JP2012216840A - Three-dimensional integrated circuit laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a three-dimensional integrated circuit laminate which is filled with an interlaminar filler composition having both of high heat conductivity and low dielectric constant.SOLUTION: A three-dimensional integrated circuit laminate comprises: a semiconductor substrate laminate formed by stacking at least two or more layers of semiconductor substrates in which a semiconductor device layer is formed thereon; and a first interlaminar filler layer containing a resin (A) and an inorganic filler (B) having dielectric constant of 6 or lower, between the semiconductor substrates.

Description

  The present invention relates to a three-dimensional integrated circuit laminate in which semiconductor substrates are laminated.

  In recent years, in order to improve the performance of semiconductor devices such as higher speed and higher capacity, in addition to miniaturization of transistors and wiring, the performance has been improved by three-dimensional (3D) stacking by stacking two or more semiconductor substrates. Research and development is underway.

  Specifically, after forming a thin film of an interlayer filler composition by underfill process in which a filler is poured from the side between the substrates after bonding the semiconductor substrate, or by applying on a wafer, a B-stage is formed, and then the semiconductor is formed by dicing. A process is proposed in which a three-dimensional integrated circuit laminate is formed by cutting out a substrate, repeating temporary bonding using pressure heating using this semiconductor substrate, and finally performing main bonding (solder bonding) under pressure heating conditions. (See Non-Patent Documents 1 and 2).

  Various problems have been pointed out for the practical application of such a three-dimensional integrated circuit device. One of them is a problem of heat dissipation from heat generated from devices such as transistors and wiring. This problem is caused by the fact that the thermal conductivity of the interlayer filler composition used when stacking semiconductor substrates is generally very low compared to metals, ceramics, etc. There is concern about performance degradation such as malfunction of semiconductor devices due to heat storage.

  Another problem is the problem of the dielectric constant of the interlayer filler composition used for stacking semiconductor devices. In recent years, the operating frequency of semiconductor devices has been increasing year by year, and not only the inside of a semiconductor substrate but also the signal transmission between semiconductor substrates requires a conduction speed exceeding GHz. At this time, if the dielectric constant of the interlayer filler composition used for stacking the semiconductor devices is high, it may cause a signal transmission delay in the wiring between the substrates, resulting in a decrease in the operating speed of the entire device. ing.

  One technique for solving these problems is to increase the thermal conductivity of the interlayer filler composition applied between the substrates of the three-dimensional integrated circuit laminate. For example, by applying a high thermal conductivity epoxy resin as a single resin constituting the interlayer filler composition, or by combining such a high thermal conductivity resin with a high thermal conductivity inorganic filler, the interlayer filler composition Attempts have been made to increase the thermal conductivity of these. For example, a resin composition having high thermal conductivity using an epoxy resin having a mesogen and a curing agent has been reported (Patent Document 1). Further, it is disclosed that thermal conductivity is improved by blending a resin having high thermal conductivity boron nitride as a filler instead of a conventional silica-based filler as an inorganic filler (Patent Document 2).

Japanese Patent No. 4118691 Japanese translation of PCT publication No. 2008-510878

“Electronics Package Technology (CMC Technical Library)”, CM Publishing (2003), p. 102 Proceedings of the 23rd Electronics Packaging Society Conference, Japan Institute of Electronics Packaging (2009), p. 61

In the three-dimensional integrated circuit laminate in which the semiconductor substrates are laminated, the distance between the semiconductor substrates is expected to be 50 μm or less in order to further improve performance such as signal transmission speed and capacity. There is a need for a three-dimensional integrated circuit laminate in which the fine substrates are joined together with an interlayer filler composition having high thermal conductivity and low dielectric constant.
As a conventional technique for filling a space between substrates, an underfill process for bonding a semiconductor substrate and an organic substrate or organic substrates to each other has been proposed. However, after applying flux to the electrical connection terminals, bonding is performed, and after the flux is washed, the filler is filled from the side between the substrates by using a capillary phenomenon. It has become difficult to uniformly fill.

  As a method of laminating a semiconductor substrate on another substrate, an OBAR method is also proposed in which an interlayer filler is applied to a substrate and then bonding between the substrates is performed. However, the thermal conductivity of the interlayer filling material used in the OBAR method is comparable to the material of the underfill process, and is insufficient for the thermal conductivity between the semiconductor substrates of the three-dimensional integrated circuit stack. It was.

  The present invention has been made in view of the above problems. In a laminate of a semiconductor substrate such as a silicon substrate on which a semiconductor device layer is formed and a laminate of the laminate and an organic substrate, a specific resin and an inorganic substrate are provided. To provide a three-dimensional integrated circuit laminate filled with an interlayer filler composition having both high thermal conductivity and low dielectric constant by laminating a semiconductor substrate with an interlayer filler composition combined with a filler. It is the purpose.

  As a result of intensive studies, the present inventors have found that the following invention can solve the above problems, and have completed the present invention.

That is, the present invention relates to the following inventions.
<1> A semiconductor substrate laminate in which at least two semiconductor substrates on which a semiconductor device layer is formed is laminated, and a resin (A) and an inorganic filler (B) having a dielectric constant of 6 or less are provided between the semiconductor substrates. A three-dimensional integrated circuit laminate having a contained first interlayer filler layer.
<2> The three-dimensional integrated circuit laminate according to <1>, wherein the semiconductor substrate is a silicon substrate.
<3> The three-dimensional integrated circuit laminate according to <1> or <2>, wherein the thermal conductivity of the first interlayer filler layer is 0.8 W / (m · K) or more.
<4> The three-dimensional integrated circuit laminate according to any one of <1> to <3>, wherein the inorganic filler (B) has a thermal conductivity of 2 W / (m · K) or more.
<5> The three-dimensional integrated circuit laminate according to any one of <1> to <4>, wherein a dielectric constant of the first interlayer filler layer is 5 or less.
<6> Any of <1> to <5>, wherein the first interlayer filler layer contains 50 to 400 parts by weight of the inorganic filler (B) per 100 parts by weight of the resin (A). A three-dimensional integrated circuit laminate according to claim 1.
<7> The three-dimensional integrated circuit laminate according to any one of <1> to <6>, wherein the resin (A) is a resin mainly composed of an epoxy resin.
<8> The three-dimensional integrated circuit laminate according to any one of <1> to <7>, wherein the inorganic filler (B) is boron nitride.
<9> The three-dimensional integrated circuit laminate according to any one of <1> to <8>, wherein a thickness of the first interlayer filler layer is 1 μm or more and 50 μm or less.
<10> The three-dimensional integrated circuit laminate according to any one of <1> to <9>, wherein a solder connection terminal for connecting an electric signal is included in the first interlayer filler layer between the semiconductor substrates. .
<11> The semiconductor substrate laminate is further mounted on an organic substrate, and a second interlayer containing a resin (a) and an inorganic filler (b) between the semiconductor substrate laminate and the organic substrate. The three-dimensional integrated circuit laminate according to any one of <1> to <10>, which has a filler layer.
<12> The three-dimensional integrated circuit laminate according to <11>, wherein a dielectric constant of the second interlayer filler layer is 6 or less.
<13> The three-dimensional integrated circuit laminate according to <11> or <12>, wherein the thermal conductivity of the second interlayer filler layer is 0.4 W / (m · K) or more.
<14> The three-dimensional integrated circuit laminate according to any one of <11> to <13>, wherein the thickness of the second interlayer filler layer is 50 μm or more and 300 μm or less.

  According to the present invention, high heat dissipation and high-speed operation are possible by laminating a semiconductor substrate on which a semiconductor device layer is formed with a first interlayer filler layer having high thermal conductivity and low dielectric constant. A three-dimensional integrated circuit stack can be formed.

1 is a conceptual cross-sectional view of a three-dimensional integrated circuit laminate (first three-dimensional integrated circuit laminate) according to a first embodiment of the present invention. It is a schematic diagram of the cross-sectional structure of a semiconductor substrate. It is a conceptual sectional view of the three-dimensional integrated circuit layered product (second three-dimensional integrated circuit layered product) concerning the 2nd embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

(1) First three-dimensional integrated circuit laminate The three-dimensional integrated circuit laminate of the present invention has a semiconductor substrate laminate in which at least two semiconductor substrates on which semiconductor device layers are formed are laminated. In between, it has the 1st interlayer filler layer containing resin (A) and the inorganic filler (B) whose dielectric constant is 6 or less.

FIG. 1 is a conceptual cross-sectional view of a three-dimensional integrated circuit laminate (hereinafter referred to as “first three-dimensional integrated circuit laminate”) according to a first embodiment of the present invention. In FIG. 1, in order to facilitate understanding of the structure of the three-dimensional integrated circuit laminate, the thicknesses and sizes of the other constituent members with respect to the semiconductor substrate are shown larger than actual.
As shown in FIG. 1, a first three-dimensional integrated circuit laminate 1 includes a semiconductor substrate laminate in which semiconductor substrates 10, 20, and 30 each having semiconductor device layers 11, 21, and 31 formed thereon are laminated in three layers. Consists of. In this embodiment, the semiconductor substrate is laminated in three layers, but this is an example, and any number of layers may be used as long as it is two or more layers.
Between the semiconductor substrate 10 and the semiconductor substrate 20 and between the semiconductor substrate 20 and the semiconductor substrate 30, first interlayer filler layers 40 and 50 containing a resin (A) and an inorganic filler (B) are provided, respectively. is doing.

In FIG. 2, the schematic diagram of the cross-section of the semiconductor substrate 10 is shown. A semiconductor device layer 11 including a fine electronic circuit is formed on the semiconductor substrate 10. In order to protect the semiconductor device layer 11 from the outside world, a buffer coat film 12 made of polyimide resin or the like is formed on the surface thereof. Further, in the three-dimensional integrated circuit laminate 1, the semiconductor substrate 10 has the same configuration as that of the semiconductor substrate 10, and the semiconductor substrate 10 and the semiconductor device layer 21 on the semiconductor substrate 20 adjacent to the semiconductor substrate 10 can be electrically connected. The substrate 10 is provided with a semiconductor substrate through electrode 13, a land terminal 14 and a solder bump 15 provided so as to penetrate the substrate.
Further, in the first three-dimensional integrated circuit laminate 1, in order to ensure electrical connection between semiconductor device layers in adjacent semiconductor substrates (the semiconductor substrate 10 and the semiconductor substrate 20, and the semiconductor substrate 20 and the semiconductor substrate 30). The semiconductor substrates 10, 20 and 30 are provided with semiconductor substrate through electrodes 13, 23 and 33, land terminals 24 and 34, and solder bumps 15, 25 and 35 provided so as to penetrate the substrate. The land terminal 24 and the solder bump 15, and the land terminal 34 and the solder bump 25 exist in the form included in the first interlayer filler layers 40 and 50, respectively, and the semiconductor substrate 10, the semiconductor substrate 20, and the semiconductor substrate 20. And the function of connecting electrical signals between the semiconductor substrate 30 and the semiconductor substrate 30.

  A solder connection terminal comprising land terminals 24 and 34 and solder bumps 15 and 25 for electrical signal connection between the semiconductor substrates on which the semiconductor device layers are formed in the first interlayer filler layers 40 and 50. However, the present invention is not limited to this as long as electrical connection of the semiconductor device layers on the respective semiconductor substrates can be secured.

  Hereinafter, the first three-dimensional integrated circuit laminate including the semiconductor substrate laminate of the present invention will be described in detail.

(1-1) Semiconductor substrate As the semiconductor substrate in the first three-dimensional integrated circuit laminate, any material that can be used as a substrate in the manufacture of an integrated circuit can be used, but a silicon substrate is preferably used. Is done. The silicon substrate may be used as it is according to the diameter of the substrate, or may be used after thinning to 100 μm or less by backside polishing such as backside etching or backgrinding.
As solder bumps, fine solder balls may be used, and after forming openings by lithography, resist plating is performed by solder plating directly on the base of the openings or after nickel or copper posts are formed. After removing, solder bumps may be formed by heat treatment. The solder composition is not particularly limited, but a solder containing tin as a main component is preferably used in consideration of electrical bondability and low-temperature bondability.
The land terminal can be formed by forming a thin film using PVD or the like on a semiconductor substrate and then removing unnecessary portions by lithography using a resist film and dry or wet etching. The material of the land terminal is not particularly limited as long as it can be bonded to the solder bump, but gold or copper can be preferably used in consideration of the bondability with solder and the reliability.

(1-2) First Interlayer Filler Layer The first interlayer filler layer is formed between the semiconductor substrates and contains a resin (A) and an inorganic filler (B).

The inorganic filler (B) must have a dielectric constant of 6 or less, and preferably 5 or less. By setting the dielectric constant of the inorganic filler (B) to 6 or less, the first interlayer filler layer can obtain low dielectricity satisfying the performance as a semiconductor substrate laminate with an appropriate addition amount.
In addition, although the dielectric constant of an inorganic filler (B) can be measured by arbitrary methods, generally it can obtain | require after inserting a sample between metal electrodes and measuring a capacity | capacitance and a dielectric loss tangent.
An arbitrary frequency can be used for the measurement of the dielectric constant, but a frequency of 10 MHz is preferably used from the viewpoint of measurement accuracy. Further, as the operating frequency of the semiconductor is increased, it is more preferable to use 100 MHz to 10 GHz for the dielectric constant measurement frequency.

  In particular, the dielectric constant of the first interlayer filler layer is preferably 5 or less. A dielectric constant of the first interlayer filler layer exceeding 5 is not preferable because it causes a signal transmission delay in the wiring between the substrates, resulting in a decrease in the operation speed of the entire device.

The thermal conductivity of the first interlayer filler layer is preferably 0.8 W / m or more, and more preferably 1.0 W / (m · K) or more.
When the thermal conductivity of the first interlayer filler layer is less than 0.8 W / m, the thermal conductivity between the semiconductor substrates is not sufficient, and heat accumulates in the semiconductor substrate, resulting in a high temperature, causing a malfunction. Therefore, it is not preferable.

The thermal conductivity of the inorganic filler (B) contained in the first interlayer filler layer is preferably 2 W / (m · K) or more.
When the thermal conductivity of the inorganic filler (B) is 2 W / (m · K) or more, the thermal conductivity is about 5 times higher than that of the resin (A), and the interlayer filler layer can be added with an appropriate addition amount. The thermal conductivity can be sufficiently improved.

  Moreover, it is preferable that content of the inorganic filler (B) contained in a 1st interlayer filler layer is 50 to 400 weight part per 100 weight part of resin (A). More preferably, it is 75 parts by weight or more and 300 parts by weight or less. By setting it as such content, the 1st interlayer filler layer can maintain sufficient heat conductivity, and can maintain the viscosity of the grade which can form a uniform coating film.

  The thickness of the first interlayer filler layer is preferably 1 μm or more and 50 μm or less. More preferably, they are 3 micrometers or more and 45 micrometers or less, More preferably, they are 5 micrometers or more and 40 micrometers or less. When the thickness is increased, the distance between wirings as a semiconductor becomes longer, and signal wiring delay is caused. Therefore, the merit by three-dimensionally laminating the substrates decreases, which is not preferable. When the thickness is reduced, the distance between the wirings is shortened and the wiring delay of the signal can be reduced, but the processing including the film thickness uniformity of the interlayer filler layer becomes extremely difficult. By setting it as the said thickness, workability and performance can be made compatible.

Hereinafter, each component in the composition constituting the first interlayer filler layer (hereinafter sometimes referred to as “first interlayer filler composition”) will be described in detail.
A 1st interlayer filler composition contains resin (A) and an inorganic filler (B), and also contains a hardening | curing agent (C), a flux (D), etc. as needed.

[Resin (A)]
The resin (A) has a thermal conductivity of 0.2 W / (m · K) in order to obtain sufficient thermal conductivity when combined with the inorganic filler (B) as the first interlayer filler composition. The above is preferable.
In addition, the resin (A) preferably has a melt viscosity at 50 ° C. of 2000 Pa · s or more and 10000 Pa · s in order to perform alignment with the substrate to be bonded after forming a thin film on the substrate and before temporary bonding. More preferably, it is s or more.
Further, when the main bonding is performed after temporary bonding, the resin (A) has a melt viscosity at 120 ° C. in order to melt the first interlayer filler composition by heating and connect the electric bonding terminals. 100 Pa · s or less is preferable, and 20 Pa · s or less is more preferable.

Specific examples of the resin (A) include epoxy resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, polyester resin, allyl resin, alkyd resin, urethane resin, silicon resin, acrylic resin, polyimide resin, and the like. Can do. Among these resins, thermosetting resins excellent in heat resistance and various electric characteristics are preferable. Among thermosetting resins, a resin mainly composed of an epoxy resin is preferable from the viewpoint of processability before curing, B-staging film properties, other curing characteristics, cured film properties, and the like, and a resin composed only of an epoxy resin is more preferable.
Here, “mainly composed of epoxy resin” means that the proportion of the epoxy resin in the resin (A) is 50% by weight or more, preferably 60% by weight or more (including 100% by weight). It is.

Hereinafter, the case where an epoxy resin is used as an example of a preferable resin (A) will be described.
Any epoxy resin can be used as the epoxy resin. The epoxy resin may be only an epoxy resin having one type of structural unit, or a plurality of epoxy resins having different structural units may be combined.

Here, in combination with coating properties or film-forming properties and adhesiveness, in order to obtain a highly heat-conductive cured product by reducing voids at the time of bonding, at least a phenoxy resin (hereinafter referred to as “epoxy resin” (to be described later) as an epoxy resin. A1) ”is preferably included, and the weight ratio of the epoxy resin (A1) to the total amount of the epoxy resin is preferably contained in the range of 5 to 95% by weight. More preferably, it is contained in the range of 10 to 90% by weight, still more preferably 20 to 80% by weight.
Hereinafter, the epoxy resin (A1) will be described.

[Epoxy resin (A1)]
The phenoxy resin usually refers to a resin obtained by reacting an epihalohydrin and a dihydric phenol compound, or a resin obtained by reacting a divalent epoxy compound and a divalent phenol compound. Among these, a phenoxy resin that is an epoxy resin having a molecular weight of 200 or more is particularly referred to as an epoxy resin (A1). In addition, the upper limit of the weight average molecular weight of the epoxy resin (A1) is preferably 50000 or less, and more preferably 30000 or less.

  The epoxy resin (A1) is preferably a phenoxy resin having at least one skeleton selected from the group consisting of naphthalene skeleton, fluorene skeleton, biphenyl skeleton, anthracene skeleton, pyrene skeleton, xanthene skeleton, adamantane skeleton and dicyclopentadiene skeleton. . Among them, a phenoxy resin having a fluorene skeleton and / or a biphenyl skeleton is particularly preferable because the heat resistance is further improved.

As described above, the epoxy resin may include a plurality of epoxy resins having different structural units.
The epoxy resin other than the epoxy resin (A1) is preferably an epoxy resin having two or more epoxy groups in the molecule (hereinafter sometimes referred to as “epoxy resin (A2)”). Bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene Various epoxy resins, such as a type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and a polyfunctional phenol type epoxy resin, can be mentioned.
These can be used alone or as a mixture of two or more.

  The weight average molecular weight of the epoxy resin (A2) is preferably 100 to 5000, more preferably 200 to 4000, from the viewpoint of controlling the melt viscosity. When the weight average molecular weight is lower than 100, the heat resistance tends to be inferior. When the weight average molecular weight is higher than 5000, the melting point of the epoxy resin tends to be high, and the bonding property tends to decrease.

  Further, the resin (A) may contain a resin other than the epoxy resin (A1) and the epoxy resin (A2) (hereinafter referred to as “other resin”) as long as the purpose is not impaired.

In the resin (A), the ratio of the epoxy resin (A1) in the total resin including the epoxy resin (A1) and the epoxy resin (A2) is 10 to 90% by weight, preferably 20 to 80% by weight. The “all resins including the epoxy resin (A1) and the epoxy resin (A2)” means that when the resin (A) is only the epoxy resin (A1) and the epoxy resin (A2), the epoxy resin (A1) And the epoxy resin (A2), and when other resins are included, it means the total of the epoxy resin (A1), the epoxy resin (A2), and the other resins.
When the ratio of the epoxy resin (A1) is 10% by weight or more, the effect of improving the thermal conductivity by blending the epoxy resin (A1) can be sufficiently obtained, and the desired high thermal conductivity can be obtained. it can. When the proportion of the epoxy resin (A1) is less than 90% by weight and the epoxy resin (A2) is 10% by weight or more, the compounding effect of the epoxy resin (A2) is exhibited, and the curability and physical properties of the cured product are sufficient. It will be a thing.

[Inorganic filler (B)]
As described above, the inorganic filler (B) used in the present invention must have a dielectric constant of 6 or less, and preferably 5 or less. A dielectric constant exceeding 6 is not preferable because it causes a signal transmission delay in the wiring between the substrates, resulting in a decrease in the operation speed of the entire device.
When the dielectric constant is 6 or less, preferably 5 or less, the signal transmission delay can be reduced, and the calculation processing speed of the semiconductor device can be improved.

  The inorganic filler (B) used in the present invention preferably has a high thermal conductivity, and is preferably 2 W / (m · K) or more as described above.

As the inorganic filler (B), alumina (Al ₂ O ₃ : thermal conductivity 30 W / (m · K)), aluminum nitride (AlN: thermal conductivity 260 W / (m · K)), boron nitride (BN: heat) Conductivity 3 W / (m · K) (thickness direction), 275 W / (m · K) (in-plane direction)), silicon nitride (Si ₃ N ₄ : thermal conductivity 23 W / (m · K)), silica ( SiO ₂ : Thermal conductivity of 1.4 W / (m · K)), etc., but the inorganic filler (B) is a device in which it has a combination of stability against oxygen, water and high temperature exposure and low dielectric properties. The inorganic filler (B) is preferably Al ₂ O ₃ , AlN, BN, or SiO ₂ , and BN is particularly preferable. These inorganic fillers (B) may be used alone or in a combination of two or more in any combination and ratio.

In addition, as for the inorganic material used as an inorganic filler (B), powder may have aggregated immediately after a commercial item or a synthesis | combination. Therefore, the inorganic material used as the inorganic filler (B) is preferably pulverized to an appropriate particle size (usually 10 μm or less).
The method for pulverizing the inorganic material is not particularly limited, and a conventionally known pulverization method such as a method of stirring and mixing with a pulverizing medium such as zirconia beads or jet injection can be applied.
In addition, the inorganic filler (B) may be appropriately subjected to surface treatment in order to improve dispersibility in the resin (A) or the coating solution. In addition, a heat-treated filler may be used to increase crystallinity or to remove moisture.

  As described above, the content of the inorganic filler (B) is preferably 50 to 400 parts by weight, more preferably 75 to 300 parts by weight per 100 parts by weight of the resin (A). is there. If the content of the inorganic filler (B) is less than 50 parts by weight, sufficient thermal conductivity may not be obtained, and if it exceeds 400 parts by weight, the viscosity of the composition increases and a uniform coating film is formed. Problems such as inability to form may occur.

[Curing agent (C)]
As the resin (A), the first interlayer filler composition may contain a curing agent (C). When using an epoxy resin, the hardening | curing agent (C) used by this invention shows the substance which contributes to the crosslinking reaction between the epoxy groups of an epoxy resin.
There is no restriction | limiting in particular as a hardening | curing agent (C), Generally, what is generally known as an epoxy resin hardening | curing agent can be used. For example, phenolic curing agents, aliphatic amines, polyether amines, alicyclic amines, aromatic amines and other amine curing agents, acid anhydride curing agents, amide curing agents, tertiary amines, imidazoles and the like Derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan curing agents, isocyanate curing agents, blocked isocyanate curing agents, and the like.

  Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, 1,3-bis. (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cle All novolak, xylenol novolak, poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2 , 4-Benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2, -Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol, etc. The

  Specific examples of the amine curing agent include aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, Examples include diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine, and the like. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ethylamine , Diaminodiethyl Examples include rudimethyldiphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene.

  Specific examples of acid anhydride curing agents include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) Anhydride, Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, Methylhymic anhydride, Tetrahydrophthalic anhydride, Trialkyltetrahydrophthalic anhydride, Methylcyclohexene dicarboxylic anhydride, Methylcyclohexene tetracarboxylic Acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic dianhydride, het anhydride, nadic anhydride, methyl nadic anhydride, 5- ( 2, -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene-2-succinic acid Examples of the anhydride include 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride.

  Examples of the amide type curing agent include dicyandiamide and polyamide resin.

  Examples of the tertiary amine include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. .

  Examples of imidazole and derivatives thereof include 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazo Lithium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-di Mino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and adducts of an epoxy resin and the imidazoles.

  Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like, and phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, Examples include tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.

  Moreover, these hardening | curing agents may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.

  Among these curing agents, imidazole or a derivative thereof is preferably used among these. In addition, when the organic carboxylic acid and organic carboxylic acid ester which have the hardening effect | action of an epoxy resin are used as the flux (D) mentioned later, you may use this organic carboxylic acid as a hardening | curing agent (C).

Moreover, content of the hardening | curing agent (C) in a 1st interlayer filler composition is 0.1-60 weight part normally with respect to 100 weight part of resin (A) which has an epoxy resin as a main component. is there.
Here, when the curing agent is a phenol-based curing agent, an amine-based curing agent, or an acid anhydride-based curing agent, the equivalent ratio of the epoxy group in the epoxy resin to the functional group in the curing agent is 0.8 to 1. It is preferable to use it in the range of 5. Outside this range, unreacted epoxy groups and functional groups of the curing agent may remain, and desired physical properties may not be obtained.
Curing agents are amide-based curing agents, tertiary amines, imidazoles and their derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents. In the case of a curing agent, a blocked isocyanate curing agent, etc., it is preferably used in the range of 0.1 to 20 parts by weight relative to 100 parts by weight of the epoxy resin in the epoxy resin composition.

[Flux (D)]
Specifically, the flux (D) means that the metal electric signal terminals such as solder bumps and the surface oxide film of the land are dissolved and removed, and the wettability of the solder bumps on the land surface is improved when soldering the metal terminals. Furthermore, a solder connection for electrical signal connection between semiconductor substrates, which is a compound having a function of preventing reoxidation of the metal terminal surface of the solder bump and having a semiconductor device layer formed in the first interlayer filler layer When it contains a terminal, it is contained in the first interlayer filler composition.

  As the flux (D) used in the present invention, fats such as succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, citric acid, lactic acid, acetic acid, propionic acid, butyric acid, oleic acid, stearic acid, etc. Aromatic carboxylic acids such as aromatic carboxylic acids, benzoic acid, salicylic acid, phthalic acid, trimellitic acid, trimellitic anhydride, trimesic acid, benzenetetracarboxylic acid, organic carboxylic acids such as terpene carboxylic acids such as abietic acid and rosin, And an organic carboxylic acid ester which is a hemiacetal ester converted by reacting an organic carboxylic acid with an alkyl vinyl ether, glutamic acid hydrochloride, aniline hydrochloride, hydrazine hydrochloride, cetylpyridine bromide, phenylhydrazine hydrochloride, tetrachloronaphthalene, Methyl hydrazine hydrochloride, methyl amide Organic halogen compounds such as hydrochloride, ethylamine hydrochloride, diethylamine hydrochloride, butylamine hydrochloride, amines such as urea, diethylenetriamine hydrazine, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, hexaethylene glycol, glycerin, trimethylol Polyhydric alcohols such as ethane, trimethylolpropane, 2,3,4-trihydroxybenzophenone, triethanolamine, erythritol, pentaerythritol, bis (2-hydroxymethyl) iminotris- (hydroxymethyl) methane, ribitol, hydrochloric acid, Inorganic acids such as hydrofluoric acid, phosphoric acid, borohydrofluoric acid, potassium fluoride, sodium fluoride, ammonium fluoride, copper fluoride, nickel fluoride, fluoride Fluorides such as lead, potassium chloride, sodium chloride, cuprous chloride, nickel chloride, ammonium chloride, zinc chloride, stannous chloride and other chlorides, potassium bromide, sodium bromide, ammonium bromide, tin bromide And bromides such as zinc bromide. These compounds may be used as they are or may be microencapsulated using a coating agent made of an organic polymer or an inorganic compound. These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.

Among these, polyhydric alcohols, organic carboxylic acids, and organic carboxylic acid esters are preferable from the solubility in the resin (A) and various solvents.
The melting temperature of the flux (D) is 90 ° C. to 220 ° C. in order to exhibit functions such as dissolution of the oxide film on the solder surface, improvement of the wettability of the solder surface, and prevention of reoxidation of the solder surface before soldering. It is preferably 100 ° C to 200 ° C, more preferably 120 ° C to 180 ° C.
Further, when the flux (D) is an organic carboxylic acid or an organic carboxylic acid ester, it is preferable that the carboxylic acid is hardly decomposed or volatilized / evaporated at a temperature of 220 ° C. to 260 ° C. during solder joining. In this case, the decomposition temperature and boiling point are preferably 250 ° C. or higher, more preferably 270 ° C. or higher, and most preferably 290 ° C. or higher. As polyhydric alcohols, trimethylolpropane, erythritol, pentaerythritol, ribitol and the like can be preferably used. As the organic carboxylic acid, glutaric acid, adipic acid, trimellitic acid and the like can be preferably used.
The temperature at which the organic carboxylic acid ester generates carboxylic acid by thermal decomposition and exhibits its function is preferably 130 ° C. or higher, more preferably 140 ° C., still more preferably 160 ° C. or higher, and most preferably 180 ° C. or higher. is there.

  Examples of organic carboxylic acids used as raw materials for organic carboxylic acid esters include monocarboxylic acids such as lactic acid, acetic acid, propionic acid, butyric acid, oleic acid, stearic acid, benzoic acid, abietic acid, and rosin, oxalic acid, malonic acid, succinic acid, and glutar Acids, adipic acid, malic acid, tartaric acid, isophthalic acid, pyromellitic acid, maleic acid, fumaric acid, itaconic acid, and other dicarboxylic acids, citric acid, 1,2,4-trimellitic acid, tris (2-carboxyethyl) Tricarboxylic acid such as isocyanurate, tetracarboxylic acid such as pyromellitic acid and butanetetracarboxylic acid, and the like can be used. Of these, polycarboxylic acids having two or more carboxyl groups are preferred in terms of reactivity as a flux.

  Moreover, as alkyl vinyl ethers used as raw materials for organic carboxylic acid esters, those having an alkyl group having 1 to 6 carbon atoms are preferable, and among them, the alkyl group is a methyl group, an ethyl group, a propyl group, or a butyl group. Is particularly preferred. Among these alkyl groups, the lower the electron donating property, the higher the temperature dissociation property, so the alkyl group is preferably secondary or primary.

  Among these, as the organic carboxylic acid ester, Santacid G (dialkyl vinyl ether block bifunctional polymer carboxylic acid), Santacid H (monoalkyl vinyl ether block bifunctional low molecular weight carboxylic acid), Santacid I (monoalkyl vinyl ether block bifunctional carboxylic acid) , Both of which are manufactured by NOF Corporation).

  In the present invention, the content of the flux (D) is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight of the resin (A). If the content is less than 0.1 parts by weight, there is a risk of poor solder connection due to a decrease in oxide film removability, and if it exceeds 10 parts by weight, there is a risk of poor connection due to an increase in the viscosity of the composition.

  The first interlayer filler composition may contain various additives within a range not impairing the effects of the present invention for the purpose of further improving the functionality.

As such other additives, as an additive component for improving the adhesion between the substrate and the matrix resin and the inorganic filler, a coupling agent such as a silane coupling agent or a titanate coupling agent, Examples thereof include an ultraviolet ray inhibitor, an antioxidant, a plasticizer, a flame retardant, a colorant, and a dispersant for improving the storage stability.
Any of these may be used alone or in a combination of two or more in any combination and ratio.

Among the above additives, it is preferable to include a coupling agent from the viewpoint of improving the adhesion between the resin component and the inorganic filler (B).
Here, as the silane coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ, -Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltri Aminosilane such as ethoxysilane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysila And vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, and epoxy, amino and vinyl polymer type silanes.

  On the other hand, titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate It is done.

  There is no restriction | limiting in particular in the compounding quantity of another additive, It is used with the compounding quantity of a normal resin composition to such an extent that required functionality is obtained.

  In addition, it is preferable that the addition amount of a coupling agent shall be about 0.01 to 2.0 weight% with respect to the total solid in a resin composition among other additives. If the amount of the coupling agent is small, the effect of improving the adhesion between the matrix resin and the inorganic filler due to the incorporation of the coupling agent cannot be sufficiently obtained. There is a problem that the agent bleeds out.

  In forming the first interlayer filler layer, the above-mentioned first interlayer filler composition may be applied as it is on the semiconductor substrate, but the coating liquid containing an organic solvent (E) is further added. It may be used in the form. Hereinafter, the organic solvent (E) will be described.

[Organic solvent (E)]
Examples of the organic solvent (E) that can be used include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), methyl amyl ketone (MAK), and cyclohexanone (CHN), and ethyl acetate and butyl acetate. Esters, ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, alcohols such as methanol and ethanol, hexane And alkanes such as cyclohexane, and aromatics such as toluene and xylene.
Among these, considering the solubility of the resin and the boiling point of the solvent, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters and ethers are preferable, and in particular, ketones of methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are used. Particularly preferred.
These organic solvents may be used alone or in a combination of two or more in any combination and ratio.

The mixing ratio of the organic solvent (E) with respect to other components is not particularly limited, but is preferably 20% by weight to 70% by weight, particularly preferably 30% by weight to 60% by weight, based on the other composition. is there. By setting it as such a mixing ratio, a favorable coating film can be formed by arbitrary coating methods by using the coating liquid of this invention.
If the mixing ratio of the organic solvent (E) is less than 20% by weight, the viscosity of the composition may increase and a good coating film may not be obtained, or if it exceeds 70% by weight, a predetermined film thickness may not be obtained. May come up with problems.

The coating solution may contain various additives.
Examples of such additives include surfactants, emulsifiers, low elasticity agents, diluents, antifoaming agents, ion trapping agents, and the like that improve the dispersibility of each component in the coating solution in addition to the additives described above. Is mentioned.

Here, as the surfactant, any of conventionally known anionic surfactants, nonionic surfactants, and cationic surfactants can be used.
For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl Examples include sulfonates, sulfosuccinate esters, alkylbetaines, amino acids, and the like.
In addition, fluorine surfactants in which some or all of the CH bonds are CF bonds in these surfactants can also be preferably used.
The addition amount of the surfactant is preferably about 0.001 to 5% by weight with respect to the total solid content in the resin composition. If it is less than 0.001% by weight, the predetermined film thickness uniformity may not be obtained, and if it exceeds 5% by weight, phase separation from the resin component may occur, which is not preferable.

The manufacturing method of a coating liquid is not specifically limited, What is necessary is just to be a conventionally well-known method, and can manufacture by mixing the structural component of a coating liquid.
The mixing order is arbitrary as long as there is no particular problem such as reaction or precipitation. Among the components of the coating liquid, any two components or three or more components are blended in advance, and then the remaining components are mixed. You may mix all at once.
As described above, the inorganic filler (B) is preferably pulverized so as not to form an aggregate having a large particle diameter, but may be pulverized before the production of the coating liquid or mixed with other components. Then, it may be crushed. The method for grinding the inorganic material is not particularly limited, and conventionally known grinding methods can be applied.

(1-3) Manufacturing Method of First Three-Dimensional Integrated Circuit Laminate Hereinafter, a manufacturing method of the first three-dimensional integrated circuit laminate will be described.
A first three-dimensional integrated circuit laminate comprising a semiconductor substrate laminate constitutes each layer of the three-dimensional integrated circuit, and a precursor of the first interlayer filler layer described above is formed on the semiconductor substrate on which the semiconductor device layer is formed. A step of forming a coating film of the first interlayer filler composition to be obtained, and pressure-bonding these semiconductor substrates to form a semiconductor substrate laminate having a first interlayer filler layer between the semiconductor substrates Manufactured using a method including steps.
Hereinafter, each step will be specifically described.

  First, solder bumps and land terminals are formed as electrical connection terminals between the substrates on the upper and lower surfaces of the semiconductor substrate on which the semiconductor device layer is formed, as necessary. The details of the semiconductor substrate, solder bump, and land terminal are as described above.

Next, a coating film of the interlayer filler composition is formed on the semiconductor substrate.
The coating film of the first interlayer filler composition is obtained by dissolving the first interlayer filler composition dissolved / dispersed in the organic solvent (E), using a dipping method, a spin coating method, a spray coating method, a blade method, or any other arbitrary method. Can be formed by a method. In order to remove the solvent and low molecular components from the obtained coating film, baking treatment is performed at an arbitrary temperature of 50 to 150 ° C. to form a B-staged film. At this time, the baking treatment may be performed at a constant temperature, but in order to smoothly remove the volatile components in the composition, the baking treatment may be performed under reduced pressure conditions. Further, a baking process by stepwise temperature rise may be performed within a range in which the curing of the resin does not proceed. For example, baking can be performed at 60 ° C., then 80 ° C., and 120 ° C. for about 5 to 90 minutes each.
Moreover, you may use the 1st interlayer filler composition which does not contain the above-mentioned organic solvent (E) as it is. For example, a film made of the first interlayer filler composition may be formed on the semiconductor substrate by any method using a material that is heated and melted in a temperature range in which the resin does not start to be cured.
Moreover, since the first interlayer filler composition has sufficient extensibility suitable for film forming, the first interlayer filler composition may be formed by forming a film and placing the film on a semiconductor substrate.

Next, the film made of the first interlayer filler composition formed by the above method is heated to develop tackiness, and then temporarily bonded to the semiconductor substrate to be bonded. Although it depends on the composition of the resin (A), the temperature for temporary bonding is preferably 80 to 150 ° C. When the bonding of the semiconductor substrates is a plurality of layers, the temporary bonding may be repeated for the number of layers of the substrates, or the substrates on which the B-staging film is formed are stacked and then heated to be temporarily combined. It may be adhered. Preferably between the substrates during the temporary adhesion is needed ^{1gf / cm 2 ~50Kgf / cm 2} , more preferably it is preferred to carry out with a load of ^{10gf / cm 2 ~10Kgf / cm 2} .

After the temporary bonding, the semiconductor substrate is finally bonded. The temporarily bonded semiconductor substrate is pressure-bonded at 200 ° C. or higher, preferably 220 ° C. or higher, thereby reducing the melt viscosity of the resin of the first interlayer filler composition and connecting the electrical terminals between the semiconductor substrates. At the same time, the flux in the composition can be activated to achieve solder bonding between the semiconductor substrates. The upper limit of the heating temperature is a temperature at which the resin (A) to be used is not decomposed or altered, and is appropriately determined depending on the type and grade of the resin, but is usually 300 ° C. or lower.
Further, it is preferable that preferably between the substrates ^{10gf / cm 2 ~10Kgf / cm 2} , more preferably carried out under a load of 50gf / cm ² ~5Kgf / cm ² if necessary when the pressure bonding .

(2) Second three-dimensional integrated circuit laminate The three-dimensional integrated circuit laminate of the present invention is such that the above-described semiconductor substrate laminate is further mounted on an organic substrate. A second interlayer filler layer containing the resin (a) and the inorganic filler (b) may be formed therebetween.
That is, the above-mentioned semiconductor substrate laminate (first three-dimensional integrated circuit laminate) is further mounted on the organic substrate, and the resin (a) and the inorganic are interposed between the semiconductor substrate laminate and the organic substrate. It is a three-dimensional integrated circuit laminate in which a second interlayer filler layer containing a filler (b) is formed.
FIG. 3 is a conceptual cross-sectional view of a three-dimensional integrated circuit laminate (hereinafter referred to as “second three-dimensional integrated circuit laminate”) according to a second embodiment of the present invention. In FIG. 3, in order to facilitate understanding of the structure of the three-dimensional integrated circuit laminate, the thicknesses and sizes of the other constituent members with respect to the semiconductor substrate and the organic substrate are shown larger than actual.
As shown in FIG. 3, in the second three-dimensional integrated circuit laminate 100, the above-described semiconductor substrate laminate 1 is further mounted on the organic substrate 101, and the semiconductor substrate laminate 1 and the organic substrate 101 are separated from each other. A second interlayer filler layer 102 containing a resin (a) and an inorganic filler (b) is formed therebetween.

  Hereinafter, the second three-dimensional integrated circuit laminate will be described in detail. The semiconductor substrate laminate is the same as the first three-dimensional integrated circuit laminate described above, and a description thereof will be omitted.

(2-1) Organic substrate The organic substrate is a pattern conversion substrate (interposer) for high-density mounting that connects an array of electrodes with solder balls as external electrodes and a semiconductor substrate, and mounts a three-dimensional integrated circuit laminate. In order to ensure the consistency of the coefficient of thermal expansion with the printed circuit board or the flexible circuit board, the organic substrate having a multilayer circuit structure having a wiring layer in the resin plate is preferable. An epoxy resin or the like is preferably used as the resin component constituting the organic substrate, and copper (Cu) is preferably used as the wiring layer. It may be connected to an organic substrate via bumps or the like, and the organic substrate may be electronically connected to terminals of the printed circuit board via arrayed electrodes.

(2-2) Second interlayer filler layer The second interlayer filler layer is formed between the semiconductor substrate laminate and the organic substrate, and contains a resin (a) and an inorganic filler (b). .
The dielectric constant of the second interlayer filler layer is preferably 6 or less, and more preferably 5 or less.
A dielectric constant exceeding 6 is not preferable because it causes a signal transmission delay in the wiring between the semiconductor substrate laminate and the organic substrate, resulting in a decrease in the operating speed of the entire device.
It is preferable that the dielectric constant is 6 or less, preferably 5 or less because the transmission delay of the signal can be reduced, and the processing speed of the semiconductor device can be improved.

  The second interlayer filler layer preferably has a thermal conductivity of 0.4 W / (m · K) or more, more preferably 0.8 W / (m · K) or more. It is particularly preferably 0 W / (m · K) or more.

  The thickness of the second interlayer filler layer is preferably 50 μm or more and 300 μm or less. More preferably, they are 60 micrometers or more and 250 micrometers or less, More preferably, they are 70 micrometers or more and 200 micrometers or less. When the thickness is increased, the stacked body of the semiconductor substrate stack and the organic substrate becomes bulky, and it is not preferable because small packaging becomes difficult. Further, if the thickness is reduced, it is not preferable because the difference in expansion coefficient between the semiconductor substrate laminate and the organic substrate due to a change in the operating temperature of the device may cause peeling at the interface between the inorganic and organic substrates. By setting it as the said thickness, workability and performance can be made compatible.

Hereinafter, each component in the composition constituting the second interlayer filler layer (hereinafter sometimes referred to as “second interlayer filler composition”) will be described.
A 2nd interlayer filler composition contains resin (a) and an inorganic filler (b), and also contains a hardening | curing agent (c), flux (d), etc. as needed.
In the second interlayer filler composition, detailed description of the same parts as the first interlayer filler composition is omitted.

[Resin (a)]
The resin (a) has a thermal conductivity of 0.15 W / (m · K) as a second interlayer filler composition in order to obtain sufficient thermal conductivity when combined with the inorganic filler (b). The above is preferable.
In addition, the resin (a) is required to have a melt viscosity at 50 ° C. of 2000 Pa · s or more in order to perform alignment with the substrate to be bonded after the thin film is formed on the substrate and before temporary bonding. -It is preferable that it is more than s.
Further, when carrying out the main bonding after temporary bonding, the resin (a) has a melt viscosity at 120 ° C. in order to melt the first interlayer filler composition by heating and connect the electric bonding terminals. 100 Pa · s or less is preferable, and 20 Pa · s or less is more preferable.

Specific examples of the resin (a) include epoxy resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, polyester resin, allyl resin, alkyd resin, urethane resin, silicon resin, acrylic resin, polyimide resin, and the like. be able to. In addition, you may use resin (A) of the said 1st interlayer filler composition as resin (a).
Among these resins, thermosetting resins excellent in heat resistance and various electric characteristics are preferable. Among thermosetting resins, a resin mainly composed of an epoxy resin is preferred from the viewpoint of processability before curing, other curing characteristics, and cured film properties. Here, “mainly composed of epoxy resin” means that the proportion of the epoxy resin in the resin (a) is 50% by weight or more, preferably 60% by weight or more (including 100% by weight). It is.
In general, an underfill process has been proposed as a technique for filling a silicon substrate and an organic substrate. After bonding bumps and lands, an interlayer filler is filled from the side of the substrate using a capillary phenomenon. For this reason, this process requires a resin component that is liquid at room temperature, and generally, a liquid epoxy resin or the like is preferably used.

[Inorganic filler (b)]
The inorganic filler (b) is added to improve the thermal conductivity of the second interlayer filler composition. When the second interlayer filler composition contains the inorganic filler (b) having thermal conductivity, the second interlayer filler composition can be imparted with high thermal conductivity, and the semiconductor substrate laminate The semiconductor device can be stably operated by promoting the heat conduction between the body and the organic substrate to lower the temperature of the semiconductor device substrate.
The thermal conductivity of the inorganic filler (b) is preferably 1 W / (m · K) or more, and more preferably 2 W / (m · K) or more.
When the inorganic filler (b) has such a thermal conductivity, a second interlayer filler layer having a sufficient thermal conductivity can be obtained with an appropriate addition amount.

As the inorganic filler (b), the same inorganic filler (B) as described above can be used.
That is, alumina (Al ₂ O ₃ : thermal conductivity 30 W / (m · K)), aluminum nitride (AlN: thermal conductivity 260 W / (m · K)), boron nitride (BN: thermal conductivity 3 W / (m (K) (thickness direction), 275 W / (m · K) (in-plane direction)), silicon nitride (Si ₃ N ₄ : thermal conductivity 23 W / (m · K)), silica (SiO ₂ : thermal conductivity) 1.4 W / (m · K)) can be used. Moreover, these inorganic fillers (b) may be used individually by 1 type, and may mix and use 2 or more types by arbitrary combinations and a ratio.
In view of the reliability of the bonded device, it is preferable that the inorganic filler (b) further has stability against oxygen, water and high-temperature exposure and low dielectric properties, and as such inorganic filler, Al ₂ O ₃ , AlN , BN, and SiO ₂ , preferably Al ₂ O ₃ , AlN, and BN.

  The particle size of the inorganic filler (b) is not particularly limited, but usually the average particle size is 0.1 to 20 μm and the maximum particle size is 30 μm or less, preferably the average particle size is 0.2 to 17 μm. The maximum particle size is 25 μm or less, more preferably the average particle size is 0.3 to 15 μm, and the maximum particle size is 20 μm or less.

  In addition, content of an inorganic filler (b) is 50 to 400 weight part normally per 100 weight part of resin (a), More preferably, it is 75 to 300 weight part. If the content of the inorganic filler (b) is less than 50 parts by weight, sufficient thermal conductivity may not be obtained, and if it exceeds 400 parts by weight, the viscosity of the composition increases, and a uniform coating film is formed. There may be a problem that it cannot be formed.

[Other ingredients]
In the second interlayer filler composition, the components other than the resin (a) and the inorganic filler (b) include the curing agent (C), flux (D), and the like in the first interlayer filler composition described above. An additive is mentioned. The purpose of use, the blending amount, and the like are the same as those of the first interlayer filler composition.

(2-3) Method for Manufacturing Second Three-Dimensional Integrated Circuit Laminate The second three-dimensional integrated circuit laminate is formed on the surface of the semiconductor substrate laminate that is in contact with the organic substrate and on the organic substrate. Forming a coating film of the second interlayer filler composition serving as a precursor of the second interlayer filler layer on one or both of the surfaces in contact with the semiconductor substrate laminate, the semiconductor substrate, and the organic substrate; And a semiconductor substrate laminated body having a second interlayer filler layer between the semiconductor substrate laminated body and the organic substrate to produce the semiconductor substrate laminated body. The second interlayer filler composition may be the same as or different from the first interlayer filler composition.

  EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example, this invention is not limited to a following example, unless it deviates from the meaning.

The blending components of the interlayer filler composition used below are as follows.
・ Resin (A)
Epoxy resin (A1): Phenoxy resin
Weight average molecular weight: 26,000
Epoxy equivalent: 4,600 g / equivalent
30% by weight methyl ethyl ketone / cyclohexanone solution Epoxy resin (A2-1): Product name “YL6800” manufactured by Mitsubishi Chemical Corporation
Epoxy resin (A2-2): Product name “1032H60” manufactured by Mitsubishi Chemical Corporation
Epoxy resin (A2-3): Product name “1001” manufactured by Mitsubishi Chemical Corporation
Epoxy resin (A2-4): Product name “YX4000” manufactured by Mitsubishi Chemical Corporation
Epoxy resin (A2-5): Mitsubishi Chemical Corporation product name “1006”

・ Inorganic filler (B)
Inorganic filler (B-1): BN manufactured by Nissin Reflatec Co., Ltd. Product name “R-BN”
Inorganic filler (B-2): Sumitomo Chemical Co., Ltd. Alumina Product name “AA-07”

Curing agent (C): Shikoku Kasei Kogyo Co., Ltd. Product name “2PHZ-PW” 2-Phenyl-4,5-dihydroxymethylimidazole

・ Flux (D)
Flux (D-1): NOF Corporation Product name "Santa Cid G"
Dialkyl vinyl ether block bifunctional polymer type carboxylic acid flux (D-2): Wako Pure Chemical Industries, Ltd. Product name “Adipic acid”

・ Organic solvent (E)
Organic solvent (E1): Wako Pure Chemical Industries, Ltd. reagent special grade "Methyl ethyl ketone"
Organic solvent (E2): Wako Pure Chemical Industries, Ltd. reagent special grade "cyclohexanone"

・ Dispersant (F)
Dispersant (F-1): Product name “BYK-2155” manufactured by Big Chemie

The phenoxy resin as the epoxy resin (A1) was produced as follows.
YL6121H (epoxy equivalent of 171 g / equivalent, 1: 1 mixture of 4,4′-biphenol type epoxy resin and 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol type epoxy resin (Mitsubishi Chemical Corporation) 215 parts by weight, 3,3′-dimethyl-4,4′-biphenol (OH equivalent 107 g / equivalent, manufactured by Honshu Chemical Co., Ltd.) 127 parts by weight, 0.32 parts by weight of a 27% by weight tetramethylammonium hydroxide aqueous solution 228 parts by weight of cyclohexanone as a solvent for reaction was placed in a pressure-resistant reaction vessel equipped with a stirrer and reacted at 180 ° C. for 5 hours under a nitrogen gas atmosphere. The solvent was removed from the reaction product by a conventional method to obtain a 30% by weight resin solution. .

The thermal conductivity of the obtained resin and interlayer filler composition was determined by measuring the thermal diffusivity, specific gravity, and specific heat with the following devices and multiplying these three measured values. The dielectric constant was calculated from the volume fraction of the filler component in the interlayer filler composition based on the physical property values of each material (epoxy resin 2.8, boron nitride 3.9, alumina 9.7). .
1) Thermal diffusivity: Eye Phase Co., Ltd. “I Phase Mobile 1u”
2) Specific gravity: METTLER TOLEDO Co., Ltd. Balance XS-204 ("Solid specific gravity measurement kit" used)
3) Specific heat: Seiko Instruments Inc. DSC320 / 6200

[Example]
(1) Preparation and evaluation of interlayer filler composition film (thermal conductivity and dielectric constant)
As epoxy resin (A), 5 g of the above epoxy resin (A1) solution, 3.75 g of epoxy resin (A2-1), 0.94 g of epoxy resin (A2-2) solution (80 wt% cyclohexanone solution), epoxy resin (A2) -3) Add 2.14 g of the solution (70 wt% cyclohexanone solution) and 7.24 g of the inorganic filler (B-1), and further add 24.0 g of zirconia balls (YTZ-2) having a diameter of 2 mm, and use a revolutionary stirrer to make 2000 rpm For 33 minutes. After completion of the stirring, the beads are removed by filtration, 0.15 g of the curing agent (C) and 0.15 g of the flux (D-1) are added, and the mixture is further stirred for 6 minutes by a revolving stirrer, and the interlayer filler paste (coating solution) )
This raw material paste was applied to a release-treated glass substrate, heated at 100 ° C. for 90 minutes under reduced pressure, and the solvent was distilled off to obtain a B-staged film. A glass substrate subjected to a further release treatment is placed on this film and sandwiched, and then pressed (pressure 1 MPa) at 150 ° C. for 1 hour and subsequently at 170 ° C. for 1 hour to be molded and cured to a film thickness of 600 μm. Interlayer filler composition film 1 was obtained. This film had a thermal conductivity of 1.2 W / (m · K) and a dielectric constant of 3.2.

(2) Preparation and evaluation of interlayer filler composition film (water absorption)
2.50 g of epoxy resin (A2-2), 6.25 g of epoxy resin (A2-4) and 3.75 g of epoxy resin (A2-5) were stirred and dissolved in 12.5 g of organic solvent (E1). To this was added 0.25 g of dispersant (F-1), 0.25 g of flux (D-2) and 11.75 g of organic solvent (E1), and further 12.5 g of inorganic filler (B-1) and a diameter of 0. 100 g of 5 mm zirconia balls (YTZ-0.5) was added and stirred for 10 minutes at 2000 rpm using a self-revolving stirrer. After completion of the stirring, the beads were removed by filtration, 0.25 g of a curing agent (C) was added, and further stirred for 6 minutes with a self-revolving stirrer to obtain an interlayer filler paste (coating liquid).
This raw material paste was applied to a release-treated glass substrate, and the solvent was distilled off by heating at 80 ° C. for 30 minutes and 120 ° C. for 30 minutes under reduced pressure. A glass substrate subjected to a further release treatment is placed on this film and sandwiched, and then pressed (pressure 1 MPa) at 165 ° C. for 2 hours to be molded and cured to form an interlayer filler composition film 2 having a thickness of 500 μm. Obtained.
This cured film was dried in a vacuum oven at 125 ° C. for 5 hours, and the film weight after drying was 1.6179 g as the initial weight. Subsequently, after hold | maintaining for 10 hours in 85 degreeC and 85% high temperature and humidity oven, the weight of the film | membrane was measured. The weight of the cured film was 1.6303 g, and the rate of weight increase due to water absorption was 0.77%, which was less than 1%.

  According to the present invention, a three-dimensional integrated circuit laminate capable of high heat dissipation and high-speed operation can be formed.

DESCRIPTION OF SYMBOLS 1 1st three-dimensional integrated circuit laminated body 10, 20, 30 Semiconductor substrate 11, 21, 31 Semiconductor device layer 12, 22, 32 Buffer coating film 13, 23, 33 Semiconductor substrate penetration electrode 14, 24, 34, 103 Land Terminals 15, 25, 35 Solder bumps 40, 50 First interlayer filler layer 100 Second three-dimensional integrated circuit laminate 101 Organic substrate 102 Second interlayer filler layer

Claims (14)

  A semiconductor substrate laminate in which at least two semiconductor substrates on which semiconductor device layers are formed is laminated, and a resin (A) and an inorganic filler (B) having a dielectric constant of 6 or less are contained between the semiconductor substrates. A three-dimensional integrated circuit laminate having one interlayer filler layer.   The three-dimensional integrated circuit laminate according to claim 1, wherein the semiconductor substrate is a silicon substrate.   3. The three-dimensional integrated circuit laminate according to claim 1, wherein the first interlayer filler layer has a thermal conductivity of 0.8 W / (m · K) or more.   4. The three-dimensional integrated circuit laminate according to claim 1, wherein the inorganic filler (B) has a thermal conductivity of 2 W / (m · K) or more.   5. The three-dimensional integrated circuit laminate according to claim 1, wherein a dielectric constant of the first interlayer filler layer is 5 or less.   The first interlayer filler layer contains 50 to 400 parts by weight of the inorganic filler (B) per 100 parts by weight of the resin (A). The three-dimensional integrated circuit laminate according to item 1.   The three-dimensional integrated circuit laminate according to any one of claims 1 to 6, wherein the resin (A) is a resin mainly composed of an epoxy resin.   The three-dimensional integrated circuit laminate according to any one of claims 1 to 7, wherein the inorganic filler (B) is boron nitride.   9. The three-dimensional integrated circuit laminate according to claim 1, wherein a thickness of the first interlayer filler layer is not less than 1 μm and not more than 50 μm.   The three-dimensional integrated circuit laminate according to any one of claims 1 to 9, wherein a solder connection terminal for connecting an electric signal is included in the first interlayer filler layer between the semiconductor substrates. body.   The semiconductor substrate laminate is further mounted on an organic substrate, and a second interlayer filler layer containing a resin (a) and an inorganic filler (b) between the semiconductor substrate laminate and the organic substrate. The three-dimensional integrated circuit laminate according to any one of claims 1 to 10, wherein:   The three-dimensional integrated circuit laminate according to claim 11, wherein a dielectric constant of the second interlayer filler layer is 6 or less.   The three-dimensional integrated circuit laminate according to claim 11 or 12, wherein the thermal conductivity of the second interlayer filler layer is 0.4 W / (m · K) or more.   14. The three-dimensional integrated circuit laminate according to claim 11, wherein a thickness of the second interlayer filler layer is not less than 50 μm and not more than 300 μm.