JP2017103289A - Adhesive for semiconductor, semiconductor device, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic curing type adhesive for semiconductors which is excellent in stability after a heating step and a dicing step.SOLUTION: The adhesive for semiconductors includes a (meth) acrylic compound and a compound of the formula (1) or (2). [In the formulas (1), (2) and (3), Rrepresents a hydrogen atom, an alkyl group, or a group represented by the formula (3), and R, R, R, R, R, R, R, and Rrepresent a hydrogen atom or a methyl group, and Rand Rrepresent a methyl group or a phenyl group.]SELECTED DRAWING: Figure 1

Description

  The present invention relates to a semiconductor adhesive, a semiconductor device, and a method for manufacturing a semiconductor device.

  Conventionally, a wire bonding method using a fine metal wire such as a gold wire has been widely applied to connect a semiconductor chip and a substrate. However, in order to meet demands for high functionality, high integration, high speed, etc., for semiconductor devices, A flip chip connection method (FC connection method) in which conductive protrusions called bumps are formed on a chip or a substrate to directly connect the semiconductor chip and the substrate is becoming widespread.

  Flip chip connection methods include metal bonding using solder, tin, gold, silver, copper, etc., metal bonding by applying ultrasonic vibration, method of maintaining mechanical contact by the shrinkage force of the resin, etc. However, from the viewpoint of the reliability of the connection portion, a method of metal bonding using solder, tin, gold, silver, copper, or the like is common.

  For example, in connection between a semiconductor chip and a substrate, a COB (Chip On Board) type connection method that is actively used in BGA (Ball Grid Array), CSP (Chip Size Package), etc. is also a flip chip connection method. . The flip chip connection method is also widely used in a COC (Chip On Chip) type connection method in which bumps or wirings are formed on semiconductor chips to connect the semiconductor chips (for example, Patent Document 1 below). reference).

  For packages that are strongly required to be further reduced in size, thickness, and functionality, there are chip stack type packages, POP (Package On Package), TSV (Through-Silicon Via), etc., in which the above connection methods are stacked and multi-staged. It has begun to spread widely. Since the package can be made smaller by arranging it in a three-dimensional shape instead of a flat shape, these technologies are frequently used, and it is also effective for improving semiconductor performance, reducing noise, reducing mounting area, and reducing power consumption. It is attracting attention as a wiring technology.

  Also, from the viewpoint of improving productivity, COW (Chip On Wafer) for manufacturing a semiconductor package by bonding a semiconductor chip onto a wafer after being crimped (connected), and individualizing after bonding (connecting) the wafers together A WOW (Wafer On Wafer) for manufacturing a semiconductor package has also attracted attention. Furthermore, a gang bonding method in which a plurality of chips are aligned on a wafer or a map substrate and temporarily crimped and then a plurality of chips are crimped together to ensure connection is also attracting attention from the viewpoint of improving productivity. Yes.

JP 2008-294382 A

  In the above-described various semiconductor device manufacturing methods, a semiconductor adhesive is applied to a semiconductor wafer (chip) or a semiconductor substrate, and the semiconductor adhesive is heated and then diced to separate the semiconductor wafer. The crimping process is performed. In the dicing step, dicing is performed while cooling with pure water and washing away the cutting waste, so that the semiconductor adhesive is exposed to pure water.

  The adhesive for a semiconductor is required to be stable without changing its characteristics even after a heating process and a dicing process (immersion process) at the time of supply to a semiconductor wafer or a semiconductor substrate. However, conventional semiconductor adhesives, particularly semiconductor adhesives that can manufacture semiconductor devices without voids in a short crimping time, such as acrylic-curing adhesives, can be used in the heating process (film-like semiconductor adhesives are semiconductors). The stability after the laminating process on the wafer or the semiconductor substrate) and the dicing process (immersion process) is poor, the characteristics are changed before the press bonding process, and the productivity is lowered.

  The present invention has been made in order to solve the above-described problems, and is an adhesive for a semiconductor that is excellent in stability after a heating step and a dicing step, even if it is an acrylic curing adhesive, and the adhesive for a semiconductor. An object of the present invention is to provide a semiconductor device using the semiconductor device and a method for manufacturing the semiconductor device.

［式（１）及び（２）中、Ｒ^１は水素原子、アルキル基又は下記式（３）で表される基を示し、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は水素原子又はメチル基を示し、Ｒ^６はメチル基又はフェニル基を示す。］

［式（３）中、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は水素原子又はメチル基を示し、Ｒ^１６はメチル基又はフェニル基を示す。］
［２］ 式（１）〜（３）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５がメチル基である、［１］に記載の半導体用接着剤。
［３］ 重量平均分子量が１００００以上の高分子化合物を更に含有する、［１］又は［２］に記載の半導体用接着剤。
［４］ 上記高分子化合物の重量平均分子量が３００００以上であり、上記高分子化合物のガラス転移温度が１００℃以下である、［３］に記載の半導体用接着剤。
［５］ フィルム状である、［１］〜［４］のいずれかに記載の半導体用接着剤。
［６］ 上記（メタ）アクリル化合物が２５℃で固形である、［１］〜［５］のいずれかに記載の半導体用接着剤。
［７］ 上記式（１）又は（２）で表される化合物が、熱ラジカル発生剤である、［１］〜［６］のいずれかに記載の半導体用接着剤。
［８］ 半導体チップ及び配線回路基板のそれぞれの接続部が互いに電気的に接続された半導体装置、又は複数の半導体チップのそれぞれの接続部が互いに電気的に接続された半導体装置において上記接続部の封止に用いられる、［１］〜［７］のいずれかに記載の半導体用接着剤。
［９］ ［１］〜［８］のいずれかに記載の半導体用接着剤を用いる、半導体装置の製造方法。
［１０］ ［１］〜［８］のいずれかに記載の半導体用接着剤又はその硬化物を備える半導体装置。 The present invention provides the following [1] to [10].
[1] A semiconductor adhesive containing a (meth) acrylic compound and a compound represented by the following formula (1) or (2).

[In the formulas (1) and (2), R ¹ represents a hydrogen atom, an alkyl group or a group represented by the following formula (3), and R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a methyl group. R ⁶ represents a methyl group or a phenyl group. ]

[In the formula (3), R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or a methyl group, and R ¹⁶ represents a methyl group or a phenyl group. ]
[2] For semiconductors according to [1], in the formulas (1) to (3), R ² , R ³ , R ⁴ , R ⁵ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are methyl groups. adhesive.
[3] The adhesive for semiconductors according to [1] or [2], further containing a polymer compound having a weight average molecular weight of 10,000 or more.
[4] The semiconductor adhesive according to [3], wherein the polymer compound has a weight average molecular weight of 30000 or more, and the polymer compound has a glass transition temperature of 100 ° C. or less.
[5] The adhesive for semiconductors according to any one of [1] to [4], which is in the form of a film.
[6] The adhesive for semiconductors according to any one of [1] to [5], wherein the (meth) acrylic compound is solid at 25 ° C.
[7] The adhesive for semiconductors according to any one of [1] to [6], wherein the compound represented by the formula (1) or (2) is a thermal radical generator.
[8] In the semiconductor device in which the connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other, or in the semiconductor device in which the connection portions of the plurality of semiconductor chips are electrically connected to each other, The adhesive for semiconductors according to any one of [1] to [7], which is used for sealing.
[9] A method for manufacturing a semiconductor device, wherein the semiconductor adhesive according to any one of [1] to [8] is used.
[10] A semiconductor device comprising the semiconductor adhesive according to any one of [1] to [8] or a cured product thereof.

  ADVANTAGE OF THE INVENTION According to this invention, even if it is an acrylic hardening-type adhesive agent, the adhesive agent for semiconductors which is excellent in the stability after a heating process and a dicing process, and the semiconductor device using this adhesive agent for semiconductors, and the manufacturing method of a semiconductor device Can be provided.

1 is a schematic cross-sectional view showing an embodiment of a semiconductor device according to the present invention. It is a schematic cross section which shows other one Embodiment of the semiconductor device which concerns on this invention. It is a schematic cross section which shows other one Embodiment of the semiconductor device which concerns on this invention. It is a schematic cross section which shows other one Embodiment of the semiconductor device which concerns on this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

［式（１）及び（２）中、Ｒ^１は水素原子、アルキル基又は下記式（３）で表される基を示し、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は水素原子又はメチル基を示し、Ｒ^６はメチル基又はフェニル基を示す。］

［式（３）中、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は水素原子又はメチル基を示し、Ｒ^１６はメチル基又はフェニル基を示す。］ The adhesive according to this embodiment is suitably used as an adhesive for semiconductors, and includes a (meth) acrylic compound (hereinafter referred to as “component (a)” in some cases) and the following formula (1) or (2 ) (Hereinafter, referred to as “component (b)” in some cases).

[In the formulas (1) and (2), R ¹ represents a hydrogen atom, an alkyl group or a group represented by the following formula (3), and R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a methyl group. R ⁶ represents a methyl group or a phenyl group. ]

[In the formula (3), R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or a methyl group, and R ¹⁶ represents a methyl group or a phenyl group. ]

  The adhesive according to the present embodiment may further contain a polymer compound having a weight average molecular weight of 10,000 or more (hereinafter sometimes referred to as “component (c)”), a fluxing agent, a filler, and the like, as necessary. Good.

((A) component: (meth) acrylic compound)
The component (a) is not particularly limited as long as it is a compound having one or more (meth) acryloyl groups in the molecule. However, (a) component is a compound except the high molecular compound ((c) component) whose weight average molecular weight mentioned later is 10,000 or more. Examples of the component (a) include bisphenol A type, bisphenol F type, naphthalene type, phenol novolac type, cresol novolak type, phenol aralkyl type, biphenyl type, triphenylmethane type, dicyclopentadiene type, fluorene type, adamantane type. , Isocyanuric acid type, various polyfunctional (meth) acrylic compounds, and the like can be used. The component (a) is preferably bisphenol A, F-type skeleton, naphthalene-type skeleton, fluorene-type skeleton, adamantane-type skeleton, or isocyanuric acid-type skeleton-containing acrylate from the viewpoint of heat resistance. (A) A component can be used individually by 1 type or in combination of 2 or more types. “(Meth) acrylic compound” means “acrylic compound” and “methacrylic compound”, and “(meth) acryloyl group” means “acryloyl group” and “methacryloyl group”, respectively.

  The content of the component (a) is preferably 10 to 50% by mass and more preferably 15 to 40% by mass based on the total amount of the adhesive. When the content is less than 10% by mass, it is difficult to sufficiently control the flow of the resin after curing because there are few curing components. When the content exceeds 50% by mass, the cured product becomes too hard and the warpage of the package increases. Tend.

  The component (a) is preferably solid at room temperature (25 ° C.). The solid is less likely to generate voids than the liquid, and the viscosity (tack) of the adhesive before curing (B stage) is small and excellent in handleability. Examples of the component (a) that is solid at room temperature (25 ° C.) include bisphenol A-type skeleton-containing acrylate, fluorene-type skeleton-containing acrylate, adamantane-type skeleton-containing acrylate, and isocyanuric acid-type skeleton-containing acrylate.

  The number of functional groups of the (meth) acryloyl group in the component (a) is preferably 3 or less. If the number of functional groups is 4 or more, curing in a short time may not proceed sufficiently because the number of functional groups is large, and the curing reaction rate may decrease (when the curing network proceeds rapidly and unreacted groups remain) There).

  The molecular weight of component (a) is preferably less than 10,000, more preferably 5,000 or less. The smaller the molecular weight of the component (a), the better the reaction curing rate of the adhesive.

［式（１）及び（２）中、Ｒ^１は水素原子、アルキル基又は下記式（３）で表される基を示し、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は水素原子又はメチル基を示し、Ｒ^６はメチル基又はフェニル基を示す。］

［式（３）中、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は水素原子又はメチル基を示し、Ｒ^１６はメチル基又はフェニル基を示す。］ ((B) component: compound represented by formula (1) or (2))
The component (b) may be a peroxide compound (hydroperoxide or alkyl peroxide) represented by the following formula (1) or (2). The component (b) is preferably a thermal radical generator.

[In the formulas (1) and (2), R ¹ represents a hydrogen atom, an alkyl group or a group represented by the following formula (3), and R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a methyl group. R ⁶ represents a methyl group or a phenyl group. ]

[In the formula (3), R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or a methyl group, and R ¹⁶ represents a methyl group or a phenyl group. ]

In the formulas (1) to (3), R ² , R ³ , R ⁴ , R ⁵ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are a hydrogen atom or a methyl group. The stability after the dicing process is excellent. Further, since the peroxide is stabilized in the methyl group which is electron donating, R ² , R ³ , R ⁴ , R ⁵ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be methyl groups. preferable.

R ⁶ and R ^{16 in the} formulas (2) to (3) may be a methyl group or a phenyl group, but are preferably a phenyl group from the viewpoint of heat resistance and stability.

  The component (b) is preferably solid at room temperature (25 ° C.). The solid is higher in heat resistance than the liquid, and the stability of the adhesive after the heating step and the dicing step is more excellent.

  Examples of the component (b) include diisopropylbenzene hydroperoxide, cumene hydroperoxide, di (2-tertiarybutylperoxyisopropyl) benzene, dicumyl peroxide, tertiary butylcumyl peroxide, and the like. Among these, di (2-tertiarybutylperoxyisopropyl) benzene and dicumyl peroxide are preferable from the viewpoint of heat resistance.

  The content of the component (b) is preferably 0.5 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the component (a). When the content is less than 0.5 parts by mass, curing tends to be difficult to proceed sufficiently, and when it exceeds 10 parts by mass, curing proceeds rapidly and the number of reaction points increases, resulting in shortening of the molecular chain. , Unreacted groups remain, and voids tend to be generated or reliability is lowered.

  The component (b) can be used alone or as a mixture of two or more.

((C) component: a polymer compound having a weight average molecular weight of 10,000 or more)
The adhesive according to this embodiment can further contain a polymer compound having a weight average molecular weight of 10,000 or more. As the component (c), epoxy resin, phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal resin, Examples thereof include urethane resin and acrylic rubber. Among these, from the viewpoint of excellent heat resistance and film formability, epoxy resin, phenoxy resin, polyimide resin, acrylic resin, acrylic rubber, cyanate ester resin, and polycarbodiimide resin are preferable, epoxy resin, phenoxy resin, polyimide resin, Acrylic resin and acrylic rubber are more preferable. (C) A component can be used individually by 1 type or in mixture of 2 or more types or a copolymer.

  The mass ratio of the component (c) to the component (a) is not particularly limited, but the component (a) is preferably 0.01 to 10 parts by mass, more preferably 1 part by mass of the component (c). It is 0.05-5 mass parts, More preferably, it is 0.1-5 mass parts. (C) When component (a) is less than 0.01 part by mass with respect to 1 part by mass of component, curability may be reduced and adhesive strength may be reduced. There is a fear.

  The glass transition temperature (Tg) of the component (c) is preferably 120 ° C. or less, more preferably 100 ° C. or less, and still more preferably 85 ° C. or less, from the viewpoint of excellent adhesiveness of the adhesive to the substrate and chip. When Tg exceeds 120 ° C., bumps formed on the semiconductor chip, electrodes formed on the substrate, unevenness such as a wiring pattern cannot be embedded with an adhesive (the curing reaction may start), and air bubbles Tends to remain and voids tend to occur. In addition, Tg means Tg when measured using DSC (DSC-7 type manufactured by Perkin Elmer Co., Ltd.) under the conditions of a sample amount of 10 mg, a heating rate of 10 ° C./min, and a measurement atmosphere: air.

  The weight average molecular weight of the component (c) is preferably 10,000 or more, more preferably 30000 or more, still more preferably 40000 or more, and particularly preferably 50000 or more from the viewpoint of obtaining good film formability. In addition, in this specification, a weight average molecular weight means the weight average molecular weight when measured in polystyrene conversion using a high performance liquid chromatography (Shimadzu Corporation C-R4A).

  The adhesive according to the present embodiment can further contain a flux agent (that is, a flux activator exhibiting flux activity (activity for removing oxides, impurities, etc.)). Examples of the fluxing agent include nitrogen-containing compounds having lone pairs (imidazoles, amines, etc.), carboxylic acids, phenols, alcohols and the like. Compared with alcohols and the like, organic acids (such as carboxylic acids such as 2-methylglutaric acid) strongly express the flux activity and improve connectivity.

  The adhesive according to this embodiment further contains a filler in order to control physical properties such as viscosity and cured product, and to suppress generation of voids and moisture absorption when the semiconductor chip and the substrate are connected. May be. Examples of the filler include an inorganic filler and a resin filler. Examples of the inorganic filler include insulating inorganic fillers such as glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride. Among them, silica, alumina, titanium oxide, and boron nitride are preferable, silica, alumina, Boron nitride is more preferred. The insulating inorganic filler may be a whisker, and examples of the whisker include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. Examples of the material for the resin filler include polyurethane, polyimide, methyl methacrylate resin, methyl methacrylate-butadiene-styrene copolymer resin (MBS), and the like. Since the resin filler can impart flexibility at a high temperature such as 260 ° C. as compared with the inorganic filler, it is suitable for further improvement of reflow resistance and can be imparted with flexibility. It is also effective for improvement. A filler can be used individually by 1 type or in combination of 2 or more types. The shape, particle size and content of the filler are not particularly limited.

  The filler preferably has insulating properties from the viewpoint of excellent insulation reliability. The adhesive according to the present embodiment preferably does not contain conductive metal fillers such as silver fillers and solder fillers.

  The physical properties of the filler may be appropriately adjusted by surface treatment. The filler is preferably a filler subjected to surface treatment from the viewpoint of improving dispersibility and further improving adhesive force. Examples of the surface treatment agent include glycidyl (epoxy), amine, phenyl, phenylamino, (meth) acrylic, and vinyl compounds.

  As the surface treatment, silane treatment with a silane compound such as epoxy silane, amino silane, or acrylic silane is preferable because of the ease of surface treatment. As the surface treatment agent, a glycidyl-based, phenylamino-based or (meth) acrylic-based compound is preferable from the viewpoint of excellent dispersibility and fluidity and further improving the adhesive force. As the surface treatment agent, phenyl and (meth) acrylic compounds are preferable from the viewpoint of storage stability.

  The average particle size of the filler is preferably 1.5 μm or less from the viewpoint of preventing biting during flip chip connection, and more preferably 1.0 μm or less from the viewpoint of excellent visibility (transparency).

  The content of the filler is preferably 30 to 90% by mass, more preferably 40 to 80% by mass based on the total solid content of the adhesive. When the content is less than 30% by mass, heat dissipation is low, and there is a tendency that voids are generated and the moisture absorption rate is increased. When the content exceeds 90% by mass, the viscosity increases, the fluidity of the adhesive decreases, the filler bites into the connection part (trapping), etc., and the connection reliability tends to decrease.

  The adhesive according to this embodiment may further contain additives such as an ion trapper, an antioxidant, a silane coupling agent, a titanium coupling agent, and a leveling agent. These additives can be used alone or in combination of two or more. What is necessary is just to adjust content of these additives suitably so that the effect of each additive may express.

  The adhesive according to this embodiment can be pressure-bonded at a high temperature of 200 ° C. or higher. The adhesive according to the present embodiment is more effective when used in a flip chip package that forms a connection by melting a metal such as solder.

  The curing reaction rate when the adhesive according to this embodiment is held at 200 ° C. for 5 seconds is preferably 80% or more, and more preferably 90% or more. If the curing reaction rate at 200 ° C. (solder melting temperature or lower) / 5 seconds is lower than 80%, solder may scatter and flow during connection (solder melting temperature or higher), which may reduce connection reliability. The curing reaction rate was measured in a temperature range of 30 ° C. to 300 ° C. with a heating rate of 20 ° C./min using DSC (DSC-7 model manufactured by Perkin Elmer) after putting 10 mg of uncured adhesive in an aluminum pan. Can be obtained.

  If the adhesive contains an anionically polymerizable epoxy resin (particularly, an epoxy resin having a weight average molecular weight of less than 10,000), it may be difficult to adjust the curing reaction rate to 80% or more. It is preferable that content of an epoxy resin is 20 mass parts or less with respect to 80 mass parts of (a) component, and it is more preferable that an adhesive agent does not contain an epoxy resin. The curing system is preferably a radical polymerization system.

  The adhesive according to this embodiment is preferably in the form of a film (film adhesive) from the viewpoint of improving productivity. A method for producing the film adhesive will be described below.

  First, the resin varnish is prepared by adding the component (a), the component (b), the component (c), and other components, if necessary, to an organic solvent and then dissolving or dispersing them by stirring, mixing, kneading, or the like. . Then, after applying the resin varnish using a knife coater, roll coater, applicator, die coater, comma coater, etc. on the base film subjected to the release treatment, the organic solvent is reduced by heating, and the base film A film adhesive is formed thereon. Further, before reducing the organic solvent by heating, a film adhesive may be formed on the wafer by a method of drying the solvent after spin-coating a resin varnish on the wafer or the like to form a film.

  The base film is not particularly limited as long as it has heat resistance capable of withstanding the heating conditions when the organic solvent is volatilized. The polyester film, the polypropylene film, the polyethylene terephthalate film, the polyimide film, the polyetherimide film, the poly Examples include ether naphthalate film and methylpentene film. The base film is not limited to a single layer composed of one of these films, and may be a multilayer film composed of two or more films.

  As conditions for volatilizing the organic solvent from the resin varnish after application, specifically, heating at 50 to 200 ° C. for 0.1 to 90 minutes is preferable. As long as there is no effect on voids and viscosity adjustment after mounting, it is preferable that the organic solvent volatilizes to 1.5% or less.

  The adhesive according to the present embodiment is preferably used for a semiconductor device (suitable as a semiconductor adhesive), and a semiconductor device in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or In the semiconductor device in which the connection portions of the plurality of semiconductor chips are electrically connected to each other, it is particularly preferably used for sealing the connection portions.

  A semiconductor device using the adhesive according to this embodiment will be described. The connection portion in the semiconductor device may be either metal bonding between the bump and the wiring or metal bonding between the bump and the bump. In the semiconductor device, for example, flip chip connection for obtaining electrical connection via an adhesive may be used.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device (COB type connection mode between a semiconductor chip and a substrate). As shown in FIG. 1A, the first semiconductor device 100 is disposed on the semiconductor chip 10 and the substrate (circuit wiring board) 20 facing each other, and on the surfaces facing each other of the semiconductor chip 10 and the substrate 20, respectively. The wiring 15 includes connection bumps 30 that connect the semiconductor chip 10 and the wiring 15 of the substrate 20 to each other, and an adhesive 40 that is filled in the gap between the semiconductor chip 10 and the substrate 20 without any gaps. The semiconductor chip 10 and the substrate 20 are flip-chip connected by wiring 15 and connection bumps 30. The wiring 15 and the connection bump 30 are sealed with an adhesive 40 and are shielded from the external environment.

  As shown in FIG. 1B, the second semiconductor device 200 includes a semiconductor chip 10 and a substrate 20 that face each other, a bump 32 that is disposed on each surface of the semiconductor chip 10 and the substrate 20 that face each other, and a semiconductor It has the adhesive 40 with which the space | gap between the chip | tip 10 and the board | substrate 20 was filled without gap. The semiconductor chip 10 and the substrate 20 are flip-chip connected by connecting opposing bumps 32 to each other. The bumps 32 are sealed with an adhesive 40 and are shielded from the external environment.

  FIG. 2 is a schematic cross-sectional view showing another embodiment of a semiconductor device (COC type connection mode between semiconductor chips). As shown in FIG. 2A, the third semiconductor device 300 is the same as the first semiconductor device 100 except that two semiconductor chips 10 are flip-chip connected by wirings 15 and connection bumps 30. is there. As shown in FIG. 2B, the fourth semiconductor device 400 is the same as the second semiconductor device 200 except that the two semiconductor chips 10 are flip-chip connected by the bumps 32.

  There is no restriction | limiting in particular as the semiconductor chip 10, Various semiconductors, such as an element semiconductor comprised from the same kind of elements, such as silicon and germanium, and compound semiconductors, such as gallium arsenide and indium phosphide, can be used.

  The substrate 20 is not particularly limited as long as it is a printed circuit board, and does not require a metal layer formed on the surface of an insulating substrate mainly composed of glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, or the like. A circuit board on which wiring (wiring pattern) is formed by etching away a portion, a circuit board on which wiring (wiring pattern) is formed by metal plating on the surface of the insulating substrate, and a conductive substance on the surface of the insulating substrate A circuit board on which wiring (wiring pattern) is formed by printing can be used.

  The connection parts such as the wiring 15 and the bumps 32 are gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), nickel, tin, lead, etc. And may contain a plurality of metals.

  The surface of the wiring (wiring pattern) is mainly composed of gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, or the like. A metal layer may be formed. This metal layer may be composed of only a single component or may be composed of a plurality of components. Moreover, you may have the structure where the some metal layer was laminated | stacked. Copper and solder are generally used because they are inexpensive.

  As materials for the conductive protrusions called bumps, the main components are gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), tin, nickel, etc. May be used, and may be composed of only a single component or may be composed of a plurality of components. Moreover, you may form so that the structure where these metals were laminated | stacked may be made | formed. The bump may be formed on a semiconductor chip or a substrate. Copper and solder are generally used because they are inexpensive.

  Also, a semiconductor device (package) as shown in FIG. 1 or FIG. 2 is laminated and gold, silver, copper, solder (main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper), You may electrically connect with tin, nickel, etc. Copper and solder are preferred because they are generally used because they are inexpensive. For example, as seen in the TSV technology, an adhesive may be flip-chip connected or stacked between semiconductor chips to form a hole penetrating the semiconductor chip and connected to the electrode on the pattern surface.

  FIG. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device (semiconductor chip laminated type (TSV)). As shown in FIG. 3, in the fifth semiconductor device 500, the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 10 via the connection bumps 30, so that the semiconductor chip 10 and the interposer 50 are connected. Is flip-chip connected. The gap between the semiconductor chip 10 and the interposer 50 is filled with the adhesive 40 without any gaps. On the surface of the semiconductor chip 10 opposite to the interposer 50, the semiconductor chip 10 is repeatedly laminated via the wiring 15, the connection bump 30 and the adhesive 40. The wirings 15 on the pattern surface on the front and back sides of the semiconductor chip 10 are connected to each other by through electrodes 34 filled in holes that penetrate the inside of the semiconductor chip 10. In addition, as a material of the penetration electrode 34, copper, aluminum, etc. can be used.

  With such TSV technology, a signal can be obtained from the back surface of a semiconductor chip that is not normally used. Furthermore, since the through electrode 34 passes vertically through the semiconductor chip 10, the distance between the semiconductor chips 10 facing each other or between the semiconductor chip 10 and the interposer 50 can be shortened and flexible connection is possible. The adhesive according to the present embodiment is suitably used as a sealing material between the semiconductor chips 10 facing each other or between the semiconductor chip 10 and the interposer 50 in such a TSV technology.

  Further, in a bump forming method with a high degree of freedom such as area bump chip technology, a semiconductor chip can be directly mounted on a mother board without using an interposer. The adhesive according to this embodiment is also suitably used when such a semiconductor chip is directly mounted on a mother board. Note that the adhesive according to the present embodiment is suitably used when sealing the gap between the substrates when two printed circuit boards are stacked.

  The method for manufacturing a semiconductor device according to the present embodiment connects a semiconductor chip and a printed circuit board, or a plurality of semiconductor chips using the adhesive according to the present embodiment. In the semiconductor device manufacturing method according to the present embodiment, for example, the semiconductor chip and the printed circuit board are connected to each other via an adhesive, and the connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other. A step of obtaining a device, or a step of connecting a plurality of semiconductor chips to each other via an adhesive and electrically connecting respective connecting portions of the plurality of semiconductor chips to each other to obtain a semiconductor device.

  In the method for manufacturing a semiconductor device according to the present embodiment, the connection portions can be connected to each other by metal bonding. That is, the connection portions of the semiconductor chip and the printed circuit board are connected to each other by metal bonding, or the connection portions of the plurality of semiconductor chips are connected to each other by metal bonding.

  As an example of the method for manufacturing the semiconductor device according to this embodiment, a method for manufacturing the sixth semiconductor device 600 shown in FIG. 4 will be described. The sixth semiconductor device 600 includes a substrate (for example, a glass epoxy substrate) 60 having a wiring (copper wiring) 15 and a semiconductor chip 10 having a wiring (for example, copper pillar, copper post) 15, with an adhesive 40 interposed therebetween. It is connected. The wiring 15 of the semiconductor chip 10 and the wiring 15 of the substrate 60 are electrically connected by connection bumps (solder bumps) 30. A solder resist 70 is disposed on the surface of the substrate 60 where the wiring 15 is formed, except for the position where the connection bump 30 is formed.

  In the sixth method for manufacturing a semiconductor device 600, first, an adhesive (film adhesive or the like) 40 is pasted on the substrate 60 on which the solder resist 70 is formed. Affixing can be performed by a hot press, roll lamination, vacuum lamination, or the like. The supply area and thickness of the adhesive 40 are appropriately set depending on the size of the semiconductor chip 10 or the substrate 60, the bump height, and the like. The adhesive 40 may be affixed to the semiconductor chip 10, and after the adhesive 40 is affixed to the semiconductor wafer, the semiconductor chip 10 is affixed with the adhesive 40 by dicing into pieces. May be. After the adhesive 40 is attached to the substrate 60 or the semiconductor chip 10, the connection bumps 30 on the wiring 15 of the semiconductor chip 10 and the wiring 15 of the substrate 60 are aligned using a connection device such as a flip chip bonder. Then, the semiconductor chip 10 and the substrate 60 are pressed while being heated at a temperature equal to or higher than the melting point of the connection bump 30 (when solder is used for the connection portion, the solder portion preferably takes 240 ° C. or more). 60 is connected, and the gap between the semiconductor chip 10 and the substrate 60 is sealed and filled with the adhesive 40. The connection load depends on the number of bumps, but is set in consideration of absorption of bump height variation, control of the amount of bump deformation, and the like. The connection time is preferably a short time from the viewpoint of improving productivity. It is preferable to melt the solder, remove the oxide film, surface impurities, etc., and form a metal joint at the connection.

  The short connection time (crimping time) means that the time required for 240 ° C. or more (for example, time when using solder) is 4 seconds or less during connection formation (final crimping). The connection time is preferably 3 seconds or less.

  After the alignment, the semiconductor device may be manufactured by temporarily fixing, melting the solder bumps by heat treatment in a reflow furnace, and connecting the semiconductor chip and the substrate. Temporary fixing does not require the necessity of forming a metal bond, so it can have lower load, shorter time, and lower temperature than the above-mentioned main pressure bonding, and there are merits such as improvement of productivity and prevention of deterioration of connection parts. . After the semiconductor chip and the substrate are connected, the adhesive may be cured by performing a heat treatment in an oven or the like. The heating temperature is a temperature at which the curing of the adhesive proceeds, preferably complete curing. The heating temperature and the heating time may be set as appropriate. In this case, the obtained semiconductor device includes a cured product of the adhesive.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.

(Examples 1-4 and Comparative Examples 1-2)
Using the components shown below in the formulation shown in Table 1, a film adhesive was prepared according to the following method. Moreover, each characteristic was evaluated in accordance with the following method about the obtained film adhesive. The results are shown in Table 1.

Component (a): fluorene skeleton-containing acrylate (Osaka Gas Chemical Co., Ltd., EA0200, bifunctional group)
-(B) component (b-1): Dicumyl peroxide (the NOF Corporation make, park mill D)
(B-2): Di (2-tertiary butyl peroxyisopropyl) benzene (manufactured by NOF Corporation, perbutyl P)
(B-3): Cumene hydroperoxide (manufactured by NOF Corporation, Park Mill H)
(B-4): Diisopropylbenzene hydroperoxide (manufactured by NOF Corporation, Park Mill P)
Other peroxides (x-1): Ditertiary butyl peroxide (manufactured by NOF Corporation, Perbutyl D)
(X-2): 1,1,3,3-tetramethylbutyl hydroperoxide (manufactured by NOF Corporation, Perocta H)
-Component (c): Acrylic rubber (manufactured by Hitachi Chemical Co., Ltd., KH-CT865, Tg: 0 to 12 ° C, weight average molecular weight: 450,000 to 650000)
Filler (d-1): Silica filler (manufactured by Admatechs, SE2050, average particle size 0.5 μm)
(D-2): Methacrylic surface-treated nanosilica filler (manufactured by Admatechs, YA050C-SM, hereinafter referred to as “SM nanosilica”, average particle size of about 50 nm)
(D-3): Organic filler (Rohm and Haas Japan Co., Ltd., EXL-2655: Core-shell type organic fine particles)

(Method for producing film adhesive)
An organic solvent (methyl ethyl ketone) was added to the component (a) and the filler so that NV (nonvolatile content) was 60% by mass. Thereafter, φ1.0 mm and φ2.0 mm beads were added in the same mass as the solid content, and the mixture was stirred for 30 minutes with a bead mill (Fritsch Japan Co., Ltd. planetary pulverizer P-7). Then, (c) component was added and it stirred for 30 minutes again by the bead mill. After stirring, the component (b) or other peroxide was added and stirred, and then the used beads were removed by filtration. The produced varnish was coated with a small precision coating apparatus (Yurui Seiki) and dried (70 ° C./10 min) in a clean oven (manufactured by ESPEC) to obtain a film adhesive.

(1) Stability evaluation A sample obtained by heat-treating a film-like adhesive at 80 ° C./60 s using a vacuum laminator (Nikko Materials Co., Ltd., V130), and after the heat treatment, 20 minutes in pure water Samples soaked in water were prepared, and the heat capacities were measured immediately after each treatment and after standing for 1 week at room temperature (25 ° C.). In the measurement of the heat capacity, a sample amount of 10 mg was put into an aluminum pan using DSC (Perkin Elmer, DSC-7 type), and the temperature was measured from 30 to 300 ° C. at a heating rate of 10 ° C./min. The reaction rate was calculated by the following equation, where ΔH when measuring the initial (immediately after treatment) sample was ΔH1, and ΔH when measuring the sample after standing for 1 week was ΔH2.
(ΔH1−ΔH2) / ΔH1 × 100 = reaction rate (%)
Samples having a reaction rate of less than 10% were evaluated as A, samples having a reaction rate of 10% or more but less than 20% were evaluated as B, and samples having a reaction rate of 20% or more were evaluated as C. If the evaluation result is A or B, it can be said that the stability is excellent.

(2) Manufacturing method of semiconductor device A glass epoxy substrate (glass epoxy base material) having a film-like adhesive cut out for one week (8 mm × 8 mm × 0.045 mm ^t ) and a solder resist (manufactured by Taiyo Ink Co., AUS308) : 420 μm thickness, copper wiring: 9 μm thickness, pitch 80 μm, spacing between Cu wiring and Cu wiring is 40 μm) using a vacuum laminator (Nikko Materials Co., Ltd., V130) at 80 ° C./60 s and soldering A semiconductor chip with a bump (chip size: 7.3 mm × 7.3 mm × 0.15 mm ^t , bump height: copper pillar + solder meter approximately 45 μm, number of bumps 328, nitride film coating) is mounted on FCB3 (manufactured by Panasonic) (Mounting conditions: pressure head temperature 130 ° C./1 s + 250 ° C./4 s, 75 N), semiconductor device shown in FIG. To obtain a semiconductor device having the same structure as. The stage temperature in the FCB 3 on which the substrate was placed during the pressure bonding was 80 ° C.

(3) Connection evaluation After mounting the glass epoxy substrate and the semiconductor chip with solder bumps (daisy chain connection) on FCB3, the possibility of initial conduction was measured using a multimeter (manufactured by ADVANTEST, R6871E). The case where the initial connection resistance value was 10.0 to 15Ω was evaluated as A (good connection), and the other cases were evaluated as B (connection failure).

DESCRIPTION OF SYMBOLS 10 ... Semiconductor chip, 15 ... Wiring, 20, 60 ... Substrate, 30 ... Connection bump, 32 ... Bump, 34 ... Through electrode, 40 ... Adhesive, 50 ... Interposer, 70 ... Solder resist, 100, 200, 300, 400 , 500, 600... Semiconductor device.

Claims (10)

The adhesive for semiconductors containing a (meth) acrylic compound and the compound represented by following formula (1) or (2).

[In the formulas (1) and (2), R ¹ represents a hydrogen atom, an alkyl group or a group represented by the following formula (3), and R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a methyl group. R ⁶ represents a methyl group or a phenyl group. ]

[In the formula (3), R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or a methyl group, and R ¹⁶ represents a methyl group or a phenyl group. ] The adhesive for semiconductors of Claim 1 whose R < ² >, R < ³ >, R < ⁴ >, R < ⁵ >, R < ¹² >, R <^13> , R <^14> and R < ¹⁵ > are methyl groups in Formula (1)-(3).   The adhesive for semiconductors of Claim 1 or 2 which further contains the high molecular compound whose weight average molecular weight is 10,000 or more.   The semiconductor adhesive according to claim 3, wherein the polymer compound has a weight average molecular weight of 30,000 or more and a glass transition temperature of the polymer compound of 100 ° C. or less.   The adhesive for semiconductors as described in any one of Claims 1-4 which is a film form.   The semiconductor adhesive according to any one of claims 1 to 5, wherein the (meth) acrylic compound is solid at 25 ° C.   The semiconductor adhesive according to claim 1, wherein the compound represented by the formula (1) or (2) is a thermal radical generator.   A semiconductor device in which respective connection portions of a semiconductor chip and a printed circuit board are electrically connected to each other, or a semiconductor device in which respective connection portions of a plurality of semiconductor chips are electrically connected to each other, for sealing the connection portion. The adhesive for semiconductors as described in any one of Claims 1-7 used.   The manufacturing method of a semiconductor device using the adhesive agent for semiconductors as described in any one of Claims 1-8. A semiconductor device provided with the adhesive for semiconductors as described in any one of Claims 1-8, or its hardened | cured material.

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