction rate was 240 seconds after immersion in a 3.0% by weight tetramethylammonium hydroxide aqueous solution of 20 ° C to 25 ° C. When it is 1.0% by weight or less, it will have more alkali resistance. At this time, in the aforementioned step of forming the printed circuit board, even if an alkali is used, a printed circuit board with higher accuracy can be manufactured.

[Packaging step, peeling step, dicing]

Next, the obtained printed circuit board 2 (the support 1 is a peelable attacher) is used as a package wafer. Specifically, after the electrodes 31 of the semiconductor wafer 3 and the connecting conductor portion 21 of the printed circuit board 2 are arranged to face each other (refer to FIG. 10), the two are connected and the semiconductor wafer 3 is packaged on the printed circuit board 2 ( (See Figure 11). Note that, in FIG. 11, the respective protrusions of the connection-use conductive portion 21 and the electrode 31 after the package are omitted. After that, the adhesive layer 20 b is aged, and then each wafer 3 on the printed circuit board 2 is sealed with a resin (not shown). For the resin sealing, a sheet-like sealing resin sheet may be used, or a liquid-like resin sealing material may be used. Thereafter, the surface opposite to the support 1 of the release layer 5 is used as an interface, and the support 1 and the release layer 5 are simultaneously peeled. As peel Methods include, for example, solvent peeling using N-methyl-2-pyrrolidone or peeling by heating. When peeling is performed by heating, the lower limits of the heating temperature can be set to, for example, 50 ° C, 80 ° C, 100 ° C, 150 ° C, and 180 ° C. The upper limit of the temperature during the peeling step is preferably 260 ° C, more preferably 230 ° C, and still more preferably 200 ° C. In the aforementioned peeling step, the time for which the temperature is maintained under the aforementioned temperature conditions varies depending on the temperature, but is preferably 0.05 to 120 minutes, and more preferably 0.1 to 30 minutes. Still, in the steps subsequent to the aforementioned packaging step, it is preferable to avoid exposure to a heat above 260 ° C. This can suppress melting of solder and the like. Therefore, a semiconductor device 4 in which the semiconductor wafer 3 is packaged on the printed circuit board 2 can be obtained.

In addition, the printed circuit board 2 after the support 1 is peeled off may be subjected to a process of imparting solder balls.

The above is an example of a method for manufacturing a semiconductor device according to this embodiment, but the method for manufacturing a semiconductor device according to the present invention is not limited to the above example, and may be appropriately changed within the scope of the gist of the present invention.

[Example]

The following examples illustrate the preferred embodiments of the present invention in detail. However, as long as the materials, blending amounts, and the like described in this embodiment are not particularly limited, the gist of the present invention is not limited to these gist. The term “part” means “part by weight”.

(Example 1) <Production of Resin Sheets>

The following (a) to (f) were dissolved in methyl ethyl ketone to obtain a resin composition solution having a concentration of 26.8% by weight. This resin composition solution was coated on a release-treated film (release liner) made of a polyethylene terephthalate film having a thickness of 38 μm and subjected to a mold release treatment at 130 ° C. Dry for 2 minutes. Thereby, a resin sheet having a thickness of 100 μm was produced.

(a) 50 parts of acrylic resin (Teisan Resin SG-70L manufactured by Nagase ChemteX)

(b) Cresol novolac epoxy resin (EOCN1020-4P manufactured by Nippon Kayaku Co., Ltd.) 4.752 parts

(c) Biphenyl type phenol resin (MEH-7851SS manufactured by Meiwa Chemical Co., Ltd.) 4.848 parts

(d) Silica filler (SE2050MC (60%) by Admatechs)

(e) Silane coupling agent ((KBM-303 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.08 part

(f) 0.101 part of imidazole compound (2PHZ-PW manufactured by Shikoku Kasei Co., Ltd.) as a hardening accelerator

(Example 2) <Production of Resin Sheets>

The following (a) to (f) were mixed with a mixer, and kneaded with a biaxial kneader at 120 ° C. for 2 minutes, and then extruded through a mold to obtain a resin sheet having a thickness of 20 μm.

(a) 280 parts of epoxy resin (YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd.)

(b) Phenol resin (300 parts of MEH-7851-SS manufactured by Meiwa Chemical Co., Ltd.)

(c) Silica filler (FB-9454, manufactured by Denki Kogyo Co., Ltd.) 3,300 parts

(d) Silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts

(e) Hardening accelerator (2P4MHZ-PW manufactured by Shikoku Chemical Industry Co., Ltd.) 6 parts

(f) Carbon (# 40 manufactured by Mitsubishi Chemical Corporation)

(Measurement of weight loss rate when immersed in hydrofluoric acid)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, it was immersed in 0.5% hydrofluoric acid (HF) at 23 ° C for 60 seconds. After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight loss rate when immersed in tetramethylammonium hydroxide aqueous solution)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, it was immersed in a 3% tetramethylammonium hydroxide aqueous solution (TMAH) at 23 ° C for 5 minutes. After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight reduction rate when immersed in SC-1)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, SC-1 (in a weight ratio composition, ammonia water (15% by weight): hydrogen peroxide: water = 1: 2: 5) was immersed in 23 ° C for 100 seconds. After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1. (Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight reduction rate when immersed in SC-2)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, immerse SC-2 (in a weight ratio of hydrochloric acid (38% by weight): hydrogen peroxide: water = 1: 2: 5) at 23 ° C for 160 seconds. After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight reduction rate when immersed in hydrogen peroxide water)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, it was immersed in 30% hydrogen peroxide water at 23 ° C for 840 seconds. After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight loss rate when immersed in methyl ethyl ketone)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, it was immersed in methyl ethyl ketone (MEK) at 23 ° C for 2400 seconds. After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight reduction rate when immersed in degreasing solution)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, it was immersed in a degreasing solution (Rapid clean P-1000, manufactured by JX Nippon Mining & Metals, Inc.) at 50 ° C for 300 seconds. After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, return to room temperature in a desiccator, and The weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight loss rate when immersed in aqueous nitric acid solution)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, it was immersed in a 70% nitric acid aqueous solution at 23 ° C for 30 seconds. After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight reduction rate when immersed in a pre-plating treatment solution)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, it was immersed in a plating pretreatment liquid (SUPERZINCATEPROCESSSZII, manufactured by JX Nippon Mining & Metals, Inc.) at 23 ° C for 30 seconds. Rinse twice with ultrapure water for 3 minutes at room temperature (23 ° C) Then, it dried at 120 degreeC for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight reduction rate when immersed in nickel plating solution)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, it was immersed in a nickel plating solution (KG-535-0: KG-535-1 = 3: 1 manufactured by JX Nippon Mining & Metals) for 1800 seconds at 80 ° C. After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of weight reduction rate when immersed in gold plating solution)

First, the resin sheets related to Examples 1 and 2 were cut into 30 mm × 100 mm, and dried at 120 ° C. for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight before immersion) was measured. Next, the solution for gold plating (JX Nippon Mining & CF-500SS (Metals). After washing at room temperature (23 ° C) twice with ultrapure water for 3 minutes, it was dried at 120 ° C for 30 minutes. After that, the temperature was returned to room temperature in a desiccator, and the weight (weight after immersion) was measured.

The weight reduction rate is obtained by the following formula. The results are shown in Table 1.

(Weight reduction rate (% by weight)) = [1-((weight after immersion) / (weight before immersion))] × 100

(Measurement of glass transition temperature (Tg) of resin sheet)

The measurement of the tensile storage modulus was performed using a solid viscoelasticity measuring device (manufactured by Rheometric Scientific Corporation, format: RSA-III). Specifically, the resin sheet was heated at 180 ° C. for 1 hour and was thermally cured to obtain a measurement sample having a sample size of 400 mm in length × 10 mm in width × 200 μm in thickness from the cured product, and then the measurement sample was set for film stretching measurement. The jig was used to measure the tensile storage elastic modulus and depletion elastic modulus in a temperature range of -50 to 300 ° C under the conditions of a frequency of 1 Hz and a heating rate of 10 ° C / min, and calculated tan δ (G "( The glass transition temperature (Tg) was obtained by depleting the value of the elastic modulus) / G '(storage elastic modulus). As a result, the glass transition temperature of the resin sheet of Example 1 was 105 ° C. Furthermore, Example 2 The glass transition temperature of the resin sheet was 110 ° C.

20a‧‧‧Resin sheet (base insulating layer)

Claims (3)

A resin sheet is used to form a wiring circuit board that can be connected to electrodes formed on a semiconductor wafer, and is characterized in that it contains an epoxy resin and a phenol resin, and is thermally hardened at 180 ° C for 1 hour, and then immersed at 20 ° C. After 2400 seconds in methyl ethyl ketone above and below 25 ° C, the weight reduction rate is 1.0% by weight or less, excluding the case where the reaction product of polyphenoxy resin and one of unsaturated carboxylic acid and acid anhydride is contained, In the case of alkoxysilane polymers. The resin sheet according to claim 1, wherein after being heat-cured at 180 ° C for 1 hour, the weight reduction rate is 1.0% by weight after being immersed in 0.5% by weight of hydrofluoric acid at a temperature of 20 ° C to 25 ° C for 60 seconds. the following. The resin sheet according to claim 1 or 2, wherein after being heat-cured at 180 ° C for 1 hour, the resin sheet is immersed in a 3.0% by weight tetramethylammonium hydroxide aqueous solution at a temperature of 20 ° C to 25 ° C for 240 seconds. The reduction rate is 1.0% by weight or less.