JP6001515B2 - SEALING MATERIAL LAMINATED COMPOSITE, SEMICONDUCTOR SEMICONDUCTOR MOUNTING BOARD, SEMICONDUCTOR SEMICONDUCTOR FORMED WAFER, SEMICONDUCTOR DEVICE, AND SEMICONDUCTOR DEVICE MANUFACTURING METHOD - Google Patents

Description

  The present invention relates to a sealing material that can be collectively sealed at a wafer level, and further includes a semiconductor element forming wafer sealed with a sealing material, a substrate on which a semiconductor element is mounted, and a semiconductor in which the semiconductor element forming wafer is singulated. The present invention relates to a device and a method for manufacturing a semiconductor device using the substrate-shaped sealing material.

  Conventionally, various methods have been proposed and studied for wafer level sealing of a semiconductor element mounting surface of a substrate on which a semiconductor element is mounted, or a semiconductor element forming surface of a wafer on which a semiconductor element is formed. Sealing by spin coating Examples include sealing by screen printing (Patent Document 1) and a method using a composite sheet obtained by coating a film support with a hot-melt epoxy resin (Patent Documents 2 and 3).

  Among them, as a wafer level sealing method for a semiconductor element mounting surface of a substrate on which a semiconductor element is mounted, a film having a double-sided adhesive layer is attached on top of a metal, silicon wafer, glass substrate or the like, or an adhesive is used. After applying by spin coating, etc., semiconductor elements are arranged on the substrate, bonded, and mounted to form a semiconductor element mounting surface, and then heated under pressure with a liquid epoxy resin or epoxy molding compound, etc. A method for sealing a semiconductor element mounting surface has recently been mass-produced (Patent Document 4).

  However, in the above-described method, when a small-diameter wafer having a diameter of about 200 mm (8 inches) or a small-diameter substrate such as a metal is used, sealing can be performed without any major problem even in the present situation. In the case of sealing a large-diameter substrate on which a semiconductor element is mounted or a large-diameter wafer on which a semiconductor element is formed, warping of the substrate or the wafer due to shrinkage stress of an epoxy resin or the like at the time of sealing and curing is a big problem. Also, when the semiconductor element mounting surface of a large-diameter substrate on which a semiconductor element is mounted is sealed at the wafer level, there is a problem that the semiconductor element is peeled off from a substrate such as metal due to shrinkage stress of epoxy resin or the like during sealing and curing. There has occurred. From these problems, it is a big problem that mass production by batch sealing of semiconductor devices cannot be performed.

  As a method for solving the problems associated with the increase in the diameter of a substrate on which such a semiconductor element is mounted or a wafer on which the semiconductor element is formed, a filler is filled in the sealing resin composition at nearly 90 wt%, or a sealing resin It is mentioned that the shrinkage stress at the time of curing is reduced by reducing the elasticity of the composition (Patent Documents 1, 2, and 3).

  However, when the filler is filled to the epoxy resin close to 90 wt%, the viscosity of the sealing resin composition increases, and when the sealing resin composition is cast and molded, a force is applied to the semiconductor element mounted on the substrate, A new problem has occurred that the semiconductor element is peeled off the substrate. In addition, when the sealing resin is made less elastic, the warpage of the substrate on which the sealed semiconductor element is mounted and the wafer on which the semiconductor element is formed is improved, but the sealing performance such as heat resistance and moisture resistance is reduced. A new problem occurred. Therefore, these solutions have not led to a fundamental solution.

  As described above, even when a large-diameter wafer or a large-diameter substrate such as metal is sealed, the substrate or wafer is not warped, or the semiconductor element is not peeled off from the metal or other substrate. The semiconductor element mounting surface of the substrate on which the element is mounted or the semiconductor element forming surface of the wafer on which the semiconductor element is formed can be collectively sealed at the wafer level, and after sealing, the sealing is excellent in sealing performance such as heat resistance and moisture resistance. Stopping material was sought.

JP 2002-179885 A JP 2009-060146 A JP 2007-001266 A JP-T-2004-504723

  The present invention has been made to solve the above-described problem, and even when a large-diameter substrate such as a large-diameter or thin wafer or metal is sealed, the warp of the substrate or wafer, the semiconductor element from the substrate The semiconductor element mounting surface of the substrate on which the semiconductor element is mounted or the semiconductor element forming surface of the wafer on which the semiconductor element is formed can be collectively sealed at the wafer level, and after sealing, heat resistance, moisture resistance, etc. It aims at providing the sealing material laminated composite which is excellent in the sealing performance of this, and is very versatile.

  In addition, the post-sealing semiconductor element mounting substrate and the post-sealing semiconductor element mounting wafer sealed with the sealing material laminated composite, the post-sealing semiconductor element mounting substrate and the post-sealing semiconductor element formation wafer are separated into pieces. It is an object of the present invention to provide a semiconductor device and a method for manufacturing a semiconductor device using the sealing material laminate composite.

In order to solve the above problems, in the present invention,
A sealing material laminated composite for collectively sealing a semiconductor element mounting surface of a substrate on which one or more semiconductor elements are mounted, or a semiconductor element forming surface of a wafer on which a semiconductor element is formed,
Provided is a sealing material laminated composite having a supporting base material composed of a cured or semi-cured cyanate ester resin, and an uncured resin layer formed on one side of the supporting base material and composed of an uncured thermosetting resin. .

  Thus, if it is a sealing material laminated composite which has the cyanate ester resin which can be used as a support substrate, and the uncured resin layer which consists of the uncured thermosetting resin formed on the one side, it will expand. The cyanate ester resin with a very small coefficient can suppress the shrinkage stress of the uncured resin layer at the time of sealing and curing, so it is the case when sealing large diameter substrates such as large and thin wafers and metals. However, the warpage of the substrate and the wafer and the peeling of the semiconductor element from the substrate can be suppressed, and the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted or the semiconductor element forming surface of the wafer on which the semiconductor element is formed is collectively sealed at the wafer level. A highly versatile substrate having excellent sealing performance such as heat resistance and moisture resistance can be obtained after sealing.

（式中、Ｒ^１及びＲ^２は水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^３は

を示し、ｎ＝０〜３０の整数である。Ｒ^４は水素原子又はメチルである。）
（Ｂ）下記一般式（２）で示される１分子中に２個以上の水酸基を持つフェノール化合物（ｂ−１）又は下記一般式（３）で表されるジヒドロキシナフタレン化合物（ｂ−２）、もしくはその両方

（式中、Ｒ^５及びＲ^６は水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^７は

を示し、ｍ＝０〜３０の整数である。Ｒ^４は水素原子又はメチルである。）

を含有するものであり、該シアネートエステル樹脂の硬化後のガラス転移温度が２００℃以上であり、熱膨張係数が５ｐｐｍ以下のものであることが好ましい。 The cyanate ester resin is
(A) Cyanate ester compound represented by the following general formula (1) or oligomer thereof

(Wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents

Where n = 0 to 30. R ⁴ is a hydrogen atom or methyl. )
(B) a phenol compound (b-1) having two or more hydroxyl groups in one molecule represented by the following general formula (2) or a dihydroxynaphthalene compound (b-2) represented by the following general formula (3), Or both

(Wherein R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁷ represents

Where m is an integer from 0 to 30. R ⁴ is a hydrogen atom or methyl. )

The glass transition temperature after curing of the cyanate ester resin is preferably 200 ° C. or higher, and the thermal expansion coefficient is preferably 5 ppm or lower.

  With such a cyanate ester resin, there is almost no change in the coefficient of thermal expansion at 200 ° C. or less, and distortion to the semiconductor molded product due to the change in the coefficient of thermal expansion can be suppressed. That is, the peeling phenomenon due to strain and the influence on the semiconductor element can be suppressed.

  It is preferable that the thickness of the uncured resin layer is 20 μm or more and 2000 μm or less.

  An uncured resin layer having such a thickness is sufficient to seal the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted, or the semiconductor element formation surface of the wafer on which the semiconductor element is formed, and sealing. The stopped post-sealing semiconductor element mounting substrate and the post-sealing semiconductor element formation wafer that are stopped can be prevented from becoming too thick.

  The uncured resin layer is preferably solidified at less than 50 ° C. and melted at 50 ° C. or higher and 150 ° C. or lower.

  With such an uncured resin layer, a cyanate ester resin having a very small expansion coefficient can suppress shrinkage stress at the time of curing of the uncured resin layer containing these resins. Even when a large-diameter substrate is sealed, warping of the substrate or wafer, and peeling of the semiconductor element from the substrate can be more reliably suppressed, and a semiconductor element mounting surface of the substrate on which the semiconductor element is mounted or a semiconductor element is formed. If it becomes a sealing material laminated composite which can encapsulate the semiconductor element formation surface of the wafer which was collectively at the wafer level, and if it is a composite having an uncured resin layer containing these resins, heat resistance and moisture resistance especially after sealing It becomes the sealing material laminated composite excellent in sealing performance, such as.

The present invention also provides:
A semiconductor element mounting substrate after sealing in which a semiconductor element mounting surface of a substrate on which a semiconductor element is mounted is sealed,
By covering the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted with the uncured resin layer of the encapsulant laminate composite, and heating and curing the uncured resin layer, the encapsulant laminate composite Provided is a semiconductor element mounting substrate after sealing that is collectively sealed.

  Such a post-sealing semiconductor element mounting substrate is a post-sealing semiconductor element mounting substrate in which the warpage of the substrate or the semiconductor element peeling from the substrate is suppressed.

The present invention also provides:
A semiconductor element formation wafer after sealing in which a semiconductor element formation surface of a wafer on which a semiconductor element is formed is sealed,
By covering the semiconductor element forming surface of the wafer on which the semiconductor element is formed with the uncured resin layer of the encapsulant laminate composite, and heating and curing the uncured resin layer, the encapsulant laminate composite Provided is a semiconductor element-formed wafer after sealing that is collectively sealed.

  Such a post-sealing semiconductor element formation wafer is a post-sealing semiconductor element formation wafer in which the warpage of the substrate and wafer is suppressed.

Furthermore, the present invention provides
Provided is a semiconductor device obtained by dicing the post-sealing semiconductor element mounting substrate or the post-sealing semiconductor element forming wafer into individual pieces.

  With such a semiconductor device, a semiconductor device can be manufactured from a substrate or wafer that is sealed with a sealing material laminate composite that is excellent in sealing performance such as heat resistance and moisture resistance, and warpage is suppressed. It becomes a quality semiconductor device.

Furthermore, the present invention provides
A method for manufacturing a semiconductor device, comprising:
A coating step of covering the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted, or the semiconductor element forming surface of the wafer on which the semiconductor element is formed, with the uncured resin layer of the sealing material laminate composite;
By heating and curing the uncured resin layer, the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted or the semiconductor element forming surface of the wafer on which the semiconductor element is formed is collectively sealed, and the semiconductor element after sealing A sealing step for forming a mounting substrate or a semiconductor element-formed wafer after sealing; and
Provided is a method for manufacturing a semiconductor device having a singulation process for manufacturing a semiconductor device by dicing the post-sealing semiconductor element mounting substrate or the post-sealing semiconductor element forming wafer into individual pieces.

  With such a method for manufacturing a semiconductor device, the semiconductor element mounting surface or the semiconductor element forming surface can be covered more easily and without filling defects, and a large-diameter substrate such as a thin, large-diameter wafer or metal can be encapsulated. Even if it is stopped, it is possible to obtain a post-sealing semiconductor element mounting substrate or a post-sealing semiconductor element forming wafer in which warpage of the substrate or wafer and separation of the semiconductor element from the substrate are suppressed, and By separating individual substrates or wafers into individual pieces, a high-quality semiconductor device having excellent sealing performance such as heat resistance and moisture resistance can be manufactured.

As described above, since the support base material made of a cyanate ester resin can suppress the shrinkage stress of the uncured resin layer at the time of curing and sealing, the large diameter of the sealing material laminated composite of the present invention. Even when a large-diameter substrate such as a wafer or metal is sealed, it is possible to suppress warping of the substrate or wafer or separation of the semiconductor element from the substrate such as metal. The semiconductor element mounting surface or the semiconductor element forming surface of the wafer on which the semiconductor element is formed can be collectively sealed at the wafer level, and after sealing, it has excellent sealing performance such as heat resistance and moisture resistance, and is extremely versatile. A high substrate can be obtained.
Further, the post-sealing semiconductor element mounting substrate and the post-sealing semiconductor element formation wafer sealed by the sealing material laminate composite of the present invention are warped on the substrate or the wafer, or the semiconductor element is made of a metal or other substrate. It becomes what was prevented from peeling. Further, the semiconductor element mounting substrate after sealing which is sealed by the sealing material laminated composite of the present invention using a cyanate ester resin excellent in sealing performance such as heat resistance and moisture resistance and warpage is suppressed, and sealing If it is a manufacturing method of the semiconductor device which has the process of separating a back semiconductor element formation wafer into pieces, a high quality semiconductor device can be manufactured.

It is an example of sectional drawing of the sealing material laminated composite of this invention. It is an example of sectional drawing of (a) the semiconductor element mounting substrate after sealing and (b) the semiconductor element formation wafer after sealing sealed by the sealing material laminated composite of this invention. 1A is an example of a cross-sectional view of a semiconductor device of the present invention manufactured from a semiconductor element mounting substrate after sealing, and FIG. 2B is a cross-sectional view of a semiconductor device of the present invention manufactured from a semiconductor element-formed wafer after sealing. It is an example of the flowchart of the method of manufacturing a semiconductor device from the board | substrate which mounted the semiconductor element using the sealing material laminated composite of this invention.

  Hereinafter, the encapsulating material laminated composite of the present invention, the post-sealing semiconductor element mounting substrate or the post-sealing semiconductor element forming wafer sealed by the encapsulating material laminated composite, the post-sealing semiconductor element mounting substrate or the A semiconductor device in which a semiconductor element-formed wafer is encapsulated after sealing and a method for manufacturing a semiconductor device using the sealing material laminate composite will be described in detail, but the present invention is not limited thereto.

  As described above, even when a large-diameter substrate such as a metal on which a semiconductor element is mounted or a large-diameter wafer on which a semiconductor element is formed is sealed, the substrate or the wafer is warped or the semiconductor element is Separation from the substrate can be suppressed, the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted, or the semiconductor element formation surface of the wafer on which the semiconductor element is formed can be collectively sealed at the wafer level, and heat resistance after sealing There has been a demand for a highly versatile sealing material that is excellent in sealing performance such as heat resistance and moisture resistance.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a support base material made of a cured or semi-cured cyanate ester resin and an uncured thermosetting material formed on one side of the support base material. In the case of a sealing material laminated composite having an uncured resin layer made of a resin, a support base material made of a cyanate ester resin having a very small expansion coefficient can suppress shrinkage stress during curing of the uncured resin layer. It was found that even when a large-diameter substrate such as a large-diameter wafer or metal is sealed, the warping of the substrate or wafer, and the peeling of the semiconductor element from the substrate can be suppressed by the effect of suppressing the shrinkage stress. It was. Furthermore, when the sealing material laminate composite of the present invention is used, the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted or the semiconductor element forming surface of the wafer on which the semiconductor element is formed can be collectively sealed at the wafer level, and the sealing is performed. Later, it was found that the sealing material had excellent sealing performance such as heat resistance and moisture resistance and was very versatile, and the sealing material laminated composite of the present invention was completed.

  In addition, the present inventors may warp the substrate or the wafer if it is a post-sealing semiconductor element mounting substrate and a post-sealing semiconductor element formation wafer that are collectively sealed by the sealing material laminated composite. It is found that a semiconductor element mounting substrate and a semiconductor element formation wafer after sealing in which the semiconductor element is prevented from being peeled off from the sealing, and further, the sealing in which the warpage and the peeling of the semiconductor element are suppressed in this way. It is found that a high-quality semiconductor device can be obtained by dividing the semiconductor element mounting substrate after sealing and the semiconductor element forming wafer after sealing into individual pieces, and the semiconductor element mounting substrate after sealing and the semiconductor element after sealing according to the present invention. A forming wafer and a semiconductor device were completed.

  Furthermore, the present inventors have found that the semiconductor element mounting surface or the semiconductor element forming surface can be easily covered by using the sealing material multilayer composite, and heating the uncured resin layer of the sealing material multilayer composite. It is found that the semiconductor element mounting surface or the semiconductor element forming surface can be collectively sealed by curing, and is further sealed and warped by the sealing material laminated composite having the cyanate ester resin having excellent sealing performance. The present invention has found that a high-quality semiconductor device can be manufactured by dicing and separating a post-sealing semiconductor element mounting substrate or a post-sealing semiconductor element forming wafer in which peeling of the semiconductor element is suppressed, A semiconductor device manufacturing method has been completed.

That is, the present invention
A sealing material laminated composite for collectively sealing a semiconductor element mounting surface of a substrate on which one or more semiconductor elements are mounted, or a semiconductor element forming surface of a wafer on which a semiconductor element is formed,
Provided is a sealing material laminated composite having a supporting base material composed of a cured or semi-cured cyanate ester resin, and an uncured resin layer formed on one side of the supporting base material and composed of an uncured thermosetting resin. .
Hereinafter, the support base material and the uncured resin layer which the sealing material laminate composite has will be described in detail.

<Support base material>
The support base material used in the present invention is made of a cyanate ester resin, can maintain a low linear expansion coefficient without using a fiber base material, and is excellent in moldability. The component of the cyanate ester resin is a ratio of 0.05 to 0.4 mol of the phenolic compound of component (B) or dihydroxynaphthalene or both hydroxyl groups with respect to 1 mol of cyanate group of the cyanate ester compound of component (A). The resin composition blended in can be preferably used.

（式中、Ｒ^１及びＲ^２は水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^３は

を示し、ｎ＝０〜３０の整数である。Ｒ^４は水素原子又はメチルである。） [(A) component]
(Cyanate ester compound or oligomer thereof)
As the component (A) of the cyanate ester resin used in the present invention, a cyanate ester compound represented by the following general formula (1) or an oligomer thereof can be preferably used.

(Wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents

Where n = 0 to 30. R ⁴ is a hydrogen atom or methyl. )

  This cyanate ester compound has two or more cyanate groups in one molecule. Specifically, cyanate ester of polyvalent aromatic dihydric phenol such as bis (3,5-dimethyl-4-cyanate). Phenyl) methane, bis (4-cyanatephenyl) methane, bis (3-methyl-4-cyanatephenyl) methane, bis (3-ethyl-4-cyanatephenyl) methane, bis (4-cyanatephenyl) -1,1 Ethane, bis (4-cyanatephenyl) -2,2-propane, di (4-cyanatephenyl) ether, di (4-cyanatephenyl) thioether, polyhydric acid ester of polyhydric phenol, such as phenol novolac type cyanate ester, Cresol novolac cyanate ester, phenyl aralkyl type Esters, biphenyl aralkyl type cyanate ester, and the like naphthalene aralkyl type cyanate ester.

  The aforementioned cyanate ester compound can be obtained by reacting phenols and cyanogen chloride under basic conditions. Such a cyanate ester compound can be obtained having a wide range of properties ranging from a solid having a softening point of 106 ° C. to a liquid at room temperature, from the structure, and is appropriately selected from among them in accordance with the application. be able to. Among these, those having a small equivalent of the cyanate group, that is, those having a low molecular weight between functional groups, have small curing shrinkage, and a cured product having low thermal expansion and high Tg can be obtained. Those having a large cyanate group equivalent have a slight decrease in Tg, but the triazine cross-linking interval becomes flexible, and low elasticity, high toughness, and low water absorption can be expected. The chlorine bonded or remaining in the cyanate ester compound is preferably 50 ppm or less, more preferably 20 ppm or less. If it is 50 ppm or less, there is no possibility of causing corrosion or corrosion of a Cu frame, Cu wire, or Ag plating in which chlorine or chlorine ions liberated by thermal decomposition during long-term high-temperature storage are oxidized, thereby causing no peeling or electrical failure. Moreover, since the insulation of resin does not fall, it is preferable.

[Component (B)]
The cyanate ester resin used in the present invention preferably contains a component (B) as a curing agent. In general, as a curing agent or a curing catalyst for a cyanate ester compound, a metal salt, a metal complex, a phenolic hydroxyl group having primary hydrogen or a primary amine is used. In the present invention, the phenol compound (b-1) or dihydroxy is used. A naphthalene compound (b-2) is preferably used.

（式中、Ｒ^５及びＲ^６は水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^７は

を示し、ｍ＝０〜３０の整数である。Ｒ^４は水素原子又はメチルである。） (Phenol compound (b-1))
As the component (B), a phenol compound (b-1) having two or more hydroxyl groups in one molecule represented by the following general formula (2) can be preferably used.

(Wherein R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁷ represents

Where m is an integer from 0 to 30. R ⁴ is a hydrogen atom or methyl. )

  Examples of the phenol compound include phenol resin having two or more phenolic hydroxyl groups in one molecule, bisphenol F type resin, bisphenol A type resin, phenol novolac resin, phenol aralkyl type resin, biphenyl aralkyl type resin, and naphthalene aralkyl type resin. 1 type or 2 types or more can be used together among these.

  This phenol compound (b-1) has a small phenol hydroxyl group equivalent, for example, a hydroxyl group equivalent of 120 or less has high reactivity with a cyanate group, and the curing reaction proceeds even at a low temperature of 120 ° C. or less. In this case, it is preferable to reduce the molar ratio of the hydroxyl group to the cyanate group. A preferred range is 0.05 to 0.11 mole per mole of cyanate group. In this case, there is little cure shrinkage, and a cured product with low thermal expansion and high Tg is obtained.

  On the other hand, a compound having a large phenol hydroxyl group equivalent, for example, a compound having a hydroxyl group equivalent of 175 or more, can suppress the reaction with the cyanate group and can provide a composition having good storage stability and fluidity. The preferred range is 0.1 to 0.4 mole per mole of cyanate group. In this case, a cured product having a low water absorption is obtained although Tg is slightly reduced. In order to obtain desired cured product characteristics and curability, these phenol resins can be used in combination of two or more.

(Dihydroxynaphthalene compound (b-2))
As the component (B), a dihydroxynaphthalene compound (b-2) represented by the following general formula (3) can be preferably used.

Examples of the dihydroxynaphthalene include 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2 , 6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like.
1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene and 1,6-dihydroxynaphthalene having a melting point of 130 ° C. are very reactive and promote the cyclization reaction of the cyanate group in a small amount. The reaction of 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene having a melting point of 200 ° C. or higher is relatively suppressed.

  When these dihydroxynaphthalene compounds (b-2) are used alone, the molecular weight between functional groups is small and the structure is rigid, so that the curing shrinkage is small and a cured product having a high Tg is obtained. Moreover, sclerosis | hardenability can also be adjusted by using together with the phenolic compound (b-1) which has a 2 or more hydroxyl group in 1 molecule with a large hydroxyl equivalent.

  In addition, it is desirable that the halogen element, the alkali metal, and the like in the phenol compound (b-1) and the dihydroxynaphthalene compound (b-2) are 10 ppm, particularly 5 ppm or less when extracted at 120 ° C. under 2 atm.

  The cyanate ester resin used in the present invention is the above phenol compound (b-1) alone, the above dihydroxynaphthalene compound (b-2) alone, or the phenol compound (b-1) and the dihydroxynaphthalene compound ( It is preferable to contain the combination of b-2) as (B) component.

[Inorganic filler]
The cyanate ester resin used in the present invention may further contain an inorganic filler. Examples of the inorganic filler to be blended include silicas such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, aluminosilicate, boron nitride, glass fiber, and antimony trioxide. The average particle diameter and shape of these inorganic fillers are not particularly limited.

  The thickness of the supporting substrate made of cyanate ester resin is preferably 50 μm to 1 mm, more preferably 100 μm to 500 μm. If it is 100 μm or more, it is preferable because it can be prevented from being too thin and easily deformed.

  Moreover, it is preferable that the glass transition temperature of cyanate ester resin is 200 degreeC or more. If it is 200 degreeC or more, there will be almost no change of a thermal expansion coefficient in 200 degrees C or less, and the distortion to the semiconductor molding by the change of a thermal expansion coefficient can be suppressed. That is, the peeling phenomenon due to strain and the influence on the semiconductor element can be suppressed. The glass transition temperature may be 200 ° C. or higher, but the glass transition temperature is preferably 250 ° C. or higher.

  Furthermore, the linear expansion coefficient of the cyanate ester resin is preferably 5 ppm or less, more preferably 1 ppm or more and 3 ppm or less, and particularly preferably 2 ppm or more and 3 ppm or less. If the linear expansion coefficient of the cyanate ester resin is 5 ppm or less, it is possible to suppress an increase in the difference in expansion coefficient between the substrate on which the semiconductor element is mounted or the wafer on which the semiconductor element is formed. It can be surely suppressed. In particular, a large-diameter thin film wafer having a wafer diameter of 300 mm or more and a thickness of 100 μm or less is likely to be easily broken due to slight warping or strain stress, so the linear expansion coefficient is 2 ppm- Particularly preferred is about 3 ppm.

  Such a supporting substrate reduces warpage after collectively sealing a semiconductor element mounting surface of a substrate on which a semiconductor element is mounted, or a semiconductor element forming surface of a wafer on which a semiconductor element is formed, so that one or more semiconductor elements are formed. It is important to reinforce the arrayed and bonded substrates. Therefore, it is desirable that the base material is hard and rigid.

<Uncured resin layer>
The encapsulant laminate composite of the present invention has an uncured resin layer. This uncured resin layer is made of an uncured thermosetting resin formed on one side of the above-mentioned support substrate. This uncured resin layer becomes a resin layer for sealing the semiconductor element mounting surface or the semiconductor element formation surface.

  The thickness of the uncured resin layer is preferably 20 μm or more and 2000 μm or less. If it is 20 μm or more, it is sufficient to seal the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted, or the semiconductor element forming surface of the wafer on which the semiconductor element is formed, and the filling property is poor due to being too thin. The thickness is preferably 2000 μm or less because it is possible to prevent the sealed semiconductor element mounting substrate and the semiconductor element formation wafer after sealing from becoming too thick.

The uncured thermosetting resin that forms the uncured resin layer is not particularly limited, but is usually a liquid epoxy resin, a solid epoxy resin, a silicone resin, or an epoxy resin used for sealing a semiconductor element. An uncured resin layer made of a hybrid resin made of a silicone resin is preferable. In particular, it is preferable to include any of an epoxy resin, a silicone resin, and an epoxy silicone hybrid resin that are solidified at less than 50 ° C. and melt at 50 ° C. or higher and 150 ° C. or lower. With such a thermosetting resin, a cyanate ester resin having a very small expansion coefficient that is a supporting base material can suppress the shrinkage stress during curing of an uncured resin layer containing these resins. Even when a large-diameter substrate such as a wafer or metal is sealed, the warpage of the substrate or wafer, the peeling of the semiconductor element from the substrate can be more reliably suppressed, the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted, Or if it becomes a sealing material laminated complex which can encapsulate the semiconductor element formation surface of the wafer which formed the semiconductor element at the wafer level collectively, and if it is a complex which has an uncured resin layer containing these resins, especially after sealing It becomes the sealing material laminated composite excellent in sealing performance, such as heat resistance and moisture resistance.
Hereinafter, an epoxy resin, a silicone resin, and a hybrid resin composed of an epoxy resin and a silicone resin that can be used as a thermosetting resin will be described in detail.

[Epoxy resin]
The epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol type epoxy resin, or 4, Biphenol type epoxy resin such as 4'-biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin, tetrakispheni Examples thereof include known epoxy resins which are liquid or solid at room temperature, such as roll ethane type epoxy resins, epoxy resins obtained by hydrogenating aromatic rings of phenol dicyclopentadiene novolac type epoxy resins, and alicyclic epoxy resins. If necessary, a certain amount of epoxy resin other than the above can be used in combination according to the purpose of the present invention.

  The thermosetting resin made of an epoxy resin is preferably a resin layer that seals the semiconductor element, so that halogen ions such as chlorine and alkali ions such as sodium are reduced as much as possible. As a method for reducing each ion, a method of adding 10 g of a sample to 50 ml of ion-exchanged water, sealing and leaving it in an oven at 120 ° C. for 20 hours, followed by heat extraction can be cited. Extraction at 120 ° C. It is desirable that all ions be 10 ppm or less.

  The thermosetting resin made of an epoxy resin may further contain an epoxy resin curing agent. As such a curing agent, a phenol novolak resin, various amine derivatives, an acid anhydride or an acid anhydride group partially ring-opened and a carboxylic acid generated can be used. Among these, a phenol novolac resin is desirable in order to ensure the reliability of a semiconductor device manufactured using the encapsulant laminated composite of the present invention. In particular, it is preferable to mix the mixing ratio of the epoxy resin and the phenol novolac resin so that the ratio of the epoxy group to the phenolic hydroxyl group is 1: 0.8 to 1.3.

  Furthermore, in order to accelerate the reaction between the epoxy resin and the curing agent, a metal compound such as an imidazole derivative, a phosphine derivative, an amine derivative, or an organoaluminum compound may be used as a reaction accelerator (catalyst).

  Various additives can be further blended in the thermosetting resin made of an epoxy resin as necessary. For example, various thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, silicone-based low-stress agents, waxes, halogen trapping agents and the like can be mentioned for the purpose of improving the properties of the resin. Depending on the purpose, it can be added and blended.

[Silicone resin]
As the silicone resin, a thermosetting silicone resin or the like can be used. In particular, it is desirable that the uncured resin layer made of a silicone resin contains an addition curable silicone resin composition. The addition-curable silicone resin composition includes (i) an organosilicon compound having a non-conjugated double bond (for example, an alkenyl group-containing diorganopolysiloxane), (ii) an organohydrogenpolysiloxane, and (iii) a platinum-based compound. Those containing a catalyst are particularly preferred. Hereinafter, these components (i) to (iii) will be described.

(I) Component: Organosilicon compound having non-conjugated double bond (i) As component,
R ^{1 ′} R ^{2 ′} R ^{3 ′} SiO— (R ^{4 ′} R ^{5 ′} SiO) _a— (R ^{6 ′} R ^{7 ′} SiO) _b— SiR ^{1 ′} R ^{2 ′} R ^{3 ′} (4)
(Wherein R ^{1 ′} represents a non-conjugated double bond-containing monovalent hydrocarbon group, R ^{2 ′ to} R ^{7 ′} represent the same or different monovalent hydrocarbon groups, and a and b are 0 ≦ a ≦ 500, 0 ≦ b ≦ 250, and an integer satisfying 0 ≦ a + b ≦ 500.)
And an organopolysiloxane such as a linear diorganopolysiloxane blocked at both ends of the molecular chain with an aliphatic unsaturated group-containing triorganosiloxy group.

In the general formula (4), R ^{1 ′} is a non-conjugated double bond-containing monovalent hydrocarbon group, preferably a fatty acid represented by an alkenyl group having 2 to 8 carbon atoms, particularly preferably 2 to 6 carbon atoms. Non-conjugated double bond-containing monovalent hydrocarbon group having a group unsaturated bond.

In the general formula (4), R ^{2 ′ to} R ^{7 ′} are the same or different monovalent hydrocarbon groups, preferably an alkyl group or alkenyl having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms. Group, aryl group, aralkyl group and the like. Of these, R ^{4 ′ to} R ^{7 ′} are more preferably monovalent hydrocarbon groups excluding aliphatic unsaturated bonds, particularly preferably alkyl groups having no aliphatic unsaturated bonds such as alkenyl groups, aryl groups. Group, aralkyl group and the like. Further, among these, R ^{6 ′} and R ^{7 ′} are preferably aromatic monovalent hydrocarbon groups, particularly preferably aryl groups having 6 to 12 carbon atoms such as phenyl groups and tolyl groups.

  In the general formula (4), a and b are integers satisfying 0 ≦ a ≦ 500, 0 ≦ b ≦ 250, and 0 ≦ a + b ≦ 500, and a is preferably 10 ≦ a ≦ 500, b Is preferably 0 ≦ b ≦ 150, and a + b preferably satisfies 10 ≦ a + b ≦ 500.

  The organopolysiloxane represented by the general formula (4) includes, for example, cyclic diorganopolysiloxanes such as cyclic diphenylpolysiloxane and cyclic methylphenylpolysiloxane, diphenyltetravinyldisiloxane and divinyltetraphenyldisiloxane constituting the terminal group. Although it can be obtained by an alkali equilibration reaction with disiloxane such as siloxane, in this case, the polymerization proceeds in an irreversible reaction with a small amount of catalyst in the equilibration reaction with an alkali catalyst (particularly strong alkali such as KOH). Quantitatively, only ring-opening polymerization proceeds and the end-capping rate is high, so that usually no silanol group or chloro component is contained.

（上記式において、ｋ、ｌは、０≦ｋ≦５００、０≦ｌ≦２５０、かつ０≦ｋ＋ｌ≦５００を満足する整数であり、好ましくは５≦ｋ＋ｌ≦２５０、かつ０≦ｌ／（ｋ＋ｌ）≦０．５を満足する整数である。） Specific examples of the organopolysiloxane represented by the general formula (4) include the following.

(In the above formula, k and l are integers satisfying 0 ≦ k ≦ 500, 0 ≦ l ≦ 250, and 0 ≦ k + l ≦ 500, preferably 5 ≦ k + l ≦ 250, and 0 ≦ l / (k + l ) An integer satisfying ≦ 0.5.)

  As the component (i), in addition to the organopolysiloxane having a linear structure represented by the general formula (4), a three-dimensional network structure containing a trifunctional siloxane unit, a tetrafunctional siloxane unit, or the like as necessary. It is also possible to use organopolysiloxanes having (I) The organosilicon compound having a non-conjugated double bond may be used singly or in combination of two or more.

  (I) The amount of a group having a nonconjugated double bond in the organosilicon compound having a nonconjugated double bond (for example, a monovalent hydrocarbon group having a double bond bonded to a Si atom such as an alkenyl group) is The total monovalent hydrocarbon group (all monovalent hydrocarbon groups bonded to Si atoms) is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, and particularly preferably 0. 2 to 5 mol%. If the amount of the group having a non-conjugated double bond is 0.1 mol% or more, a good cured product can be obtained when cured, and if it is 20 mol% or less, mechanical properties when cured are obtained. Is preferable because it is good.

  In addition, (i) the organosilicon compound having a non-conjugated double bond preferably has an aromatic monovalent hydrocarbon group (aromatic monovalent hydrocarbon group bonded to Si atom), and an aromatic monovalent hydrocarbon group. The content of is preferably 0 to 95 mol%, more preferably 10 to 90 mol%, particularly preferably 20 of the total monovalent hydrocarbon group (all monovalent hydrocarbon groups bonded to Si atoms). ˜80 mol%. When an appropriate amount of the aromatic monovalent hydrocarbon group is contained in the resin, there is an advantage that the mechanical properties when cured are good and the production is easy.

(Ii) Component: Organohydrogenpolysiloxane As the component (ii), an organohydrogenpolysiloxane having two or more hydrogen atoms (SiH groups) bonded to a silicon atom in one molecule is preferable. An organohydrogenpolysiloxane having two or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule acts as a crosslinking agent, and (ii) SiH groups in component and (i) component vinyl. A cured product can be formed by an addition reaction with a non-conjugated double bond-containing group such as a group or an alkenyl group.

  The organohydrogenpolysiloxane as component (ii) preferably has an aromatic monovalent hydrocarbon group. Thus, if it is organohydrogenpolysiloxane which has an aromatic monovalent hydrocarbon group, compatibility with said (i) component can be improved. Such organohydrogenpolysiloxanes may be used alone or in combination of two or more. For example, an organohydrogenpolysiloxane having an aromatic hydrocarbon group may be used as part of component (ii). Or it can be included as a whole.

The component (ii) is not limited to these, but 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrogensiloxy) Methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1-glycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-glycidoxypropyl-1,3,5,7- Tetramethylcyclotetrasiloxane, 1-glycidoxypropyl-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, trimethylsiloxy at both ends Blocked dimethylsiloxane methylhydrogenchiro Sun copolymer, both ends dimethylhydrogensiloxy-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy-blocked methylhydrogensiloxane / diphenylsiloxane Polymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, trimethoxysilane polymer, copolymer of (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit And a copolymer composed of (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units, and (C ₆ H ₅ ) SiO _3/2 units.

Moreover, the organohydrogenpolysiloxane obtained using the unit shown by the following structure can also be used.

  The molecular structure of the organohydrogenpolysiloxane of component (ii) may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or of the polymer In the case, the degree of polymerization) is preferably 2 or more, more preferably 3 to 500, and particularly preferably about 4 to 300.

  (Ii) The amount of organohydrogenpolysiloxane is such that (ii) silicon atom-bonded hydrogen atoms (SiH groups) in the component per group having a non-conjugated double bond such as an alkenyl group in the component (ii) The amount is preferably 0.7 to 3.0.

(Iii) Component: Platinum-Based Catalyst A platinum-based catalyst is used as the (iii) component. Examples of the platinum-based catalyst include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum complexes having a chelate structure, and the like. These can be used singly or in combination of two or more.

  The amount of component (iii) is a curing effective amount and may be a so-called catalytic amount, and is usually 0.1 to 0.1 parts by mass in terms of platinum group metal per 100 parts by mass of component (i) and component (ii). It is preferably 500 ppm, and particularly preferably in the range of 0.5 to 100 ppm.

  In the case of using a silicone resin as the thermosetting resin, it is preferable that halogen ions such as chlorine and alkali ions such as sodium are reduced as much as possible because it becomes a resin layer for sealing the semiconductor element. As a method for reducing each ion, a method similar to that for the epoxy resin can be exemplified, and it is desirable that any ion is 10 ppm or less by extraction at 120 ° C.

[Hybrid resin consisting of epoxy resin and silicone resin]
Examples of the epoxy resin and the silicone resin contained in the hybrid resin include the aforementioned epoxy resin and the aforementioned silicone resin.

  Since the thermosetting resin made of a hybrid resin becomes a resin layer for sealing a semiconductor element, halogen ions such as chlorine and alkali ions such as sodium are preferably reduced as much as possible. Usually, it is desirable that any ion is 10 ppm or less by extraction at 120 ° C.

[Inorganic filler]
An inorganic filler can be mix | blended with said thermosetting resin. Examples of the inorganic filler to be blended include silica such as fumed silica (fumed silica), precipitated silica, fused silica, crystalline silica, alumina, silicon nitride, aluminum nitride, aluminosilicate, boron nitride, glass Examples thereof include fibers and antimony trioxide. The average particle diameter and shape of these inorganic fillers are not particularly limited.

  In particular, as an inorganic filler to be added to a thermosetting resin made of an epoxy resin, in order to increase the bonding strength between the epoxy resin and the inorganic filler, the surface is previously coated with a coupling agent such as a silane coupling agent or a titanate coupling agent. You may mix | blend what was processed.

  Examples of such a coupling agent include epoxy functions such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Functional alkoxysilanes such as N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and γ-mercapto It is preferable to use a mercapto functional alkoxysilane such as propyltrimethoxysilane. The amount of coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

  Also when adding to the thermosetting resin which consists of a silicone resin composition, you may mix | blend what processed the surface of the said inorganic filler with the above coupling agents.

  The blending amount of the inorganic filler is preferably 100 to 1300 parts by mass, and particularly preferably 200 to 1000 parts by mass with respect to 100 parts by mass of the total mass of the thermosetting resin. If it is 100 parts by mass or more, sufficient strength can be obtained, and if it is 1300 parts by mass or less, a decrease in fluidity due to thickening is suppressed, and a poor filling property due to a decrease in fluidity is suppressed. The formed semiconductor elements and the semiconductor elements arranged and mounted on the substrate can be satisfactorily sealed. In addition, it is preferable to contain this inorganic filler in 50-95 mass% of the whole composition which comprises a thermosetting resin, especially 60-90 mass%.

<Sealing material laminate composite>
An example of a cross-sectional view of the sealing material laminate composite of the present invention is shown in FIG. The sealing material laminate composite 10 of the present invention includes a support substrate 1 made of a cured or semi-cured cyanate ester resin and an uncured material made of an uncured thermosetting resin formed on one side of the support substrate 1. The resin layer 2 is included.

[Method for producing sealing material laminated composite]
When producing a sealing material laminated composite of the present invention using a support substrate made of a cyanate ester resin, printing, dispensing, etc. on one side of the support substrate made of a cyanate ester resin under reduced pressure or vacuum Then, a thermosetting resin such as a thermosetting liquid epoxy resin or a silicone resin is further applied and heated to form a solid uncured resin layer at 50 ° C. or lower to produce a sealing material laminated composite. .

  Furthermore, various methods that have been used in conventional epoxy thermosetting resins and silicone thermosetting resins, such as press-molding and printing an uncured thermosetting resin on one side of a support substrate made of cyanate ester resin An uncured resin layer can be formed. After the formation, it is usually preferable to post-cure at a temperature of about 180 ° C. for 4 to 8 hours.

  In addition, as a method of forming an uncured resin layer composed of an uncured thermosetting resin on one side of a support substrate composed of a cyanate ester resin, an epoxy thermosetting resin or a silicone thermosetting resin that is solid at room temperature, etc. Uniform by removing by a method such as pressurizing while heating or adding a suitable amount of polar solvent such as acetone to the epoxy resin composition to form a thin film by printing etc. and heating the solvent under reduced pressure. An uncured resin layer can be formed on one side of the support substrate.

  In any method, an uncured resin layer made of an uncured thermosetting resin having a thickness of 20 to 2000 μm, particularly about 30 to 500 μm, free from voids or volatile components, on one side of a support substrate made of a cyanate ester resin. Can be formed.

[Substrate on which semiconductor element is mounted and wafer on which semiconductor element is formed]
The encapsulant laminate composite of the present invention is a composite for collectively sealing a semiconductor element mounting surface of a substrate on which a semiconductor element is mounted and a semiconductor element forming surface of a wafer on which the semiconductor element is formed. Examples of the substrate on which the semiconductor element is mounted include a substrate in which one or more semiconductor elements 3 in FIG. 2A are mounted on an inorganic, metal or organic substrate 5 with an adhesive 4. Moreover, as a wafer in which the semiconductor element was formed, for example, a wafer in which the semiconductor element 6 is formed on the wafer 7 in FIG. In addition, the board | substrate which mounts a semiconductor element includes what used various wafers, such as a silicon wafer, an organic substrate, a glass substrate, a metal substrate, etc. as the board | substrate 5, and the semiconductor element array which mounted the semiconductor element and arranged. .

<Semiconductor element mounting substrate after sealing and semiconductor element forming wafer after sealing>
FIGS. 2A and 2B show examples of cross-sectional views of the post-sealing semiconductor element mounting substrate and the post-sealing semiconductor element forming wafer sealed with the sealing material laminate composite of the present invention. The post-sealing semiconductor element mounting substrate 11 of the present invention covers the semiconductor element mounting surface of the substrate 5 on which the semiconductor element 3 is mounted with the uncured resin layer 2 (see FIG. 1) of the sealing material laminated composite 10. The cured resin layer 2 (see FIG. 1) is heated and cured to obtain a cured resin layer 2 ′, which is collectively sealed by the sealing material laminate composite 10 (FIG. 2 (a)). Further, the post-sealing semiconductor element forming wafer 12 of the present invention covers the semiconductor element forming surface of the wafer 7 on which the semiconductor element 6 is formed by the uncured resin layer 2 (see FIG. 1) of the encapsulating material laminate composite 10. The uncured resin layer 2 (see FIG. 1) is heated and cured to form a cured resin layer 2 ′, which is collectively sealed by the sealing material laminated composite 10 (FIG. 2B). .

  As described above, the uncured resin layer of the encapsulant laminate composite covers the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted or the semiconductor element forming surface of the wafer on which the semiconductor element is formed, and the uncured resin layer is heated. If the substrate is a post-sealing semiconductor element mounting substrate or a post-sealing semiconductor element formation wafer that is collectively sealed by the encapsulant laminate composite, the substrate or the wafer is warped or the semiconductor element is It becomes a post-sealing semiconductor element mounting substrate or a post-sealing semiconductor element forming wafer in which the peeling is suppressed.

<Semiconductor device>
An example of the semiconductor device of the present invention is shown in FIGS. Semiconductor devices 13 and 14 of the present invention are obtained by dicing the post-sealing semiconductor element mounting substrate 11 (see FIG. 2) or the post-sealing semiconductor element forming wafer 12 (see FIG. 2) into individual pieces. . As described above, the sealing material laminated composite 10 having a cyanate ester resin excellent in sealing performance such as heat resistance and moisture resistance is sealed, and the warpage of the substrate and the wafer and the peeling of the semiconductor element 3 from the substrate are suppressed. The semiconductor devices 13 and 14 manufactured by dicing and dicing the sealed semiconductor element mounting substrate 11 (see FIG. 2) or the sealed semiconductor element forming wafer 12 (see FIG. 2) are high-quality semiconductors. It becomes a device. When the semiconductor element mounting substrate 11 (see FIG. 2A) after sealing is diced into individual pieces, the semiconductor device 13 is mounted on the substrate 5 via the adhesive 4, and the semiconductor element 3 is mounted thereon. It becomes a semiconductor device sealed by the sealing material laminated composite 10 which has the support base material 1 which consists of resin layer 2 'and cyanate ester resin after hardening (FIG. 3 (a)). Further, when the semiconductor element forming wafer 12 after sealing (see FIG. 2B) is diced into individual pieces, the semiconductor device 14 has the semiconductor element 6 formed on the wafer 7, and the cured resin layer is formed thereon. It becomes a semiconductor device sealed by the sealing material laminated composite 10 which has the support base material 1 which consists of 2 'and cyanate ester resin (FIG.3 (b)).

<Method for Manufacturing Semiconductor Device>
The present invention is a method of manufacturing a semiconductor device,
A coating step of covering the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted by the uncured resin layer of the encapsulating material laminate composite or the semiconductor element forming surface of the wafer on which the semiconductor element is formed;
By heating and curing the uncured resin layer, the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted or the semiconductor element forming surface of the wafer on which the semiconductor element is formed is collectively sealed, and the semiconductor element is mounted after sealing. A process for manufacturing a semiconductor device by dicing the substrate or the post-sealing semiconductor element mounting substrate or the post-sealing semiconductor element forming wafer into individual pieces Provided is a method for manufacturing a semiconductor device, characterized by having a singulation step. Hereinafter, the manufacturing method of the semiconductor device of the present invention will be described with reference to FIG.

[Coating process]
The covering process according to the method for manufacturing a semiconductor device of the present invention is performed by applying the adhesive 4 by the uncured resin layer 2 of the sealing material laminated composite 10 having the support base 1 made of cyanate ester resin and the uncured resin layer 2. In this step, the semiconductor element mounting surface of the substrate 5 on which the semiconductor element 3 is mounted or the semiconductor element forming surface of the wafer (not shown) on which the semiconductor element (not shown) is formed is covered (FIG. 4A).

[Sealing process]
In the sealing process according to the method for manufacturing a semiconductor device of the present invention, the uncured resin layer 2 of the encapsulating material laminate composite 10 is heated and cured to form a cured resin layer 2 ′. A semiconductor element mounting surface of a mounted substrate 5 or a semiconductor element forming surface of a wafer (not shown) on which a semiconductor element (not shown) is formed is collectively sealed, and a semiconductor element mounting substrate 11 after sealing or a semiconductor element formation after sealing is formed. This is a process for forming a wafer (not shown) (FIG. 4B).

[Individualization process]
The singulation process according to the method for manufacturing a semiconductor device of the present invention is performed by dicing the encapsulated semiconductor element mounting substrate 11 or the encapsulated semiconductor element forming wafer (not shown) into individual pieces, thereby obtaining the semiconductor device 13. , 14 (see FIG. 3B) (FIGS. 4C and 4D).

  More specific description will be given below. In the covering step and the sealing step, by using a vacuum laminator device or the like used for lamination of a solder resist film or various insulating films, it is possible to perform covering and sealing without voids or warping. As a lamination method, any method such as roll lamination, diaphragm vacuum lamination, and air pressurization lamination can be used. Especially, combined use of vacuum lamination and an air pressurization type is preferable.

  Here, as an example, using a vacuum lamination apparatus manufactured by Nichigo Morton, a support base material made of a cyanate ester resin having a thickness of 50 μm and an uncured resin layer made of an uncured thermosetting epoxy resin having a thickness of 50 μm on one side are provided. A case where a silicon wafer having a thickness of 70 μm and a diameter of 300 mm (12 inches) is sealed with the sealing material laminated composite will be described.

  Of the plates set at 150 ° C. with built-in heaters at the top and bottom, the upper plate is in close contact with the heater with the diaphragm rubber being decompressed. A 300 mm (12 inch) silicon wafer is set on the lower plate, and the uncured resin layer surface of the encapsulating material laminate composite is set on one side of the silicon wafer so as to match the semiconductor formation surface of the silicon wafer. Thereafter, the lower plate rises, and the upper and lower plates are brought into close contact with each other by an O-ring installed so as to surround the silicon wafer set on the lower plate, whereby the vacuum chamber is depressurized. . When the inside of the vacuum chamber is sufficiently depressurized, the piping valve connected to the vacuum pump is closed between the diaphragm rubber on the upper plate and the heater, and compressed air is sent in. As a result, the upper diaphragm rubber expands, the silicon wafer and the sealing material laminated composite are sandwiched between the upper diaphragm rubber and the lower plate, vacuum lamination is performed, and at the same time, the thermosetting epoxy resin of the uncured resin layer is cured. Advances and sealing is completed. A curing time of about 3 to 20 minutes is sufficient. When vacuum lamination is completed, the inside of the vacuum chamber is returned to normal pressure, the lower plate is lowered, and the sealed silicon wafer is taken out. By the above process, the wafer can be sealed without voids or warping. The taken-out silicon wafer is usually post-cured at a temperature of 150 to 180 [deg.] C. for 1 to 4 hours to stabilize electrical characteristics and mechanical characteristics.

  The coating and sealing process using the above vacuum lamination apparatus is not limited to the illustrated thermosetting epoxy resin, but can also be used in the case of a silicone resin or a mixed resin of epoxy and silicone.

  With such a method of manufacturing a semiconductor device, the semiconductor element mounting surface or the semiconductor element forming surface can be easily covered without filling defects with the uncured resin layer of the encapsulating material laminate composite in the covering step. In addition, since a support base material made of a cyanate ester resin can suppress shrinkage stress during curing of the uncured resin layer, a semiconductor element mounting surface or a semiconductor element is formed in the sealing process because a sealing material laminated composite is used. Even when a thin large-diameter wafer or a large-diameter substrate such as metal is encapsulated, the sealing of the substrate and the wafer is prevented from being warped and peeling of the semiconductor element from the substrate. A semiconductor element mounting substrate after stopping or a semiconductor element forming wafer after sealing can be obtained. Further, in the singulation process, the post-sealing semiconductor element mounting substrate or the post-sealing semiconductor element is sealed with a sealing material laminated composite excellent in sealing performance such as heat resistance and moisture resistance and warpage is suppressed. Since the semiconductor device can be diced from the formed wafer and separated into individual pieces, the semiconductor device manufacturing method can manufacture a high-quality semiconductor device.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown about the manufacturing method of the semiconductor device using the sealing material laminated composite of this invention, and this invention is demonstrated in detail, this invention is not limited to these.

[Example 1]
[Production of support substrate]
Cyanate ester compound 1 Primaset PT-60 (Lonza cyanate group equivalent 119) 90 parts by mass, phenol compound TD-2131 (DIC phenolic hydroxyl group equivalent 110) 10 parts by mass, fused spherical silica (fine powder) 920 parts by mass, After blending 1.5 parts by weight of carnauba wax and uniformly mixing with a high-speed mixer, a cyanate ester resin composition was produced by uniformly kneading with two heated rolls.
Cyanate ester resin composition is pulverized and formed into a granular powder by compression molding (175 ° C.), and a supporting substrate made of a uniform cyanate ester resin having a glass transition temperature of 260 ° C. and a linear expansion coefficient of 3 ppm and a thickness of 150 μm ( Ia) was obtained.

[Preparation of thermosetting resin composition]
60 parts by mass of cresol novolac type epoxy resin (EOCN1020 made by Nippon Kayaku), 30 parts by mass of phenol novolac resin (made by H-4 Gunei Chemical), 400 parts by mass of spherical silica (average particle size 7 μm made by Tatsumori), catalyst TPP ( Triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 0.2 parts by mass and silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass are sufficiently mixed with a high-speed mixing device, then heated and kneaded with a continuous kneader to form a sheet. Cooled down. The sheet was pulverized to obtain a thermosetting resin composition (Ib) made of an epoxy resin as a granular powder.

[Production of encapsulant laminate composite]
The granule powder of the epoxy resin composition (Ib) was uniformly dispersed on the support substrate (Ia). The upper and lower mold temperatures are set to 80 ° C., a fluororesin-coated PET film (peeling film) is set on the upper mold, and the inside of the mold is depressurized to a vacuum level so that the thickness of the uncured resin layer becomes 80 μm. To 3 minutes to form a sealing material laminated composite substrate (Ic). After molding, it was cut into a disk shape having a diameter of 300 mm (12 inches).

[Coating and sealing of wafer on which semiconductor element is formed]
Next, coating and sealing were performed using a vacuum lamination apparatus in which the plate temperature manufactured by Nichigo Morton was set to 130 ° C. First, a 300 mm (12 inch) silicon wafer having a thickness of 70 μm with a semiconductor element formed on the lower plate is set, and the uncured sealing material composite (Ic) from which the release film is removed is uncured. The epoxy resin composition (Ib) surface, which is a resin layer, was covered with the silicon wafer surface. Then, the plate was closed and cured by sealing by vacuum compression molding for 5 minutes. After curing and sealing, the silicon wafer sealed with the sealing material laminated composite (Ic) was further post-cured at 150 ° C. for 2 hours to obtain a semiconductor element-formed wafer (Id) after sealing. .

[Example 2]
[Preparation of thermosetting resin composition]
60 parts by mass of cresol novolac type epoxy resin (EOCN1020 made by Nippon Kayaku), 30 parts by mass of phenol novolac resin (made by H-4 Gunei Chemical Co., Ltd.), 300 parts by mass of spherical silica (average particle size 7 μm made by Tatsumori), catalyst TPP ( Triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 0.2 parts by mass and silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass are sufficiently mixed with a high-speed mixing device, then heated and kneaded with a continuous kneader to form a sheet. Cooled down. The sheet was pulverized to obtain an epoxy resin composition (II-b) as a granular powder.

[Production of encapsulant laminate composite]
The supporting base material (Ia) was set on a lower mold of a compression molding apparatus capable of heating and compressing under reduced pressure, and the granular powder of the epoxy resin composition (II-b) was uniformly dispersed thereon. The upper and lower mold temperatures are set to 80 ° C., a fluororesin-coated PET film (peeling film) is set on the upper mold, and the inside of the mold is depressurized to a vacuum level so that the thickness of the uncured resin layer becomes 80 μm. The mixture was compression molded for 3 minutes to prepare a sealing material laminated composite (II-c). After molding, it was cut into a disk shape having a diameter of 300 mm (12 inches).

[Coating and sealing of wafer on which semiconductor element is formed]
Next, coating and sealing were performed using a vacuum lamination apparatus in which the plate temperature manufactured by Nichigo Morton was set to 130 ° C. First, a 300 mm (12 inch) silicon wafer having a thickness of 70 μm with a semiconductor element formed on the lower plate was set, and the uncured encapsulant laminate (II-c) from which the release film was removed was removed. The epoxy resin (II-b) surface, which is a resin layer, was covered with the silicon wafer surface. Then, the plate was closed and cured by sealing by vacuum compression molding for 5 minutes. After curing and sealing, the silicon wafer sealed with the sealing material laminated composite (II-c) was further post-cured at 150 ° C. for 2 hours to obtain a semiconductor element-formed wafer (II-d) after sealing. .

[Example 3]
[Production of support substrate]
Cyanate ester compound 2 Primaset PT-60 (Lonza cyanate group equivalent 119) 78 parts by mass, phenol compound * MEH-7800SS (Maywa Kasei) phenolic hydroxyl group equivalent 175) 22 parts by mass, fused spherical silica (fine powder) 920 Cyanate ester resin composition was manufactured by mix | blending a mass part and 1.5 mass parts of carnauba wax, uniformly mixing with a high-speed mixer, and then kneading uniformly with a heated two roll.
A cyanate ester resin composition (III-a) having a glass transition temperature of 220 ° C. and a linear expansion coefficient of 4 ppm and a thickness of 180 μm is obtained by pulverizing the cyanate ester resin composition and compression molding (175 ° C.) as a granular powder. Obtained.

[Preparation of thermosetting resin composition]
60 parts by mass of cresol novolac type epoxy resin (EOCN1020 made by Nippon Kayaku), 30 parts by mass of phenol novolac resin (made by H-4 Gunei Chemical), 400 parts by mass of spherical silica (average particle size 7 μm made by Tatsumori), catalyst TPP ( Triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 0.2 parts by mass and silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass are sufficiently mixed with a high-speed mixing device, then heated and kneaded with a continuous kneader to form a sheet. Cooled down. The sheet was pulverized to obtain an epoxy resin composition (III-b) as a granular powder.

[Production of encapsulant laminate composite]
The support base material (III-a) was set on a lower mold of a compression molding apparatus capable of heating and compressing under reduced pressure, and the granular powder of the epoxy resin composition (III-b) was uniformly dispersed thereon. Set the upper and lower mold temperatures to 80 ° C, set the upper mold with a fluororesin-coated PET film (peeling film), depressurize the mold to the vacuum level, and compress for 3 minutes so that the resin thickness becomes 80 µm Molding was performed to produce a sealing material laminated composite (III-c). After molding, it was cut into a disk shape having a diameter of 300 mm (12 inches).

[Coating and sealing of substrates on which semiconductor elements are mounted]
Next, it coat | covered and sealed using the vacuum lamination apparatus which set the plate temperature by Nichigo Morton company to 170 degreeC. First, 400 silicon chips (shape: 5 mm), which are individual semiconductor elements, are bonded to a lower plate on a metal substrate having a thickness of 300 mm (12 inches) and a thickness of 100 μm via an adhesive whose adhesive strength decreases at high temperatures. An epoxy resin composition (III-) which is an uncured resin layer of a sealing material laminated composite (III-c) in which a silicon wafer in which x7 mm and a thickness of 100 μm are aligned and mounted is set and a release film is removed thereon b) The surface was coated in accordance with the semiconductor element mounting surface. Then, the plate was closed and cured by sealing by vacuum compression molding for 5 minutes. After curing and sealing, post-curing was performed at 170 ° C. for 4 hours to obtain a semiconductor element mounting substrate (III-d) after sealing.

[Example 4]
[Preparation of thermosetting resin composition]
60 parts by mass of polyfunctional epoxy resin (EPPN-502H made by Nippon Kayaku), 30 parts by mass of phenol novolac resin (DL-92 made by Meiwa Kasei), 400 parts by mass of spherical silica (average particle size 1 μm made by Adma), catalyst TPP ( Triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 0.2 parts by mass and silane coupling agent (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass are sufficiently mixed with a high-speed mixing device, then heated and kneaded with a continuous kneader to form a sheet. Cooled down. The sheet was pulverized to obtain an epoxy resin composition (IV-b) as a granular powder.

[Production of encapsulant laminate composite]
The support base material (III-a) was set on a lower mold of a compression molding apparatus capable of heating and compressing under reduced pressure, and the granular powder of the epoxy resin composition (IV-b) was uniformly dispersed thereon. Set the upper and lower mold temperatures to 80 ° C, set the upper mold with a fluororesin-coated PET film (peeling film), depressurize the mold to the vacuum level, and compress for 3 minutes so that the resin thickness becomes 80 µm Molding was performed to produce a sealing material laminated composite (IV-c). After molding, it was cut into a disk shape having a diameter of 300 mm (12 inches).

[Coating and sealing of substrates on which semiconductor elements are mounted]
Next, it coat | covered and sealed using the vacuum compression molding apparatus which set the plate temperature by Apic Yamada Co., Ltd. to 175 degreeC. First, 400 silicon chips (shape: 5 mm ×× 5 mm × 12 mm) are bonded to an upper plate through an adhesive whose adhesive strength decreases at a high temperature on a metal substrate having a thickness of 300 mm (12 inches) and a thickness of 100 μm. 7 mm, 100 μm thick) An epoxy resin (IV-b) surface which is an uncured resin layer of a sealing material laminated composite (IV-c) on which a silicon wafer having an aligned and mounted structure is set and a release film is removed thereon Was coated according to the semiconductor element mounting surface. Then, the plate was closed and cured by sealing by vacuum compression molding for 5 minutes. After curing and sealing, post-curing was performed at 170 ° C. for 4 hours to obtain a semiconductor element mounting substrate (IV-d) after sealing.

[Comparative Example 1]
[Substrate on which semiconductor elements are mounted]
400 silicon chips (shape: 5 mm × 7 mm, thickness) which are separated semiconductor elements on a metal substrate having a diameter of 300 mm (8 inches) and a thickness of 500 μm via an adhesive whose adhesive strength decreases at high temperature 125 μm) were aligned and mounted.

[Coating and sealing of substrates on which semiconductor elements are mounted]
This substrate is set on a lower mold of a compression molding apparatus capable of heating and compressing under reduced pressure, and then the epoxy resin composition (Vb) granular powder produced in the same manner as in Example 3 is uniformly dispersed thereon. It was. The upper and lower mold temperatures are set to 170 ° C, and a fluororesin-coated PET film (peeling film) is set on the upper mold, the inside of the mold is depressurized to a vacuum level, and compressed for 3 minutes so that the resin thickness becomes 50 μm. Molded and cured and sealed. After curing and sealing, post-curing was performed at 170 ° C. for 4 hours to obtain a semiconductor element mounting substrate (Vd) after sealing.

  As described above, the sealed semiconductor element formation wafers (Id) to (II-d) sealed in Examples 1 to 4 and Comparative Example 1, and the sealed semiconductor element mounting substrate (III-d), ( IV-d), (Vd) warpage, appearance, adhesion state between resin and substrate, and presence / absence of peeling of semiconductor element from metal substrate were investigated. The results are shown in Table 1. Here, as for the appearance, it was determined whether or not there were voids and unfilled. In addition, the adhesion state was determined to be good if there was no peeling during molding.

  Moreover, the post-sealing semiconductor element mounting substrate and the post-sealing semiconductor element formation wafer of Examples 1 to 4 and Comparative Example 1 were diced into individual pieces, and the following heat resistance test and moisture resistance test were performed. In the heat resistance test, a heat cycle test (holding at -25 ° C. for 10 minutes and holding at 125 ° C. for 10 minutes for 1000 cycles) was performed on the test piece, and it was evaluated whether continuity could be obtained after the test. In the moisture resistance test, a DC test voltage of 10 V was applied to both electrodes of the circuit under the conditions of a temperature of 85 ° C. and a relative humidity of 85% for this test piece, and a migration tester (IMV, MIG-86) was used. Thus, it was evaluated whether a short circuit occurred. As a result, it was revealed that Examples 1 to 4 have excellent heat resistance and moisture resistance.

  From the above results, the sealing material laminated composite of the present invention can suppress the warpage of the substrate or wafer, the peeling of the semiconductor element from the substrate, and the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted, or the semiconductor element The semiconductor element formation surface of the wafer on which the wafer is formed can be collectively sealed at the wafer level, and after sealing, the semiconductor element mounting substrate after sealing and the semiconductor element formation after sealing have excellent sealing performance such as heat resistance and moisture resistance. It became clear that a wafer was obtained.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

DESCRIPTION OF SYMBOLS 1 ... Support base material, 2 ... Uncured resin layer, 2 '... Resin layer after hardening, 3 ... Semiconductor element,
4 ... Adhesive, 5 ... Substrate, 6 ... Semiconductor element, 7 ... Wafer,
10 ... Sealing material laminated composite, 11 ... Semiconductor element mounting substrate after sealing,
12 ... Semiconductor element formation wafer after sealing, 13 ... Semiconductor device, 14 ... Semiconductor device.

Claims (7)

A sealing material laminated composite for collectively sealing a semiconductor element mounting surface of a substrate on which one or more semiconductor elements are mounted, or a semiconductor element forming surface of a wafer on which a semiconductor element is formed,
A support substrate made of a cured or semi-cured cyanate ester resin, and an uncured resin layer made of an uncured thermosetting resin formed on one side of the support substrate ,
The cyanate ester resin is
(A) Cyanate ester compound represented by the following general formula (1) or oligomer thereof

(Wherein R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents

Where n = 0 to 30. R ⁴ is a hydrogen atom or methyl. )
(B) a phenol compound (b-1) having two or more hydroxyl groups in one molecule represented by the following general formula (2) or a dihydroxynaphthalene compound (b-2) represented by the following general formula (3), Or both

(Wherein R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁷ represents

Where m is an integer from 0 to 30. R ⁴ is a hydrogen atom or methyl. )

The glass transition temperature after curing of the cyanate ester resin is 200 ° C. or more, and the thermal expansion coefficient is 5 ppm or less,
The thermosetting resin is an epoxy resin, a silicone resin, or a hybrid resin composed of an epoxy resin and a silicone resin . 2. The encapsulating material laminate composite according to claim 1, wherein the uncured resin layer has a thickness of 20 μm or more and 2000 μm or less. The encapsulating material laminated composite according to claim 1 or 2 , wherein the uncured resin layer is solidified at less than 50 ° C and melted at 50 ° C or more and 150 ° C or less. A semiconductor element mounting substrate after sealing in which a semiconductor element mounting surface of a substrate on which a semiconductor element is mounted is sealed,
The semiconductor element mounting surface of the board | substrate which mounted the semiconductor element with the uncured resin layer which the sealing material laminated composite of any one of Claim 1 thru | or 3 has is covered, and the said uncured resin layer is heated. A semiconductor element mounting substrate after sealing, wherein the substrate is sealed by the sealing material laminate composite by curing. A semiconductor element formation wafer after sealing in which a semiconductor element formation surface of a wafer on which a semiconductor element is formed is sealed,
The semiconductor element formation surface of the wafer in which the semiconductor element was formed is covered with the uncured resin layer of the encapsulating material laminate composite according to any one of claims 1 to 3, and the uncured resin layer is heated. A post-encapsulation semiconductor element-formed wafer characterized by being cured and collectively encapsulated by the encapsulant laminate composite. A semiconductor device, wherein the post-sealing semiconductor element mounting substrate according to claim 4 or the post-sealing semiconductor element formation wafer according to claim 5 is diced into individual pieces. A method for manufacturing a semiconductor device, comprising:
The uncured resin layer having a sealant laminated composite body according to any one of claims 1 to 3, the semiconductor element mounting surface of the substrate mounted with the semiconductor element, or a wafer provided with a semiconductor element semiconductor A coating process for coating the element forming surface;
By heating and curing the uncured resin layer, the semiconductor element mounting surface of the substrate on which the semiconductor element is mounted or the semiconductor element forming surface of the wafer on which the semiconductor element is formed is collectively sealed, and the semiconductor element after sealing A sealing step for forming a mounting substrate or a semiconductor element-formed wafer after sealing; and
A method of manufacturing a semiconductor device, comprising: a step of dividing a semiconductor device mounting substrate or a post-sealing semiconductor element forming wafer into individual pieces by dicing the individual wafers.

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