TW201802973A - Sheet for producing three-dimensional integrated laminated circuit and method for producing three-dimensional integrated laminated circuit - Google Patents

Abstract

This sheet 1 for producing a three-dimensional integrated laminated circuit, which is interposed between a plurality of semiconductor chips having through-electrodes and is used to adhere the semiconductor chips to each other and obtain a three-dimensional integrated laminated circuit, is provided with at least a curable adhesive layer 13, wherein the adhesive layer 13 includes a thermally conductive filler and the standard deviation of the thickness (T2) of the adhesive layer 13 is 2.0 [mu]m or less. This sheet 1 for producing a three-dimensional integrated laminated circuit can be used to produce a three-dimensional integrated laminated circuit having excellent heat dissipation properties.

Description

Plate for manufacturing three-dimensional product volume layer circuit and method for manufacturing three-dimensional product volume layer circuit

The present invention relates to a plate suitable for manufacturing a three-dimensional bulk-layer circuit and a method for manufacturing a three-dimensional bulk-layer circuit using the same.

In recent years, from the viewpoint of increasing the capacity and function of electronic circuits, the development of a three-dimensional multi-layer volume layer circuit (hereinafter referred to as a "multi-layer circuit") in which a plurality of semiconductor wafers are three-dimensionally laminated is developed. Department in progress. In this kind of multilayer circuit, in order to miniaturize. It is highly functional and uses a semiconductor wafer having a through electrode (TSV) penetrating from the circuit formation surface to the opposite surface. At this time, the stacked semiconductor wafers are electrically connected by contact between the through-electrodes (or bumps provided at the ends of the through-electrodes) provided in each of them.

When manufacturing such a laminated circuit, in order to ensure the above-mentioned electrical connection and mechanical strength, a resin composition is used to electrically connect the through electrodes to each other, and at the same time, the semiconductor wafers are bonded to each other. For example, Patent Document 1 proposes a method in which a film-shaped adhesive, commonly referred to as a non-conductive film (NCF), is interposed between semiconductor wafers, and the semiconductor wafers are adhered to each other. .

However, in the above-mentioned multilayer circuit, since a plurality of semiconductors The wafers are laminated, so it is very easy to generate heat when a current flows through the circuit. The heat generation of the multilayer circuit may cause a decrease in the calculation processing capability or an erroneous operation, which may cause the performance of the multilayer circuit to be deteriorated. In addition, when the laminated circuit generates excessive heat, the laminated circuit may be deformed, damaged, or malfunctioned. Therefore, the above-mentioned laminated circuit is required to have high heat dissipation to ensure reliability.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-010368

However, in a multilayer circuit manufactured using a conventional adhesive, there is a problem that it is not always possible to achieve good heat dissipation.

The present invention has been made in view of such an actual situation, and an object thereof is to provide a plate for manufacturing a three-dimensional bulk volume circuit having excellent heat release properties. Another object of the present invention is to provide a method for manufacturing such a three-dimensional integrated volume layer circuit.

In order to achieve the above object, the first system of the present invention provides a three-dimensional bulk-layer circuit manufacturing plate, which is interposed between a plurality of semiconductor wafers having a through electrode, and the three semiconductor wafers are bonded to each other to form a three-dimensional circuit. The three-dimensional bulk-layer circuit manufacturing plate used for the three-dimensional bulk-layer circuit is characterized in that the above-mentioned three-dimensional bulk-layer circuit manufacturing plate has at least a hardenable adhesive layer, and the adhesive layer contains Thermally conductive filler, and the standard deviation of the thickness (T2) of the adhesive layer is 2.0 μm or less (invention 1).

In the above-mentioned invention (Invention 1), the sheet for manufacturing a three-dimensional bulk-layer circuit is because the adhesive layer contains a thermally conductive filler having high thermal conductivity, and the standard deviation of the thickness (T2) of the adhesive layer is in the above range. The multilayer circuit system manufactured using this plate is excellent in heat radiation. Therefore, by using the plate for manufacturing a three-dimensional multilayer volume circuit of the above invention (Invention 1), a multilayer circuit having high reliability can be manufactured.

In the above invention (Invention 1), the thermally conductive filler is preferably composed of a material selected from a metal oxide, silicon carbide, carbide, nitride, and metal hydroxide (Invention 2).

In the above invention (Inventions 1, 2), the content of the thermally conductive filler in the adhesive layer is preferably 35% by mass or more and 95% by mass or less (Invention 3).

In the above invention (Inventions 1 to 3), the thermal conductivity of the thermally conductive filler at 23 is 10 W / m. K or higher is preferred (Invention 4).

In the above invention (Inventions 1 to 4), the average particle diameter of the thermally conductive filler is preferably 0.01 μm or more and 20 μm or less (Invention 5).

In the above invention (Inventions 1 to 5), the thermal conductivity of the adhesive layer after curing is 0.5 W / m. Above K, 8.0W / m. K is preferred (invention 6).

In the above inventions (Inventions 1 to 6), it is preferable that the material constituting the adhesive layer contains a thermosetting component, a high molecular weight component, and a curing catalyst (Invention 7).

In the above inventions (Inventions 1 to 7), the glass transition temperature of the high molecular weight component is preferably 50 ° C or higher (Invention 8).

In the above inventions (Inventions 1 to 8), the material constituting the adhesive layer is preferably a flux-containing component (Invention 9).

In the above invention (Inventions 1 to 9), the thickness of the adhesive layer is preferably 2 μm or more and 500 μm or less (Invention 10).

In the above invention (Inventions 1 to 10), the plate for manufacturing a three-dimensional bulk volume circuit preferably further includes: an adhesive layer, which is laminated on one side of the adhesive layer; and a substrate, which The layer is laminated on the opposite side of the adhesive layer from the adhesive layer (Invention 11).

In the above invention (Invention 11), the thickness of the substrate is preferably 10 μm or more and 500 μm or less (Invention 12).

In the above invention (Invention 11 or 12), the ratio (T2 / T1) of the thickness (T2) of the adhesive layer to the thickness (T1) of the substrate is preferably 0.01 or more and 5.0 or less (Invention 13).

In the above inventions (Inventions 10 and 11), the storage elastic modulus of the adhesive at 23 ° C is preferably 1 × 10 ³ Pa or more and 1 × 10 ⁹ Pa or less (Invention 14).

In the above inventions (Inventions 11 to 14), the tensile elastic modulus of the substrate at 23 ° C is preferably 100 MPa or more and 5000 MPa or less (Invention 15).

The second aspect of the present invention provides a method for manufacturing a three-dimensional bulk-layer circuit, which includes the following steps: one side of the adhesive layer of the aforementioned three-dimensional bulk-layer circuit manufacturing plate (Inventions 1 to 10) or The step of bonding the adhesive layer on the opposite side of the adhesive layer to at least one side of the semiconductor wafer having a through electrode; The semiconductor wafer is cut simultaneously with the adhesive layer of the three-dimensional bulk-layer circuit manufacturing sheet, and the individual pieces are attached. A step of applying a semiconductor wafer with an adhesive layer; a method of electrically connecting the through electrodes to each other and alternately disposing the adhesive layer and the semiconductor wafer by singulating the plurality of semiconductor wafers with the adhesive layer A step of laminating a plurality of layers to obtain a semiconductor wafer laminate; and a step of hardening the adhesive layer on the semiconductor wafer laminate and adhering the semiconductor wafers constituting the semiconductor wafer laminate to each other (Invention 16).

When the plate for manufacturing a three-dimensional bulk-layer circuit of the present invention is used, a three-dimensional bulk-layer circuit having excellent heat release properties can be manufactured. When the manufacturing method of the present invention is used, it is possible to manufacture such a three-dimensional product volume layer circuit.

1、2‧‧‧Three-dimensional multi-layer circuit board manufacturing

11‧‧‧ Substrate

12‧‧‧ Adhesive layer

13‧‧‧ Adhesive layer

14‧‧‧ peeling sheet

FIG. 1 is a cross-sectional view of a plate for manufacturing a three-dimensional multi-layer bulk-layer circuit according to the first embodiment of the present invention.

Fig. 2 is a cross-sectional view of a plate for manufacturing a three-dimensional multi-layer bulk circuit in a second embodiment of the present invention.

[Forms for Implementing Invention]

Hereinafter, embodiments of the present invention will be described.

[Three-dimensional product volume layer circuit manufacturing plate]

Fig. 1 is a cross-sectional view showing a plate 1 for manufacturing a three-dimensional multi-layer bulk-layer circuit of the first embodiment. As shown in FIG. 1, the plate 1 for manufacturing a three-dimensional bulk volume circuit of the present embodiment (hereinafter referred to as “manufacturing plate 1”), The adhesive layer 13 is provided with a release sheet 14 laminated on at least one side of the adhesive layer 13. The release sheet 14 may be omitted.

Fig. 2 is a cross-sectional view showing a plate 2 for manufacturing a three-dimensional multi-layered bulk circuit of the second embodiment. As shown in FIG. 2, the plate 2 for manufacturing a three-dimensional multilayer volume circuit for the present embodiment (hereinafter, referred to as a “manufacturing plate 2”) is provided with a base material 11 and laminated on the base material. An adhesive layer 12 on at least one side of 11 and an adhesive layer 13 laminated on the adhesive layer 12 on the side opposite to the substrate 11. In addition, the release sheet 14 may be laminated on the surface of the adhesive layer 13 opposite to the adhesive layer 12.

In the three-dimensional multi-layer bulk-layer circuit manufacturing plates 1 and 2 of this embodiment, the adhesive layer 13 contains a thermally conductive filler having a high thermal conductivity. In addition, in the three-dimensional multi-layer bulk-layer circuit manufacturing plates 1 and 2 of this embodiment, the standard deviation of the thickness (T2) of the adhesive layer 13 is 2.0 μm or less.

Generally, since a multilayer circuit is a laminate of a plurality of semiconductor wafers, it contains a large amount of circuits that serve as heat sources, and also has a structure that does not easily release heat. Therefore, when the current flows in the multilayer circuit, the multilayer circuit is liable to generate heat, and at the same time, the generated heat is not easily dissipated to the outside.

However, in the multilayer circuit manufactured using the three-dimensional multilayer bulk circuit circuit manufacturing plates 1 and 2 of this embodiment, the semiconductor wafers are bonded to each other by the adhesive layer 13 containing a thermally conductive filler and having excellent heat release properties, so the heat is It is easy to release from the end of this adhesive layer 13. In addition, since the standard deviation of the thickness (T2) of the adhesive layer 13 is in the above range, the thickness of the adhesive 13 constituting the multilayer circuit becomes uniform, and the thickness of the multilayer circuit itself becomes uniform. As a result, the multilayer circuit Excellent internal heat conduction. With the above, the laminated circuit The overall exothermic property is excellent, and it is possible to suppress excessive temperature rise even when a current is caused to flow. As a result, a laminated circuit having high reliability can be manufactured.

On the other hand, since a multilayer circuit is a laminate of a plurality of semiconductor wafers, it is generally difficult to make the multilayer circuit a uniform thickness. This is because even if the thickness of the semiconductor wafer or the adhesive layer constituting the laminated circuit is slightly different from the required thickness, the semiconductor wafer and the adhesive layer are laminated, so the offset is accumulated, and as a result, One of the important reasons that the laminated circuit deviates greatly from the required thickness. In addition, when a through electrode or a bump of a semiconductor wafer is buried in an adhesive layer, a void may be generated. Due to the void, a thickness of an adhesive layer of a laminated circuit may be partially changed. Especially in the multilayer circuit, because there are interfaces between the semiconductor wafer and the adhesive layer that may generate voids, the probability of voids is high, making the thickness of the multilayer circuit even more difficult. However, in the three-dimensional bulk-layer circuit manufacturing plates 1 and 2 of this embodiment, the standard deviation of the thickness (T2) of the adhesive layer 13 is within the above range, and the thickness of the adhesive layer 13 can be suppressed from being changed. The required thickness is offset, whereby the laminated circuit can be made uniform in thickness. In addition, since the standard deviation of the thickness (T2) of the adhesive layer 13 is within the above range, when a through-electrode or bump of a semiconductor wafer is buried in the adhesive layer 13, generation of voids can be suppressed, and it can be embedded well. Therefore, the laminated circuit can also be made into a uniform thickness.

The plates 1 and 2 for manufacturing a three-dimensional bulk-layer circuit in this embodiment are interposed between a plurality of semiconductor wafers having a through electrode, and are used to connect the plurality of semiconductor wafers to each other to form a three-dimensional bulk-layer circuit. . One or both ends of the through electrode may also protrude from the surface of the semiconductor wafer. Further, the semiconductor wafer may further include a bump, and in this case, the bump may be provided at one end or both ends of the through electrode.

In the three-dimensional multi-layer circuit board 1 and 2 of this embodiment, the adhesive layer 13 is hardenable. Here, the term “having a hardening property” means that the adhesive layer 13 can be hardened by heating or the like. That is, the adhesive layer 13 is unhardened in the state which comprises the manufacturing plates 1 and 2. The adhesive layer 13 may be thermosetting or energy ray-curable. However, the adhesive layer 13 is preferably thermosetting because it can harden well when the manufacturing plates 1 and 2 are used in a laminated circuit manufacturing method. Specifically, when the manufacturing plates 1 and 2 are used in a manufacturing method of a laminated circuit, as described later, the adhesive layer 13 is singulated in a state where it is attached to a semiconductor wafer. Thereby, a laminated body of the semiconductor wafer and the individualized adhesive layer 13 can be obtained. In this multilayer system, the surface on the side of the adhesive layer 13 is a laminated body attached to a semiconductor wafer, and the adhesive layer 13 is hardened in this state. In general, semiconductor wafers do not have transmittance to energy rays, or in most cases, the transmittance is very low. Even in this case, if the adhesive layer 13 has thermosetting properties, the adhesive layer 13 can be quickly made. To harden.

Adhesive layer

(1) Materials

In the three-dimensional bulk-layer circuit manufacturing plates 1 and 2 of this embodiment, the material constituting the adhesive layer 13 contains a thermally conductive filler. In addition, it is preferable that the material further contain a thermosetting component, a curing agent, a curing catalyst, a high molecular weight component, a component having a flux function, and the like.

(1-1) Thermally conductive filler

The material constituting the adhesive layer 13 contains a thermally conductive filler. Here, the so-called thermally conductive filler means a filler having a high thermal conductivity, for example, a thermal conductivity of 10 W / m at 25 ° C. A filler of K or higher means preferably 20 W / m. Fillers above K refer to a particularly good 30 W / m. Fillers above K. The upper limit of the thermal conductivity of the thermally conductive filler at 25 ° C is not limited, but is usually 300 W / m. K or less.

As described above, when the adhesive layer 13 contains a thermally conductive filler, the adhesive layer 13 exhibits excellent heat release properties by interacting with the laminated circuit with a uniform thickness. In addition, since the adhesive layer 13 contains a thermally conductive filler, the obtained laminated circuit has higher rigidity and is less likely to undergo dimensional changes due to environmental changes.

As the thermally conductive filler, a material selected from the group consisting of metal oxides such as zinc oxide, magnesium oxide, aluminum oxide, titanium oxide, and iron oxide, carbides such as silicon carbide, calcium carbonate, boron nitride, and aluminum nitride is used. Fillers composed of metal hydroxides such as nitrides and magnesium hydroxide, and talc materials are preferred. Among these, from the viewpoint of achieving more excellent heat release properties, carbonization selected from the group consisting of metal oxides such as zinc oxide, magnesium oxide, aluminum oxide, titanium oxide, and iron oxide, silicon carbide, and calcium carbonate is used. Fillers made of materials such as nitrides, nitrides such as boron nitride, aluminum nitride, and metal hydroxides such as magnesium hydroxide are preferred. For these materials, powders may be used as fillers, or spheroidized beads may be used as fillers, or single crystal fibers may be used as fillers. The thermally conductive fillers obtained from the above materials can be used alone or in combination of two or more. The thermally conductive filler is preferably non-conductive.

The shape of the thermally conductive filler is not particularly limited. It has at least one shape selected from the group consisting of granular, needle-like, plate-like, and amorphous. Among these, it is preferable to use a granular heat conductive filler. When the thermally conductive filler is granular, the filling rate of the thermally conductive filler in the adhesive layer 13 is increased, and an efficient heat conduction path is formed in the adhesive layer 13. As a result, the adhesive layer 13 has a better heat release. Sex.

When the thermally conductive filler is granular, the lower limit of the average particle diameter is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. The upper limit of the average particle diameter of the thermally conductive filler is preferably 20 μm or less, more preferably 5 μm or less, and particularly preferably 1 μm or less. When the average particle diameter of the thermally conductive filler is in the above range, the adhesive layer 13 is more excellent in heat release, and at the same time, the film forming property of the adhesive layer 13 is good, and the thermal conductivity in the adhesive layer 13 can be improved. Filling rate of the filler. In addition, the average particle diameter of the thermally conductive filler in the present specification refers to a particle diameter calculated by measuring the major axis diameter of 20 thermally selected fillers arbitrarily selected using an electron microscope, and calculating the arithmetic mean thereof.

When the thermally conductive filler is granular, the maximum particle diameter of the thermally conductive filler is preferably 50 μm or less, and more preferably 25 μm or less. When the maximum particle diameter of the thermally conductive filler is 50 μm or less, it is easy to fill the thermally conductive filler into the adhesive layer 13. As a result, the adhesive layer 13 has a better heat release property. In addition, since the maximum particle diameter of the inorganic filler is 50 μm or less, the through electrodes (or bumps provided at the ends of the through electrodes) of the multilayer circuit are easily electrically connected to each other, and can be efficiently manufactured with high reliability. Layered circuit of sex.

When the thermally conductive filler is granular, the particle size of the thermally conductive filler is The cloth (CV value) is preferably 15% or more, especially 30% or more. The particle size distribution (CV value) is preferably 80% or less, and particularly preferably 60% or less. By setting the particle size distribution of the thermally conductive filler to the above range, it is possible to efficiently achieve uniform heat release. The CV value is an index of variation in particle size, which means that the larger the CV value, the larger the variation in particle size. Therefore, especially with a CV value of 15% or more, the variation in the particle diameter becomes good, and particles having a small size easily enter the gap between the particles. Thereby, the thermally conductive filler can be efficiently filled, and the adhesive layer 13 exhibiting high heat release properties can be easily obtained. In addition, when the CV value is 80% or less, the particle diameter of the thermally conductive filler can be suppressed from becoming larger than the thickness of the adhesive layer 13. As a result, it is possible to suppress the occurrence of unevenness on the surface of the adhesive layer 13 opposite to the adhesive layer 12, and it is easy to obtain good adhesiveness. In addition, when the CV value is 80% or less, it is easy to form the adhesive layer 13 having uniform performance. The particle size distribution (CV value) of the thermally conductive filler can be measured by electron microscope observation of the thermally conductive filler, and the major axis diameter can be measured for 200 or more particles, and the standard deviation of the major axis diameter can be determined as This standard deviation is obtained by dividing the value of the above average particle diameter.

When the shape of the thermally conductive filler is acicular, the average axial length (average axial length in the long axis direction) of the thermally conductive filler is preferably 0.01 μm or more, particularly preferably 0.05 μm or more, and further 0.1 μm. The above is better. The average axial length is preferably 10 μm or less, particularly preferably 5 μm or less, and further preferably 1 μm or less.

The aspect ratio of the thermally conductive filler is preferably 1 or more, and particularly preferably 5 or more. The aspect ratio is preferably 20 or less, and particularly preferably 15 or less. The aspect ratio of the thermally conductive filler is the above-mentioned range It is because an efficient heat conduction path is formed in the adhesive layer 13 so that the adhesive layer 13 has a better heat radiation property. The aspect ratio can be a value obtained by dividing the average diameter of the minor axis number of the thermally conductive filler by the average diameter of the major axis number. Here, the average number of minor axes and the average number of major axes refer to the measurement of the minor axis and major axis diameters of 20 thermally conductive fillers arbitrarily selected by electron microscope photography, and are calculated by setting their respective arithmetic mean values. The number average particle size.

The specific gravity of the thermally conductive filler is preferably 1 g / cm ³ or more, and particularly preferably 3 g / cm ³ or more. The specific gravity is preferably 10 g / cm ³ or less, and particularly preferably 6 g / cm ³ or less. When the specific gravity is in the above range, the exothermic property of the adhesive layer 13 becomes more excellent.

The content of the thermally conductive filler in the adhesive layer 13 is based on the total amount of the materials constituting the adhesive layer 13, and the lower limit value is preferably 35% by mass or more, and more preferably 40% by mass or more. It is particularly preferred to be 50% by mass or more. The upper limit of the content of the thermally conductive filler is preferably 95% by mass or less, and more preferably 90% by mass or less. The material constituting the adhesive layer 13 has a thermally conductive filler content of 35% by mass or more, and the adhesive layer 13 has a better heat release property, and the three-dimensional multi-layer bulk-layer circuit manufacturing board of this embodiment is used. Sheets 1 and 2 can efficiently produce a multilayer circuit having excellent heat release properties. In addition, when the content is 95% by mass or less, the content of components other than the thermally conductive filler in the material constituting the adhesive layer 13 becomes relatively high, so that the adhesive layer 13 can exhibit better adhesiveness.

(1-2) Thermosetting ingredients

嗪樹脂、苯氧基樹脂等，該等能夠單獨使用1種或組合2種以上而使用。該等之中，從接著性等的觀點而言，係以環氧樹脂及酚樹脂為佳，以環氧樹脂為特佳。 The material constituting the adhesive layer 13 is preferably one containing a thermosetting component. The thermosetting component is not particularly limited as long as it is an adhesive component generally used for connection of semiconductor wafers. Specific examples include epoxy resin, phenol resin, melamine resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimide resin, and benzo

A azine resin, a phenoxy resin, etc. can be used individually by 1 type or in combination of 2 or more types. Among these, epoxy resins and phenol resins are preferable, and epoxy resins are particularly preferable from the viewpoint of adhesiveness and the like.

烷等之分子內的碳-碳雙鍵藉由例如氧化而導入環氧基而成之所謂脂環型環氧化物。此外，亦能夠使用具有聯苯骨架、二環己二烯骨架、萘骨架等之環氧樹脂。該等環氧樹脂可單獨1種、或組合2種以上而使用。 Epoxy resins have the property of undergoing three-dimensional network formation upon heating to form a solid hardened product. As such an epoxy resin, various conventionally known epoxy resins can be used, and specific examples include phenols such as bisphenol A, bisphenol F, resorcinol, phenol novolac, and cresol novolac. Glycidyl ether; Glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; Rings of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid Oxypropyl ether; epoxy-type or alkyl-epoxy-type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline isocyanurate is substituted with glycidyl group; For example, vinyl cyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5, 5-spiro (3,4-epoxy) cyclohexane-m-di

A carbon-carbon double bond in a molecule such as an alkane is a so-called alicyclic epoxide in which an epoxy group is introduced by oxidation, for example. In addition, an epoxy resin having a biphenyl skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, or the like can also be used. These epoxy resins can be used individually by 1 type or in combination of 2 or more types.

The content of the thermosetting component in the material constituting the adhesive layer 13 is based on the total amount of the material constituting the adhesive layer 13, and the lower limit value thereof is preferably 5 mass% or more, and 10 mass% or more. For the better. The upper limit of the content of the thermosetting component is preferably 75% by mass or less. 55 mass% or less is more preferred. When the content of the thermosetting component is in the above range, it becomes easy to adjust the aforementioned exothermic onset temperature and exothermic peak temperature to the aforementioned range.

(1-3) Hardener. Hardening catalyst

When the material constituting the adhesive layer 13 contains the aforementioned thermosetting component, it is preferable that the material further contains a curing agent and a curing catalyst.

The curing agent is not particularly limited, and examples thereof include phenols, amines, and thiols, and can be appropriately selected according to the type of the thermosetting component. For example, when an epoxy resin is used as the curable component, phenols are preferred from the viewpoint of reactivity with the epoxy resin and the like.

Examples of the phenols include bisphenol A, tetramethyl bisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, triphenylmethane-type phenol, tetrakis Phenol, novolac-type phenol, cresol novolac resin, etc. can be used alone or in combination of two or more.

The curing catalyst is not particularly limited, and examples thereof include imidazole-based, phosphorus-based, amine-based, and the like, and they can be appropriately selected according to the types of the aforementioned thermosetting components and the like. As the hardening catalyst, it is preferable to use a latent hardening catalyst, which does not activate under predetermined conditions, but activates when it is heated to a temperature higher than the sticking temperature at which the solder melts. The latent curing catalyst is also preferably used as a microencapsulated latent curing catalyst.

For example, when an epoxy resin is used as a hardening component, an imidazole-based hardening catalyst is used as a hardening catalyst from the viewpoints of reactivity with the epoxy resin, storage stability, physical properties of hardened materials, and hardening speed. Media is better. As imidazole-based curing catalysts, known substances can be used, but from excellent curing properties, In terms of preservation stability and connection reliability, an imidazole catalyst having a triazine skeleton is preferred. These can be used individually or in combination of 2 or more types. Moreover, these can also be used as a microencapsulated latent hardening catalyst. The melting point of the imidazole-based hardening catalyst is preferably 200 ° C or higher, and particularly preferably 250 ° C or higher, from the viewpoint of excellent hardenability, storage stability, and connection reliability.

In this embodiment, the content of the hardening catalyst of the material constituting the adhesive layer 13 is based on the total amount of the material constituting the adhesive layer 13, and the lower limit value is preferably 0.1% by mass or more, and 0.2 A mass% or more is more preferred, and a mass of 0.4 mass% or more is particularly preferred. The upper limit of the content of the hardening catalyst is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the material constituting the adhesive layer 13 has a content of the curing catalyst of at least the above-mentioned lower limit value, the thermosetting component can be sufficiently cured. On the other hand, when the content of the curing catalyst is equal to or less than the above-mentioned upper limit value, the storage stability of the adhesive layer 13 becomes good.

(1-4) High molecular weight ingredients

The material constituting the adhesive layer 13 is preferably a high molecular weight component other than the thermosetting component. By including the high molecular weight component, the material's 90 ° C. melt viscosity and average linear expansion coefficient easily meet the numerical ranges described below, and the reliability of the obtained multilayer circuit is higher.

Examples of the high molecular weight component include (meth) acrylic resins, phenoxy resins, polyester resins, polyurethane resins, polyimide resins, polyimide resins, and siloxane-modified polyimide resins. Fluorene imine resin, polybutadiene resin, polypropylene resin, styrene-butadiene-styrene copolymer, styrene-ethylene-butene-styrene copolymer, polyacetal resin, polyethylene butyral Led by aldehyde resin Polyvinyl acetal resin, butyl rubber, chloroprene rubber, polyamide resin, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-acrylic acid copolymer, acrylonitrile-butadiene-benzene Ethylene copolymer, polyvinyl acetate, nylon, etc. can be used alone or in combination of two or more.

In addition, "(meth) acrylic acid" in this specification means both acrylic acid and methacrylic acid. The same applies to other similar terms such as "(meth) acrylic resin".

Among the high molecular weight components, it is preferable to use one or more members selected from the group consisting of a polyvinyl acetal resin, a polyester resin, and a phenoxy resin. The material constituting the above-mentioned manufacturing sheet is made to contain these high molecular weight components, and both the 90 ° C. melt viscosity and the average linear expansion coefficient become lower values. As a result, these values fall within the numerical range described later. easily.

Here, the polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol using an aldehyde, and the polyvinyl alcohol is obtained by saponifying polyvinyl acetate. Examples of the aldehyde used in the acetalization include n-butyraldehyde, n-hexanal, and n-valeraldehyde. As the polyvinyl acetal resin, a polyvinyl butyral resin obtained by acetalization using n-butyraldehyde is also preferred.

Examples of the polyester resin include a polymer obtained by polycondensing a dicarboxylic acid component and a diol component such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene oxalate resin. Ester resins; modified polyester resins such as urethane-modified polyester resins obtained by reacting polyisocyanate compounds with these; polyester resins obtained by grafting acrylic resins and / or vinyl resins, etc. Moreover, it can be used individually by 1 type or in combination of 2 or more types.

The material constituting the adhesive layer 13 contains polyvinyl acetal. When a resin or a polyester resin is used as the high-molecular weight component, it is particularly preferred that the resin further contains a phenoxy resin. When a phenoxy resin is further contained, the material constituting the adhesive layer 13 has a 90 ° C melt viscosity and an average linear expansion coefficient that more easily satisfy the numerical ranges described later.

The phenoxy resin is not particularly limited, and examples thereof include bisphenol A type, bisphenol F type, bisphenol A / bisphenol F copolymerization type, biphenol type, and biphenyl type.

The lower limit of the softening point of the high molecular weight component is preferably 50 ° C or higher, more preferably 100 ° C or higher, and particularly preferably 120 ° C or higher. The upper limit of the softening point of the high molecular weight component is preferably 200 ° C or lower, more preferably 180 ° C or lower, and particularly preferably 150 ° C or lower. By including a high molecular weight component having a softening point of the above lower limit value or more, the average linear expansion coefficient of the material constituting the adhesive layer 13 can be reduced, and it is easy to satisfy a numerical range described later. When the softening point is equal to or less than the above-mentioned upper limit value, embrittlement of the adhesive layer 13 can be suppressed. The softening point is a value measured in accordance with ASTM D1525.

The lower limit of the glass transition temperature of the high molecular weight component is preferably 50 ° C or higher, more preferably 60 ° C or higher, and particularly preferably 80 ° C or higher. The upper limit of the glass transition temperature of the high molecular weight component is preferably 250 ° C or lower, more preferably 200 ° C or lower, and particularly preferably 180 ° C or lower. By including a high molecular weight component having a glass transition temperature of the above lower limit value or more, the average linear expansion coefficient of the material constituting the adhesive layer 13 can be reduced, and the numerical range described later can be easily satisfied. When the glass transition temperature is equal to or lower than the above upper limit, the compatibility with other materials becomes excellent. The glass transition temperature of the high molecular weight component is a value measured using a differential scanning calorimeter.

The weight average molecular weight of the high molecular weight component is preferably 10,000 or more, more preferably 30,000 or more, and particularly preferably 50,000 or more. The upper limit value is preferably 1 million or less, more preferably 700,000 or less, and particularly preferably 500,000 or less. When the weight-average molecular weight is equal to or more than the above-mentioned lower limit value, it is preferable because the melt viscosity can be reduced while maintaining the film forming property. When the weight-average molecular weight is equal to or less than the above-mentioned upper limit, it is preferable because the compatibility with low-molecular-weight components such as thermosetting components is improved. In addition, the weight average molecular weight in this specification is a standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

The content of the high molecular weight component in the material constituting the adhesive layer 13 is based on the total amount of the material constituting the adhesive layer 13, and the lower limit value is preferably 3% by mass or more, and 5% by mass or more. More preferably, it is especially preferable that it is 7 mass% or more. The upper limit of the content of the high molecular weight component is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 80% by mass or less. When the content of the high-molecular-weight component is greater than or equal to the above-mentioned lower limit value, the 90 ° C. melt viscosity of the material constituting the adhesive layer 13 can be made lower, and the aforementioned numerical range can be easily satisfied. On the other hand, when the content of the high-molecular-weight component is equal to or less than the above-mentioned upper limit value, the average linear expansion coefficient of the material constituting the adhesive layer 13 can be further reduced, and the numerical range described later can be easily satisfied.

(1-5) Ingredients with flux function

In this embodiment, when the through-electrodes or bumps of a semiconductor wafer are bonded by solder, the material constituting the adhesive layer 13 contains a component having a flux function (hereinafter referred to as a "flux component") as good. The flux component is a substance having a function of removing a metal oxide film formed on an electrode surface, and is capable of By making the electrical connection between the electrodes of the solder more reliable, the connection reliability at the soldered portion can be improved.

The flux component is not particularly limited, and a component having a phenolic hydroxyl group and / or a carboxyl group is preferred, and a component having a carboxyl group is particularly preferred. The component having a carboxyl group has a flux function, and when a later-described epoxy resin is used as a thermosetting component, it also functions as a hardener. Therefore, the component having a carboxyl group is consumed as a hardener after the soldering is completed, so it is possible to suppress a defect caused by an excessive flux component.

Specific examples of the flux component include glutaric acid, 2-methylglutaric acid, o-antanilic acid, diphenolic acid, adipic acid, ossalic acid, benzoic acid, diphenylglycolic acid, Azelaic acid, benzylbenzoic acid, malonic acid, 2,2-bis (hydroxymethyl) propionic acid, gallic acid, o-methoxybenzoic acid, m-hydroxybenzoic acid, succinic acid, 2,6- Dimethoxymethyl p-cresol, hydrazine benzoate, carbohydrazide, dihydrazine malonate, dihydrazine succinate, dihydrazine glutarate, hydrazine oxalate, imine diacetic acid Dihydrazine, dihydrazine iconate, trihydrazine citrate, thiocarbohydrazide, bezophenone hydrazone, 4,4'-oxodisulfenazine, adipic acid A hydrazine, a rosin derivative, etc. can be used individually by 1 type or in combination of 2 or more types.

Examples of the rosin derivative include gum rosin, tall rosin, wood rosin, polymerized rosin, hydrogenated rosin, methylated rosin, rosin ester, rosin-modified maleic acid resin, Rosin modified phenol resin, rosin modified alkyd resin, etc.

Among these, it is particularly preferable to use at least one selected from the group consisting of 2-methylglutaric acid, adipic acid, and rosin derivatives. 2-methylglutaric acid and adipic acid The material constituting the adhesive layer 13 has a small molecular weight but has two carboxyl groups in the molecule. Therefore, even if it is added in a small amount, it has an excellent flux function, and is particularly suitable for this embodiment. The rosin derivative has a high softening point, and can maintain a low linear expansion coefficient while imparting flux properties, and is therefore particularly suitable for this embodiment.

At least one of the melting point and the softening point of the flux component is preferably 80 ° C or higher, more preferably 110 ° C or higher, and more preferably 130 ° C or higher. When at least one of the melting point and the softening point of the flux component is within the above-mentioned range, it is preferable to obtain more excellent flux function and reduce exhaust gas. The upper limit of the melting point and softening point of the flux component is not particularly limited, and may be, for example, less than the melting point of the solder.

In this embodiment, the content of the flux component of the material constituting the adhesive layer 13 is based on the total amount of the material constituting the adhesive layer 13, and the lower limit thereof is preferably 0.1% by mass or more, and 0.2 A mass% or more is more preferable, and 0.3 mass% or more is particularly preferable. The upper limit of the content of the flux component is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. When the material constituting the adhesive layer 13 and the content of the flux component is equal to or more than the above-mentioned lower limit value, the electrical connection between the electrodes by the solder can be made more reliable, and the connection reliability at the soldered portion can be further improved Sex. On the other hand, when the content of the flux component is equal to or less than the above-mentioned upper limit value, defects such as ion migration caused by the excessive flux component can be prevented.

(1-6) Other ingredients

The adhesive layer 13 may further contain a plasticizer, a stabilizer, an adhesion-imparting agent, a coloring agent, a coupling agent, an antistatic agent, an antioxidant, a conductive particle, and a An inorganic filler other than the thermally conductive filler is used as a material constituting the adhesive layer 13.

For example, when the material constituting the adhesive layer 13 contains conductive particles and can provide anisotropic conductivity to the three-dimensional bulk-layer circuit manufacturing plates 1 and 2, it may be in a state of supporting welding or in Unlike soldering, semiconductor wafers can be electrically connected to each other.

(2) Physical properties (2-1) Thermal conductivity

In the three-dimensional bulk-layer circuit manufacturing plates 1 and 2 of this embodiment, the thermal conductivity of the adhesive layer 13 after curing is 0.5 W / m. Above K is preferred, especially 0.7W / m. Above K is preferred, further at 1.0 W / m. Above K is preferred. The thermal conductivity is 8.0 W / m. Below K is preferred, especially at 4.0 W / m. Below K is preferred, further at 3.0 W / m. K is preferred. With this thermal conductivity being 0.5W / m. Above K, the adhesive layer 13 is easy to exhibit good heat dissipation properties. By using the three-dimensional multilayer volume circuit manufacturing plates 1 and 2 of this embodiment, it is possible to efficiently manufacture a multilayer circuit having high reliability. On the other hand, the thermal conductivity is 8.0 W / m. Below K, the content of the thermally conductive filler in the adhesive layer 13 does not increase excessively. As a result, it is easy to have both good heat release property in the adhesive layer 13, adhesiveness with the adhesive layer 13, and sheet workability. The method for measuring the thermal conductivity of the adhesive layer 13 is as shown in a test example described later.

(2-2) Melt viscosity

In the three-dimensional bulk-layer circuit manufacturing plates 1 and 2 of this embodiment, the melt viscosity of the material constituting the adhesive layer 13 before curing at 90 ° C (hereinafter referred to as "90 ° C melt viscosity") , Its upper limit is 5.0 × 10 ⁵ Pa. It is preferably below s, especially 1.0 × 10 ⁵ Pa. It is preferably below s, and further preferably 5.0 × 10 ⁴ Pa. s is preferred. When the melt viscosity at 90 ° C is equal to or less than the above upper limit value, when the adhesive layer 13 is interposed between the electrodes, the unevenness on the surface of the semiconductor wafer due to the penetration electrode or the bump can be well followed, and the semiconductor wafer can be prevented. A void is generated at the interface with the adhesive layer 13. The lower limit of the melt viscosity at 90 ° C is 1.0 × 10 ⁰ Pa. Above s is preferred, especially 1.0 × 10 ¹ Pa. s or more is preferred, further 1.0 × 10 ² Pa. Above s is preferred. When the melt viscosity at 90 ° C. is equal to or more than the above-mentioned lower limit value, the material constituting the adhesive layer 13 does not flow excessively, and contamination of the device can be prevented when the adhesive layer 13 is attached or the semiconductor wafer is laminated. Therefore, the three-dimensional multi-layer bulk layer circuit manufacturing plates 1 and 2 of this embodiment are those having a higher reliability because the constituent material has a 90 ° C melt viscosity within the above range.

Here, the 90 ° C melt viscosity of the material constituting the adhesive layer 13 can be measured using a flow tester. Specifically, it is possible to measure the adhesive layer 13 having a thickness of 15 mm using a flow tester (manufactured by Shimadzu Corporation, CFT-100D) under a load of 50 kgf, a temperature range of 50 to 120 ° C, and a heating rate of 10 ° C / min. Melt viscosity.

(2-3) Average linear expansion coefficient

In this embodiment, the material constituting the adhesive layer 13 has an average linear expansion coefficient (hereinafter referred to as the "average linear expansion coefficient" for short) of the hardened material at 0 to 130 ° C, and the upper limit value is 45 ppm or less. It is particularly preferred that it is preferably 35 ppm or less, and more preferably 25 ppm or less. When the average linear expansion coefficient is equal to or less than the above-mentioned upper limit value, the difference between the linear expansion coefficient of the adhesive layer 13 and the semiconductor wafer composed of the hardened material becomes small. Based on this difference, the gap between the adhesive layer 13 and the semiconductor wafer can be reduced. Possible stress. As a result, the three-dimensional multi-layer bulk-layer circuit manufacturing plates 1 and 2 of this embodiment can connect semiconductor wafers to each other. The continuous reliability becomes higher, especially the temperature cycle test shown in the examples, and it becomes the one with higher continuous reliability.

On the other hand, the lower limit value of the average linear expansion coefficient is not particularly limited, and from the viewpoint of film formability, it is preferably 5 ppm or more, and more preferably 10 ppm or more.

Here, the average linear expansion coefficient of the material constituting the adhesive layer 13 can be measured using a thermomechanical analysis device. Specifically, a cured product obtained by forming a 45 μm thick adhesive layer 13 on a substrate and curing the adhesive layer 13 by treating at 160 ° C. for one hour was performed using a thermomechanical analysis device (Bruker AXS Corporation). Co., Ltd., TMA4030SA), the linear expansion coefficient was measured under the conditions of a load of 2 g, a temperature range of 0 to 300 ° C, and a temperature increase rate of 5 ° C / min. From this measurement result, the average linear expansion coefficient at 0 to 130 ° C can be calculated.

(2-4) Glass transition temperature

In this embodiment, the lower limit of the glass transition temperature (Tg) of the material constituting the adhesive layer 13 is preferably 150 ° C or higher, more preferably 200 ° C or higher, and 240 ° C or higher. good. When the glass transition temperature of the cured product is equal to or higher than the above-mentioned lower limit value, it is preferable because the cured product does not deform and does not easily generate stress during the temperature cycle test. On the other hand, the upper limit of the glass transition temperature of the hardened material is not particularly limited. From the viewpoint of suppressing embrittlement of the hardened material, it is preferably 350 ° C or lower, and more preferably 300 ° C or lower.

Here, the glass transition temperature of the hardened material of the material constituting the adhesive layer 13 is a dynamic viscoelasticity measuring device (manufactured by TA Instruments, DMA Q800) at a frequency of 11 Hz, an amplitude of 10 μm, and a heating rate of 3 ° C./minute. Measure the viscoelasticity when the temperature is raised from 0 ° C to 300 ° C and the tensile mode is followed. The temperature at the maximum point of tan δ (loss modulus / storage modulus).

(2-5) 5% mass reduction temperature

In the three-dimensional bulk layer circuit manufacturing plates 1 and 2 of this embodiment, the hardened material of the material constituting the adhesive layer 13 is 5% by mass weight reduction temperature measured by thermogravimetry, which is preferably 350 ° C or higher. In particular, 360 ° C or higher is preferred. When the 5% mass reduction temperature is 350 ° C. or higher, the hardened material of the adhesive layer 13 is excellent in resistance to high temperatures. Therefore, even when the cured product is exposed to a high temperature during the manufacture of the multilayer circuit, the generation of volatile components and the like due to the decomposition of the contained components of the cured product can be suppressed, and the performance of the multilayer circuit can be favorably maintained. The upper limit of the 5% mass reduction temperature is not particularly limited, but the 5% mass reduction temperature is usually preferably 500 ° C or lower.

Here, a 5% mass reduction temperature allows differential heat to be used. Thermogravimetric simultaneous measurement device. Specifically, the cured product can be obtained by forming a 45 μm thick adhesive layer 13 on a substrate, and then curing the adhesive layer 13 by treating the obtained sample at 160 ° C. for 1 hour, in accordance with JIS K7120. : 1987 and using differential heat. Simultaneous thermogravimetric measurement device (DTG-60, manufactured by Shimadzu Corporation), using nitrogen as the inflow gas, and increasing the temperature from 40 ° C to 550 ° C at a gas inflow rate of 100 ml / min and a temperature increase rate of 20 ° C / min. Thermogravimetric determination. Based on the obtained thermogravimetric curve, a temperature at which the mass is reduced by 5% relative to the mass at a temperature of 100 ° C. (a temperature at which the mass is reduced by 5%) is determined.

(2-6) Storage modulus

In the three-dimensional bulk-layer circuit manufacturing plates 1 and 2 of this embodiment, the storage elastic modulus at 23 ° C. after the adhesive layer 13 is hardened is preferably 1.0 × 10 ² MPa or more, particularly 1.0 × 10 ³ MPa or more is preferred. The storage elastic modulus is preferably 1.0 × 10 ⁵ MPa or less, and particularly preferably 1.0 × 10 ⁴ MPa or less. With the storage elastic modulus in the above range, a laminated body obtained by alternately laminating a semiconductor wafer and an individualized adhesive layer 13 when manufacturing a laminated circuit has a good strength. As a result, even when the semiconductor wafer is further laminated or the laminated body is operated, the state of the laminated body can be maintained well, and a laminated circuit having excellent quality can be manufactured.

Here, the storage elastic modulus at 23 ° C. after the adhesive layer 13 is hardened can be measured using a dynamic viscoelasticity measuring device. Specifically, a cured product obtained by forming an adhesive layer 13 having a thickness of 45 μm on a substrate and curing the adhesive layer 13 by treating at 160 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring instrument (TA Instruments Corporation). Co., Ltd., DMA Q800), and measured the viscoelasticity obtained by the tensile mode at a frequency of 11 Hz, an amplitude of 10 μm, and a temperature increase rate of 3 ° C./minute to raise the temperature from 0 ° C. to 300 ° C. From this measurement result, the storage elastic modulus (MPa) at 23 ° C. after the adhesive layer is hardened can be read.

(2-7) Heating start temperature and heating peak temperature by differential scanning calorimetry

In the three-dimensional bulk layer circuit manufacturing plates 1 and 2 of this embodiment, the adhesive layer 13 before curing is measured by a differential scanning calorimetry (DSC) method at a heating rate of 10 ° C / min. The exothermic onset temperature (TS) is preferably in the range of 70 ° C to 150 ° C, particularly in the range of 100 ° C to 150 ° C, and more preferably in the range of 120 ° C to 150 ° C. By setting the heat generation temperature (TS) to the above range, for example, it is possible to prevent the adhesive layer 13 from being hardened at an unintended stage when the heat generated when the semiconductor wafer is cut using a dicing blade is received. The manufacturing sheets 1 and 2 are also excellent in storage stability. In particular, in order to manufacture a laminated circuit, after a plurality of semiconductor wafers are laminated, a plurality of layers of the adhesive layer 13 existing between the semiconductor wafers are collectively hardened, and it is possible to suppress unintended before the completion of the semiconductor wafer lamination. This stage causes the adhesive layer 13 to harden.

In the three-dimensional bulk layer circuit manufacturing plates 1 and 2 of this embodiment, the adhesive layer 13 before curing is measured by a differential scanning calorimetry (DSC) method at a heating rate of 10 ° C / min. The fever peak temperature (TP) is preferably the fever start temperature (TS) + 5 ~ 60 ° C, especially TS + 5 ~ 50 ° C, and more preferably TS + 10 ~ 40 ° C. When the heat generation peak temperature (TP) is in the above range, when the adhesive layer 13 is hardened, the time from the start to completion of the hardening becomes shorter. Generally, when a laminated circuit is manufactured using an NCF adhesive, it takes time to harden the adhesive. Therefore, the tact time in the manufacture of the multilayer circuit is mostly determined in accordance with the curing time of the adhesive. Therefore, as described above, since the time until the adhesive layer 13 is hardened is short, the production work time can be effectively shortened. In particular, when manufacturing a multilayer circuit, in order to improve the efficiency of the process, after laminating (temporarily placing) a plurality of semiconductor wafers, a plurality of layers of the adhesive layer 13 existing between the semiconductor wafers are finally hardened. Even in this case, by setting the heating peak temperature (TP) to the above-mentioned range, it is possible to prevent an adhesive layer existing between the semiconductor wafers laminated at the beginning of the process from occurring in an unintended stage before the semiconductor wafers are laminated. 13 produces hardening.

Here, the exothermic onset temperature and the exothermic peak temperature can be measured using a differential scanning calorimeter. Specifically, the thickness is 15mm The adhesive layer 13 was heated from normal temperature to 300 ° C. using a differential scanning calorimeter (TA 2000, Q2000) at a temperature increase rate of 10 ° C./minute. From the DSC curve obtained in this way, it is possible to obtain the temperature at which the heat starts (heating start temperature) (TS) and the heat peak temperature (TP).

(2-8) thickness of adhesive layer, etc.

In the three-dimensional bulk-layer circuit manufacturing plates 1 and 2 of this embodiment, the thickness (T2) of the adhesive layer 13 is preferably 2 μm or more, particularly preferably 5 μm or more, and further preferably 10 μm or more. The thickness (T2) is preferably 500 μm or less, particularly 300 μm or less, and further preferably 100 μm or less. When the thickness (T2) of the adhesive layer 13 is 2 μm or more, the through-electrodes or bumps existing in the semiconductor wafer can be favorably buried in the adhesive layer 13. In addition, when the thickness (T2) of the adhesive layer 13 is 500 μm or less, when a semiconductor wafer having a through electrode is passed through the adhesive layer 13 and then bonded, the adhesive layer 13 does not excessively ooze on the side surface, and can be manufactured reliably High-performance semiconductor device. The thickness (T2) of the adhesive layer 13 is set to an average value when 100 points are measured at a total interval of 50 mm at the manufacturing sheet 1.

The standard deviation of the thickness (T2) of the adhesive layer 13 in the three-dimensional bulk-layer circuit manufacturing plates 1 and 2 of this embodiment is 2.0 μm or less, preferably 1.8 μm or less, and particularly 1.6 μm or less. good. When the standard deviation is greater than 2.0 μm, when the through-electrodes or bumps of the semiconductor wafer are embedded in the adhesive layer 13 using the manufacturing plates 1 and 2, voids are likely to occur, and at the same time, the adhesive layer constituting the laminated circuit The thickness of 13 and the thickness of the multilayer circuit itself become difficult to uniformize, and as a result, the heat dissipation of the multilayer circuit becomes insufficient. In particular, the laminated circuit is obtained by laminating a semiconductor wafer and an adhesive layer 13 in plural. Therefore, when the standard deviation of the thickness (T2) of the adhesive layer 13 is greater than 2.0 μm, the uniformity of the thickness of the obtained multilayer circuit is impaired, and the multilayer circuit cannot achieve good heat dissipation. The method for measuring the standard deviation of the thickness (T2) of the adhesive layer 13 is shown in the test example described later.

The ratio (T2 / T1) of the thickness (T2) of the adhesive layer 13 to the thickness (T1) of the substrate 11 in the three-dimensional bulk-layer circuit manufacturing sheet 2 having the second embodiment of the substrate 11 is It is preferably 0.01 or more, particularly preferably 0.1 or more, and further preferably 0.4 or more. The ratio (T2 / T1) is preferably 1.5 or less, particularly preferably 1.0 or less, and more preferably 0.9 or less. When the ratio (T2 / T1) is within the above range, the thickness balance between the substrate 11 and the adhesive layer 13 is good, and the workability when attaching the manufacturing sheet 2 to a semiconductor wafer is excellent. Applicability is easy when attaching. As a result, the lamination can be performed well and a laminated circuit having excellent quality can be manufactured. In particular, when the ratio (T2 / T1) is 0.01 or more, the relative thickness of the substrate 11 in the manufacturing sheet 1 becomes smaller, and the relative rigidity of the manufacturing sheet 1 can be suppressed low. As a result, when the manufacturing sheet 1 is attached to a semiconductor wafer, it becomes easy to embed the penetration electrodes or bumps existing in the semiconductor wafer in the adhesive layer 13 system. On the other hand, when the ratio (T2 / T1) is 1.5 or less, the relative thickness of the substrate 11 in the manufacturing sheet 1 becomes larger, and the relative rigidity of the manufacturing sheet 1 can be maintained high. . As a result, the operability of the manufacturing sheet 1 is excellent, and the manufacturing sheet 1 can be easily attached to a semiconductor wafer. The thickness (T1) of the base material 11 is an average value when a total of 100 points are measured at a 50 mm interval between the manufacturing sheet 1.

2. Adhesive layer

(1) Materials

In the plate 2 for manufacturing a three-dimensional bulk volume circuit of the second embodiment including the adhesive layer 12, the adhesive layer 12 may be made of a non-hardening adhesive or may be made of a hardening adhesive. As will be described later, when the three-dimensional multilayer bulk circuit circuit manufacturing sheet 2 of this embodiment is used in a multilayer circuit manufacturing method, the adhesive layer 13 is peeled from the laminated body of the substrate 11 and the adhesive layer 12. Therefore, from the viewpoint of facilitating the peeling, the adhesive layer 12 is preferably composed of a curable adhesive and the adhesive force is reduced by curing.

When the adhesive layer 12 is composed of a hardenable adhesive, the adhesive may be an energy ray hardenable adhesive or a thermosetting adhesive. Here, in order to harden the adhesive layer 12 and the adhesive layer 13 at different stages, when the adhesive layer 13 is thermosetting, the adhesive layer 12 is preferably composed of an energy ray-curable adhesive. When the agent layer 13 is energy ray-curable, the adhesive layer 12 is preferably composed of a thermosetting adhesive. However, since the adhesive layer 13 is preferably thermosetting for the reasons described above, the adhesive layer 12 is preferably composed of an energy ray-curable adhesive.

The non-hardening adhesive is preferably one having a required adhesive force and re-peelability. For example, an acrylic adhesive, a rubber adhesive, a silicone adhesive, or a urethane adhesive can be used. Agents, polyester-based adhesives, polyvinyl ether-based adhesives, and the like. Among these, from the viewpoint of effectively suppressing peeling at the interface between the adhesive layer 12 and the adhesive layer 13 at an unintended stage of the cutting step, an acrylic adhesive is preferred.

The energy-ray-curable adhesive may be a polymer having energy-ray-curable polymer as a main component, or a polymer having non-energy-ray-curable polymer. A compound (a polymer having no energy ray curability) and a mixture of at least one or more monomers and / or oligomers having an energy ray curable group are those having a main component. Also, it may be a mixture of an energy ray-curable polymer and a non-energy ray-curable polymer, or may be an energy ray-curable polymer and at least one or more monomers having an energy ray-curable group. A mixture of oligomers and / or oligomers may also be a mixture of these three types.

The polymer having energy ray curability is preferably a (meth) acrylate (co) polymer having a functional group (energy ray curable group) having energy ray curability introduced into a side chain. The polymer is preferably obtained by reacting an acrylic copolymer having a functional unit-containing monomer unit and an unsaturated group-containing compound having a functional group bonded to the functional group.

As the at least one or more of the monomers and / or oligomers having an energy ray-curable group, for example, an ester of a polyhydric alcohol and (meth) acrylic acid can be used.

As the non-energy-ray-curable polymer component, for example, an acrylic copolymer having the aforementioned functional unit-containing polymer unit can be used.

(2) Physical properties, etc.

In the plate 2 for manufacturing a three-dimensional bulk-layer circuit of the present embodiment, the storage elastic modulus of the adhesive layer 12 at 23 ° C. is preferably 1 × 10 ³ Pa or more, and 1 × 10 ⁴ Pa or more is special good. The storage elastic modulus is preferably 1 × 10 ⁹ Pa or less, and particularly preferably 1 × 10 ⁸ Pa or less. When the adhesive layer 12 is composed of a curable adhesive, the storage elastic modulus is set to the storage elastic modulus before curing. When the storage elastic modulus of the adhesive layer 12 at 23 ° C. is in the above range, when the manufacturing plate 2 is attached to the semiconductor wafer, the penetration electrodes or bumps existing in the semiconductor wafer can be well embedded. To the adhesive layer 13. In addition, when the non-bumped surface of the semiconductor wafer is polished on the back surface using the manufacturing plates 1 and 2, it is possible to suppress the semiconductor wafer from being warped or dimpled. The storage elastic modulus of the adhesive layer 12 at 23 ° C can be used. For example, a dynamic viscoelasticity measuring device (manufactured by TA Instruments, ARES) can be used at a frequency of 1 Hz, a measurement temperature range of -50 to 150 ° C, and a temperature increase rate. Measured at 3 ° C / min.

The thickness of the adhesive layer 12 is not particularly limited. For example, it is preferably 1 μm or more, and particularly preferably 10 μm or more. The thickness is, for example, preferably 100 μm or less, and particularly preferably 50 μm or less. When the thickness of the adhesive layer 12 is 1 μm or more, the adhesive layer 12 can exhibit good adhesion. In addition, when the thickness is 100 μm or less, the adhesive layer 12 can be prevented from becoming an unnecessary thickness, and the cost can be reduced.

3. Substrate

(1) Materials

As the material constituting the base material 11 in the three-dimensional multi-layer bulk-layer circuit manufacturing sheet 2 provided with the second embodiment of the base material 11, there is no particular limitation. However, when the manufacturing plate 2 is a dicing plate-integrated type bonding plate (cutting, wafer bonding plate), the material constituting the base material 11 is a material generally used for the base material constituting the dicing plate. Better. Examples of the material of the substrate 11 include polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, and polyethylene terephthalate. Ester, polybutylene terephthalate, polyurethane, ethylene vinyl acetate copolymer, ionic polymer, ethylene. (Meth) acrylic copolymer, ethylene. (Meth) acrylate copolymer, polystyrene, vinyl polyisoprene, polycarbonate, polyolefin, etc. Among these, 1 can be used One or a mixture of two or more.

When the manufacturing plate 2 is a back-grinding plate integrated type bonding plate, the material constituting the base material 11 is preferably a material usually used for the base material constituting the back-grinding plate. Examples of the material of such a substrate 11 include polyethylene terephthalate, polyethylene, polypropylene, and ethylene. Among resins such as a vinyl acetate copolymer, one or a mixture of two or more of them can be used.

The surface on the side of the adhesive layer 12 of the base material 11 may also be subjected to surface treatments such as a primer treatment, a corona treatment, and a plasma treatment to improve the adhesion with the adhesive layer 12.

(2) Physical properties, etc.

In the plate 2 for manufacturing a three-dimensional bulk-layer circuit of this embodiment, the tensile elastic modulus of the substrate 11 at 23 ° C is preferably 100 MPa or more, particularly 200 MPa or more, and further 300 MPa or more. good. The tensile elastic modulus is preferably 5,000 MPa or less, particularly preferably 1000 MPa or less, and further preferably 400 MPa or less. When the substrate 11 has a tensile elastic modulus at 23 ° C within the above range, when the manufacturing sheet 2 is attached to a semiconductor wafer, the through-electrodes or bumps existing in the semiconductor wafer can be well embedded. To the adhesive layer 13. In addition, when the manufacturing sheet 2 is a cut-to-piece integrated type bonding sheet, the substrate 11 is stretched at 23 ° C. and the modulus of elasticity is within the above range, and the manufacturing sheet 2 is expanded to expand the semiconductor. When the wafers are spaced from each other, it is preferable because the substrate 11 is not easily broken. The tensile elastic modulus of the base material 11 at 23 ° C can be measured using a tensile tester in accordance with JISK 7127: 1999.

The thickness (T1) of the substrate 11 is not particularly limited. For example, the thickness (T1) is 10 μm. The above is preferable, and especially 15 μm or more is preferable. The thickness (T1) is, for example, preferably 500 μm or less, and particularly preferably 100 μm or less. When the thickness (T1) of the substrate 11 is in the above range, the value (T2 / T1) of the ratio (T2 / T1) of the thickness (T2) of the adhesive layer 12 to the thickness (T1) of the substrate 11 can be easily set at The aforementioned range also has excellent operability when attaching the manufacturing plates 1 and 2 to a semiconductor wafer. As a result, it is possible to efficiently manufacture a multilayer circuit having excellent quality.

4. Peel off the sheet

The configuration of the release sheet 14 is arbitrary, and examples thereof include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polypropylene, and polyethylene. Polyolefin film and other plastic films. Such a release surface (a surface in contact with the adhesive layer 13) is preferably subjected to a release treatment. Examples of the release agent used in the release treatment include a release agent such as a silicone-based, fluorine-based, or long-chain alkyl-based release agent.

The thickness of the release sheet is not particularly limited, but is usually 20 μm or more and 250 μm or less.

5. Manufacturing method of plate for manufacturing three-dimensional product volume layer circuit

The three-dimensional bulk-layer circuit manufacturing sheet 1 of the first embodiment can be manufactured in the same manner as the conventional three-dimensional bulk-layer circuit manufacturing sheet. For example, when manufacturing the three-dimensional bulk-layer circuit manufacturing sheet 1 provided with the peeling sheet 14, it is possible to further contain a solvent or The coating liquid for the dispersion medium is coated on the release surface of the release sheet 14 using a die coater, a curtain coater, a spray coater, a slit coater, a blade coater, or the like. A coating film is formed thereon, and the coating film is dried to manufacture a manufacturing sheet 2. Coating liquid as long as The coating can be applied, and its properties are not particularly limited, and there may be a case where the component for forming the adhesive layer 13 is contained as a solute, or a case where it is contained as a dispersant. The release sheet 14 may be peeled as a process material, and the adhesive layer 13 may be protected until it is attached to the semiconductor wafer.

In addition, as a method for producing a laminated body in which two layers of release sheets 14 are laminated on both sides of the three-dimensional multilayer circuit manufacturing sheet 1, a coating solution can be applied to the aforementioned release sheet 14. A coating film is formed on the peeling surface, and it is dried to form a laminate composed of the adhesive layer 13 and the release sheet 14. The laminate is applied to the surface of the adhesive layer 13 which is opposite to the release sheet 14 and is applied. It is attached to the release surface of the other release sheet 14 to obtain a laminated body composed of the release sheet 14 / adhesive layer 13 / release sheet 14. The release sheet 14 of the laminate may be peeled as a process material, and the adhesive layer 13 may be protected until it is attached to the semiconductor wafer.

The plate 2 for manufacturing a three-dimensional bulk-layer circuit of the second embodiment can be manufactured in the same manner as the plate 2 for manufacturing a three-dimensional bulk-layer circuit. For example, the laminated body of the adhesive layer 13 and the release sheet 14 and the laminated body of the adhesive layer 12 and the base material 11 can be manufactured by making the laminated layer of the adhesive layer 13 and the adhesive layer 12 in contact with each other. Body-fitted to obtain a manufacturing sheet 2.

The laminated body of the adhesive layer 13 and the release sheet 14 can be prepared by applying the aforementioned coating solution to form the adhesive layer 13 and applying the aforementioned coating method to the release surface of the release sheet 14. A coating film is formed, and this coating film is dried and obtained.

Examples of the solvent include toluene, ethyl acetate, and methyl ethyl. Organic solvents such as ketones. By formulating these organic solvents to a solution having an appropriate solid content concentration, it is possible to further suppress the variation in the thickness (T2) of the adhesive layer 13 and to effectively form an adhesive having the aforementioned standard deviation for the thickness (T2).剂 层 13。 Agent layer 13. From the viewpoint of uniformly applying the coating liquid, the solid content concentration of the coating liquid is particularly preferably 5% by mass or more, and particularly preferably 10% by mass or more. From the same viewpoint, the solid content concentration is preferably 55% by mass or less, and more preferably 50% by mass or less. When the solid content concentration is 5% by mass or more, it is possible to suppress the occurrence of shrinkage and the like when forming a coating film, to easily dry the solvent sufficiently, and to more easily suppress variations in the thickness or physical properties of the adhesive layer 13. As a result, it becomes easy to adjust the standard deviation of the thickness (T2) of the adhesive layer 13 within the aforementioned range. In addition, when the solid content concentration is 55% by mass or less, it is possible to suppress the agglomeration of the filler in the coating liquid, facilitate the feeding of the coating liquid, and suppress the continuous generation of coating in a direction perpendicular to the coating direction. The cloth is uneven (transverse wave-like unevenness), and the occurrence of thickness deviation of the adhesive layer 13 can be suppressed. The viscosity of the coating liquid at 25 ° C measured with a B-type viscometer was 20 mPa. Above s is preferred, especially 25mPa. Above s is preferred. The viscosity is 500 mPa. Below s is preferred, especially 100mPa. The following s is preferred.

The laminated body of the adhesive layer 12 and the base material 11 can be prepared by preparing a coating liquid containing a material constituting the adhesive layer 12 and further containing a solvent or a dispersion medium as required, and applying the coating solution in accordance with the aforementioned coating method. A coating film is formed on one surface of the base material 11, and the coating film is obtained by drying. As another method for manufacturing a laminated body of the adhesive layer 12 and the base material 11, the adhesive layer 12 is formed on a release surface of a release sheet for a manufacturing process, and then the adhesive layer 12 is rotated. After printed on one side of the substrate 11, the release sheet for the process is peeled from the adhesive layer 12 to obtain a laminated body of the adhesive layer 12 and the substrate 11.

[Manufacturing method of three-dimensional product volume layer circuit]

By using the three-dimensional multi-layered circuit manufacturing plates 1 and 2 of this embodiment, a three-dimensional multi-layered circuit can be manufactured. An example of the manufacturing method will be described below.

First, the three-dimensional bulk-layer circuit manufacturing plates 1 and 2 of this embodiment are attached to one side of a semiconductor wafer having a through electrode. Specifically, the surface on the side of the adhesive layer 13 of the three-dimensional bulk-layer circuit manufacturing plates 1 and 2 is attached to one surface of the semiconductor wafer.

In addition, a semiconductor wafer having a through electrode may be weak. Therefore, the semiconductor wafer can be reinforced by being fixed to a support such as a support glass through a temporary fixing material. At this time, after the surface on the side of the semiconductor wafer on the laminated body is bonded to the three-dimensional stacked volume circuit manufacturing plates 1 and 2, the support and the temporary fixing material are peeled off at the same time.

When the three-dimensional multi-layer bulk-layer circuit manufacturing sheet 1 of the first embodiment is used, the cutting sheet is further laminated. At this time, a dicing sheet may be attached to the semiconductor wafer, and then the manufacturing sheet 1 may be attached to a surface of the semiconductor wafer on the side opposite to the dicing sheet. Alternatively, a manufacturing wafer 1 may be attached to a semiconductor wafer, and then a dicing wafer may be attached to a surface of the semiconductor wafer opposite to the manufacturing wafer 1. Alternatively, the dicing sheet may be attached to the side of the manufacturing sheet 1 for a laminated body obtained by attaching the manufacturing sheet 1 to a semiconductor wafer. On the other hand, in the case of using the three-dimensional stacked bulk layer circuit manufacturing sheet 2 of the second embodiment, it is not necessary to further laminate the cutting sheets, and the following cutting steps can be performed on the manufacturing sheet 2.

Next, the semiconductor wafer is cut into individual wafers (dicing step). At this time, at the same time as the semiconductor wafer is cut, the adhesive layer 13 is also cut. The method of cutting the wafer is not particularly limited, and can be performed using various conventionally known cutting methods. For example, the method of cutting a semiconductor wafer using a dicing blade is mentioned. Alternatively, other cutting methods such as laser cutting may be used.

After the dicing step, the semiconductor wafer is picked up. At this time, the semiconductor wafer is picked up in a state where the singulated adhesive layer 13 is attached. That is, the semiconductor wafer to which the adhesive layer 13 is attached is peeled off from the adhesive layer of the dicing sheet or the adhesive layer 12 of the three-dimensional bulk layer circuit manufacturing sheet 2. When the adhesive layer 12 is composed of an energy ray-curable adhesive, it is preferable to irradiate the adhesive layer 12 with energy rays before picking up. Thereby, since the adhesive force of this adhesive agent is low, it becomes easy to pick up a semiconductor wafer. In addition, if necessary, before picking up, the expanded cutting plate or the three-dimensional multi-layer volume circuit manufacturing plate 2 is used to expand the interval between the semiconductor wafers.

Next, the semiconductor wafer with the adhesive layer was placed on a circuit board. The semiconductor wafer with the adhesive layer is placed on the circuit substrate so that the electrodes on the semiconductor wafer side and the electrodes on the circuit substrate face each other.

Next, the semiconductor wafer and the circuit board with the adhesive layer are heated. After pressurizing, cooling is performed. Thereby, the semiconductor wafer and the circuit substrate are bonded through the adhesive layer 13, and the electrodes of the semiconductor wafer and the electrodes on the wafer mounting portion of the circuit substrate are electrically bonded through solder bumps formed on the semiconductor wafer. The welding conditions also depend on the metal composition used. For example, when Sn-Ag is used, it is better to heat at 200 to 300 ° C for 1 to 30 seconds.

After soldering, the semiconductor wafer and circuit board The intermediate adhesive layer 13 is hardened. The hardening system can be performed, for example, by heating at 100 to 200 ° C for 1 to 120 minutes. Such a hardening step may be performed under pressure. In addition, in the case where the hardening of the adhesive layer 13 is completed in the aforementioned welding step, such a hardening step may be omitted.

Next, a semiconductor wafer with a new adhesive layer is laminated on the semiconductor wafer adhered to the circuit substrate as described above. At this time, the surface of the new semiconductor wafer with the adhesive layer on the side of the adhesive layer 13 and the surface of the semiconductor wafer laminated on the circuit substrate on the side opposite to the circuit substrate are contacted, and two The through electrodes of the semiconductor wafer are laminated in such a manner that they are electrically connected to each other. Subsequently, soldering is performed between the through electrodes of the newly laminated semiconductor wafer and the through electrodes of the semiconductor wafer laminated on the circuit substrate, and the adhesive layer 13 interposed between these semiconductor wafers is hardened. The welding and hardening of the adhesive layer 13 at this time can be performed using the method and conditions described above. Thereby, a laminated body in which two semiconductor wafers are laminated on a circuit board can be obtained.

Repeating the steps of laminating a semiconductor wafer with an adhesive layer, soldering, and curing the adhesive layer 13 on the semiconductor wafer laminated on the circuit substrate as described above, the cured product of the adhesive layer 13 can be obtained. A laminated circuit formed by a plurality of semiconductor wafers. In such a laminated circuit, since the adhesive layer 13 contains a thermally conductive filler, and the standard deviation of the thickness (T2) of the adhesive layer 13 is in the aforementioned range, the laminated circuit system is excellent in heat dissipation. Therefore, by using the three-dimensional multilayer volume circuit manufacturing plates 1 and 2 of this embodiment, a multilayer circuit having high reliability can be manufactured.

In the method for manufacturing a multilayer circuit described above, one semiconductor wafer is laminated for each layer, and soldering and curing of the adhesive layer 13 are performed. This is to improve the efficiency of the manufacturing process. After laminating a plurality of semiconductor wafers, the semiconductor wafers can be soldered together and the adhesive layer 13 can be hardened between the semiconductor wafers.

The embodiments described above are described for easy understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above-mentioned embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

[Example]

Hereinafter, the present invention will be described in more detail by revealing examples, test examples, and the like, but the present invention is not limited at all by the following test examples and the like.

[Examples 1 to 7, Comparative Example 1]

A composition containing the constituent components shown in Table 1 was diluted with methyl ethyl ketone so that the solid content concentration became 40% by mass to obtain a coating liquid. Using a B-type viscometer to measure the viscosity of the coating solution at 25 ° C was 50 mPa. s. This coating solution was coated on a silicone-treated release film (manufactured by LINTEC, SP-PET381031), and the obtained coating film was dried in an oven at 100 ° C. for 1 minute to obtain a thickness of 45 μm. The first laminated body composed of an adhesive layer and a release film.

100 parts by mass of an acrylic copolymer (weight average molecular weight: 700,000) (solid) obtained by copolymerizing 80 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of methyl acrylate, and 10 parts by mass of 2-hydroxyethyl acrylate Component conversion value; the same applies hereinafter), and 10 parts by mass of an isocyanate-based crosslinking agent (manufactured by Polyurethane Industries, CORONATE L) was mixed to prepare an adhesive composition.

The adhesive composition obtained as described above was applied to one surface of an ethylene-methacrylic acid copolymer (EMAA) film (thickness: 100 μm) as a base material to form a coating film. Subsequently, the coating film was dried at 100 ° C for 1 minute. Thereby, a second laminated body composed of an adhesive layer with a thickness of 10 μm and a substrate was obtained. The storage elastic modulus of this adhesive layer at 23 ° C. was measured by a method described later to be 4.6 × 10 ⁵ Pa.

Next, a surface of the first multilayer body on the adhesive layer side and a surface of the second multilayer body on the adhesive layer side were bonded to obtain a three-dimensional bulk volume circuit manufacturing plate.

[Comparative Example 2]

A composition containing the constituent components shown in Table 1 was diluted with methyl ethyl ketone so that the solid content concentration became 55% by mass to obtain a coating liquid. The viscosity of the coating liquid at 25 ° C was 150 mPa using a B-type viscometer. s. Except having used this coating liquid to form an adhesive layer, it carried out similarly to Example 1, and obtained the board | substrate for manufacture of a three-dimensional bulk volume circuit.

The details of the constituent components shown in Table 1 are as follows.

High molecular weight ingredients

． Bisphenol A (BPA) / Bisphenol F (BPF) copolymerized phenoxy resin: manufactured by Toto Kasei Co., Ltd., product name "ZX-1356-2", glass transition temperature of 71 ° C, weight average molecular weight 60,000

Thermosetting component

． Epoxy resin 1: Ginseng (hydroxyphenyl) methane type solid epoxy resin, manufactured by JAPAN EPOXY RESINS, product name "E1032H60", 5% weight reduction temperature 350 ° C, solid, melting point 60 ° C

． Epoxy resin 2: Bis-F liquid epoxy resin, JAPAN EPOXY Manufactured by RESINS, product name "YL-983U", epoxy equivalent 184

． Epoxy resin 3: Long chain Bis-F modified epoxy resin, made by JAPAN EPOXY RESINS, product name "YL-7175"

Hardening catalyst

． 2MZA-PW: 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, manufactured by Shikoku Chemical Industry Co., Ltd., product name "2MZA-PW "Flux composition with a melting point of 250 ° C

． Rosin derivative: Arakawa Chemical Industry, softening point: 124 ~ 134 ℃ inorganic filler

filler

． Thermally conductive filler (spherical alumina); spherical alumina, manufactured by Denki Chemical Industry Co., Ltd., product name "DAM-0", average particle size 3 μm, thermal conductivity 40 W / m. K

． Thermally conductive filler (spherical zinc oxide): spherical zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd., with an average particle diameter of 0.6 μm and a thermal conductivity of 54 W / m. K

． Thermally conductive filler (boron nitride): boron nitride, manufactured by Showa Denko Corporation, product name "UHP-2", shape: plate-like, average particle diameter 11.8 μm, aspect ratio 11.2, thermal conductivity in major axis direction 200 W / m ． K

． Fused silica filler: average particle size 3 μm, thermal conductivity 2 W / m. K

In addition, the storage elastic modulus of the adhesive layer at 23 ° C. is a laminated body of an adhesive layer having a thickness of 800 μm by laminating a plurality of adhesive layers, and punching out the laminated body of the adhesive layer. A measurement sample obtained by forming a circular shape with a diameter of 10 mm was measured at a frequency of 1 Hz and a measurement temperature range using a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments). Measure the storage elastic modulus (Pa) under the conditions of -50 ~ 150 ℃ and temperature increasing rate of 3 ℃ / min.

[Test Example 1] Measurement of thermal conductivity

For each of the examples and comparative examples, the composition containing the constituent components shown in Table 1 was diluted with methyl ethyl ketone so that the solid content concentration became 40% by mass, and applied to a silicone-treated release film. (LINTEC Corporation, SP-PET381031), the obtained coating film was dried in an oven at 100 ° C. for 1 minute to form an adhesive layer having a thickness of 40 μm. A plurality of layers of the adhesive layer obtained in accordance with this step were laminated so as to have a thickness of 2 mm. A disc-shaped adhesive layer having a diameter of 5 cm was punched out from the laminated body having a thickness of 2 mm as a sample for measurement.

This sample was heated at 130 ° C for 2 hours to harden, and then the thermal conductivity (W / m · K) was measured using a thermal conductivity measuring device (EKO Corporation, HC-110). The results are shown in Table 2.

[Test Example 2] Measurement of the thickness of the adhesive layer and the standard deviation of the thickness

With respect to the first laminates produced in the examples and comparative examples, the thickness (T2) of the adhesive layer was measured at a total interval of 50 mm at 100 points. Based on the measurement results, the average value (μm) of the thickness (T2) and the standard deviation (μm) of the thickness (T2) were calculated. The results are shown in Table 2.

[Experimental Example 3] Evaluation of heat release by temperature cycle test

Evaluation wafers having bumps formed on one side and pads formed on the other side were prepared, and a fully automatic multi-wafer placement machine (manufactured by LINTEC, RAD-2700F / 12) was used. The manufactured three-dimensional bulk-layer circuit manufacturing plate is attached to the bump-formed side of the wafer for evaluation. Surface and fixed to the ring frame.

Next, a fully automatic dicing saw (Disco 651, manufactured by DISCO Corporation) was used to simultaneously cut the adhesive layer and the wafer for evaluation, and the wafers were sliced into wafers having a size of 7.3 mm × 7.3 mm in plan view.

Next, a flip-chip bonding machine (Toray Engineering, FC3000W) was used to pick up the sliced adhesive layer and wafer at the same time, and the flip-chip was bonded to the substrate. Subsequently, the second-layer wafer with the adhesive layer attached thereto is bonded to the first-layer wafer temporarily placed on the substrate. This step is repeated to manufacture a semiconductor device in which a total of five layers of wafers are stacked on a substrate.

The obtained semiconductor device was subjected to a temperature cycle test of 1000 cycles under an environment where -55 ° C, 10 minutes, and 125 ° C, 10 minutes were set as one cycle. For the semiconductor devices before and after the test, a digital multimeter was used to measure the connection resistance between the semiconductor wafers to determine the connection resistance of the semiconductor device after the test and the connection resistance of the semiconductor device before the test. The rate of change of the value. The splicing reliability was evaluated in accordance with the following evaluation criteria. The results are shown in Table 2.

○: The change rate of the connection resistance value is 20% or less.

×: The change rate of the connection resistance value is more than 20%.

[Test Example 4] Evaluation of embedding property

A plurality of semiconductor devices were manufactured by the method described in Test Example 3. A digital microscope was used to observe the four sides of five semiconductor devices arbitrarily selected from these semiconductor devices, and to confirm the occurrence of cracks in the bumps and the state where the bumps were embedded in the adhesive layer, and the layers on each side were also measured. Product direction thickness. Based on these results, the results obtained in the examples and comparative examples were evaluated in accordance with the following evaluation criteria. Embeddedness of bumps of a plate for manufacturing a three-dimensional multi-layer circuit. The results are shown in Table 2.

○: In all of the five semiconductor devices, no cracks were generated in the bumps, and the bumps were well embedded in the adhesive layer, and the thickness in the lamination direction was the same across the four sides.

×: Among the five semiconductor devices, cracks were generated in the bumps, the bumps were not sufficiently embedded in the adhesive layer, or the thickness in the lamination direction was different between the four sides.

It can be known from Table 2 that the adhesive layer of the plate for manufacturing a three-dimensional volumetric layer circuit of the example in the example has 0.5 W / m. Excellent heat above K The standard deviation of the conductivity and the thickness (T2) of the adhesive layer is 2.0 μm or less. In addition, it was confirmed that the multilayer circuit produced using the three-dimensional multilayer bulk circuit circuit manufacturing plate obtained in the example was excellent in heat release property, the results of the temperature cycle test were good, and the embedding property of the bumps was also excellent.

On the other hand, in the adhesive layer of the three-dimensional bulk-layer circuit manufacturing sheet of the comparative example, the thermal conductivity was 0.3 W / m. Insufficient value of K is also insufficient for heat dissipation of a multilayer circuit produced using the manufacturing sheet. Furthermore, for the plate for manufacturing a three-dimensional multi-layered multilayer circuit of Comparative Example 2, the standard deviation of the thickness (T2) of the adhesive layer was 2.5 μm, the heat dissipation of the multilayer circuit was insufficient, and the embedding of the bump was poor. .

[Industrial availability]

The plate system for manufacturing a three-dimensional multilayer volume circuit of the present invention has excellent heat dissipation and can be suitably used for manufacturing a multilayer circuit having high reliability.

1‧‧‧Three-dimensional bulk layer circuit manufacturing plate

13‧‧‧ Adhesive layer

14‧‧‧ peeling sheet

Claims (16)

A plate for manufacturing a three-dimensional multi-layered multilayer circuit, which is interposed between a plurality of semiconductor wafers having through electrodes. The three-dimensional multi-layered multilayer circuit used in order to connect the plurality of semiconductor wafers to each other to form a three-dimensional multi-layered multilayer circuit. The bulk layer circuit manufacturing sheet is characterized in that the three-dimensional bulk volume circuit manufacturing sheet system has at least a hardenable adhesive layer, the adhesive layer system includes a thermally conductive filler, and the thickness of the adhesive layer The standard deviation of (T2) is 2.0 μm or less. The three-dimensional bulk-layer circuit manufacturing plate as described in item 1 of the scope of patent application, wherein the thermally conductive filler is made of a material selected from the group consisting of metal oxide, silicon carbide, carbide, nitride, and metal hydroxide. Made up. According to the three-dimensional bulk-layer circuit manufacturing sheet described in item 1 of the scope of the patent application, the content of the thermally conductive filler in the adhesive layer is 35% by mass or more and 95% by mass or less. According to the three-dimensional multi-layer bulk layer circuit manufacturing plate described in the first item of the patent application scope, wherein the thermal conductivity of the aforementioned thermally conductive filler at 23 is 10 W / m. K or more. According to the three-dimensional multi-layer bulk-layer circuit manufacturing sheet according to item 1 of the scope of the patent application, the average particle diameter of the thermally conductive filler is 0.01 μm or more and 20 μm or less. According to the three-dimensional multi-layer volume circuit manufacturing plate described in the first patent application range, wherein the thermal conductivity of the aforementioned adhesive layer after hardening is 0.5 W / m. Above K, 8.0W / m. K or less. According to the three-dimensional multi-layer bulk-layer circuit manufacturing sheet described in item 1 of the scope of the patent application, the material constituting the aforementioned adhesive layer contains a thermosetting component, a high molecular weight component, and a hardening catalyst. According to the three-dimensional bulk-layer circuit manufacturing sheet described in item 1 of the scope of patent application, the glass transition temperature of the high molecular weight component is 50 ° C or higher. According to the three-dimensional bulk-layer circuit manufacturing sheet described in item 1 of the scope of patent application, the material constituting the aforementioned adhesive layer contains a flux component. According to the three-dimensional multi-layer bulk-layer circuit manufacturing sheet described in item 1 of the scope of patent application, the thickness of the aforementioned adhesive layer is 2 μm or more and 500 μm or less. The three-dimensional bulk-layer circuit manufacturing sheet described in item 1 of the scope of the patent application, wherein the three-dimensional bulk-layer circuit manufacturing sheet further includes: an adhesive layer, which is laminated on the adhesive layer. One surface side; and a substrate, which is laminated on the side of the adhesive layer opposite to the surface of the adhesive layer. According to the three-dimensional multi-layer bulk-layer circuit manufacturing sheet according to item 11 of the scope of the patent application, the thickness of the aforementioned substrate is 10 μm or more and 500 μm or less. According to the three-dimensional bulk-layer circuit manufacturing sheet described in item 11 of the scope of patent application, the ratio (T2 / T1) of the thickness (T2) of the adhesive layer to the thickness (T1) of the substrate is 0.01 or more , Below 5.0. According to the three-dimensional multi-layer bulk-layer circuit manufacturing sheet described in item 11 of the scope of patent application, the storage elastic modulus of the aforementioned adhesive at 23 ° C. is 1 × 10 ³ Pa or more and 1 × 10 ⁹ Pa or less. According to the three-dimensional multi-layer bulk-layer circuit manufacturing sheet as described in item 11 of the scope of the patent application, the tensile elastic modulus of the aforementioned substrate at 23 ° C is 100 MPa or more. Up to 5000MPa. A method for manufacturing a three-dimensional voluminous layer circuit, which comprises the following steps: one side of the aforementioned adhesive layer of the plate for manufacturing a three-dimensional voluminous layer circuit as described in item 1 of the scope of patent application or a patent application The step of bonding the adhesive layer on the opposite side to the adhesive layer of the three-dimensional multi-layer volume circuit manufacturing plate described in item 11 to at least one side of a semiconductor wafer having a through electrode; The step of cutting the aforementioned semiconductor wafer and the aforementioned adhesive layer of the three-dimensional bulk-layer circuit manufacturing plate at the same time, and singulating into a semiconductor wafer with an adhesive layer; A step of obtaining a semiconductor wafer laminate by laminating a plurality of semiconductor wafers of the agent layer in such a manner that the through electrodes are electrically connected to each other and the adhesive layer and the semiconductor wafer are alternately arranged to obtain a semiconductor wafer laminate; and The step of curing the aforementioned adhesive layer of the laminated body, and then adhering the aforementioned semiconductor wafers constituting the aforementioned semiconductor wafer laminated body to each other.