JP2017103303A - Adhesive for semiconductor, semiconductor device, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive for semiconductors which is excellent in reflow resistance and adhesion even if being an acrylic curable type adhesive, and a semiconductor device and a method for manufacturing a semiconductor device using the same.SOLUTION: The adhesive for semiconductors includes a (meth) acrylic compound, a curing agent, and a compound represented by the following formula (1). [In the formula (1), Rrepresents a hydrogen atom, a methyl group or an ethyl group, R, R, and Reach independently represent a hydrogen atom, an alkyl group represented by -(CH)-CH, or an alkoxy group, and at least one of R, R, and Rrepresents a methoxy group, m represents an integer of 0 to 3, and n represents an integer of 1 to 6.]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

  The adhesive for semiconductors used in the various connection methods described above has improved reflow resistance and improved adhesion that can suppress poor connection, peeling and void generation even after passing through a reflow oven at around 260 ° C after moisture absorption. Is strongly demanded. However, conventional adhesives for semiconductors have low heat resistance, adhesive strength after moisture absorption, and reflow resistance, which may cause problems such as poor connection and peeling. In particular, it is difficult to improve the adhesive strength of a semiconductor adhesive that can manufacture a semiconductor device without voids in a short time, such as an acrylic curable adhesive.

  The present invention has been made in order to solve the above-described problems, and an adhesive for a semiconductor having excellent reflow resistance and adhesive force, and an adhesive for a semiconductor, are used even for an acrylic curable adhesive. It is an object to provide a semiconductor device and a method for manufacturing the semiconductor device.

［式（１）中、Ｒ^１は水素原子、メチル基又はエチル基を表し、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立に水素原子、−（ＣＨ_２）_ｍ−ＣＨ_３で表されるアルキル基、又はアルコキシ基を表し、かつＲ^２、Ｒ^３及びＲ^４の少なくとも一つはメトキシ基を表し、ｍは０〜３の整数を表し、ｎは１〜６の整数を表す。］
［２］ 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］に記載の半導体用接着剤。
［３］ 高分子化合物の重量平均分子量が３００００以上であり、高分子化合物のガラス転移温度が１００℃以下である、［２］に記載の半導体用接着剤。
［４］ フィルム状である、［１］〜［３］のいずれかに記載の半導体用接着剤。
［５］ （メタ）アクリル化合物が２５℃で固形である、［１］〜［４］のいずれかに記載の半導体用接着剤。
［６］ 硬化剤が熱ラジカル発生剤である、［１］〜［５］のいずれかに記載の半導体用接着剤。
［７］ 硬化剤が過酸化物である、［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, a curing agent, and a compound represented by the following formula (1).

In Expression (1), ^{R 1} represents a hydrogen atom, a methyl group or an ethyl ^group, R 2, ^{R 3} and ^{R 4} are each independently a hydrogen atom, _- represented by _(CH 2) m -CH ₃ It represents an alkyl group or an alkoxy group, and at least one of R ² , R ³ and R ⁴ represents a methoxy group, m represents an integer of 0 to 3, and n represents an integer of 1 to 6. ]
[2] The adhesive for semiconductors according to [1], further comprising a polymer compound having a weight average molecular weight of 10,000 or more.
[3] The semiconductor adhesive according to [2], 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.
[4] The semiconductor adhesive according to any one of [1] to [3], which is in the form of a film.
[5] The adhesive for semiconductors according to any one of [1] to [4], wherein the (meth) acrylic compound is solid at 25 ° C.
[6] The adhesive for semiconductors according to any one of [1] to [5], wherein the curing agent is a thermal radical generator.
[7] The adhesive for semiconductors according to any one of [1] to [6], wherein the curing agent is a peroxide.
[8] In a semiconductor device in which the connection portions of the semiconductor chip and the printed circuit board are electrically connected to each other, or in a semiconductor device in which the connection portions of the plurality of semiconductor chips are electrically connected to each other, sealing of the connection portions is performed. The adhesive for semiconductors in any one of [1]-[7] used for a stop.
[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 reflow resistance and adhesive force, the semiconductor device using this adhesive agent for semiconductors, and the manufacturing method of a semiconductor device are provided. Can do.

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）中、Ｒ^１は水素原子、メチル基又はエチル基を表し、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立に水素原子、−（ＣＨ_２）_ｍ−ＣＨ_３で表されるアルキル基、又はアルコキシ基を表し、かつＲ^２、Ｒ^３及びＲ^４の少なくとも一つはメトキシ基を表し、ｍは０〜３の整数を表し、ｎは１〜６の整数を表す。］ The adhesive according to the present embodiment is suitably used as an adhesive for semiconductors, and includes a (meth) acrylic compound (hereinafter sometimes referred to as “component (a)”) and a curing agent (hereinafter sometimes referred to as “ (Referred to as “component (b)”) and a compound represented by the following formula (1) (hereinafter sometimes referred to as “component (c)”).

In Expression (1), ^{R 1} represents a hydrogen atom, a methyl group or an ethyl ^group, R 2, ^{R 3} and ^{R 4} are each independently a hydrogen atom, _- represented by _(CH 2) m -CH ₃ It represents an alkyl group or an alkoxy group, and at least one of R ² , R ³ and R ⁴ represents a methoxy group, m represents an integer of 0 to 3, and n represents an integer of 1 to 6. ]

  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 referred to as “component (d)” in some cases), a flux 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 compound ((c) component) represented by the said Formula (1), and the high molecular compound ((d) component) whose weight average molecular weight mentioned later is 10,000 or more. For example, bisphenol A type, bisphenol F type, naphthalene type, phenol novolak type, cresol novolak type, phenol aralkyl type, biphenyl type, triphenylmethane type, dicyclopentadiene type, fluorene type, adamantane type, isocyanuric acid type, various types A functional (meth) acrylic compound or 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.

((B) component: curing agent)
The component (b) is not particularly limited as long as it functions as a curing agent for the component (a). As the component (b), a radical generator is preferable. Examples of the radical generator include a thermal radical generator (thermal radical generator), a photo radical generator (light radical generator), and the like. As the component (b), a thermal radical generator is preferable from the viewpoint of excellent handleability. (B) A component can be used individually by 1 type or in combination of 2 or more types.

  Examples of the thermal radical generator include azo compounds and peroxides (organic peroxides and the like). As the thermal radical generator, a peroxide is preferable and an organic peroxide is more preferable from the viewpoint of excellent handleability and storage stability. Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxyester. As the organic peroxide, hydroperoxide, dialkyl peroxide, and peroxyester are preferable from the viewpoint of storage stability. Furthermore, as the organic peroxide, hydroperoxide and dialkyl peroxide are preferable from the viewpoint of heat resistance.

  (B) 0.5-10 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for content of a component, 1-5 mass parts is more preferable. When the content is less than 0.5 parts by mass, the curing may not proceed sufficiently. When the content exceeds 10 parts by mass, the curing proceeds rapidly and the number of reaction points increases. There is a tendency that unreacted groups remain and the reliability tends to decrease.

［式（１）中、Ｒ^１は水素原子、メチル基又はエチル基を表し、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立に水素原子、−（ＣＨ_２）_ｍ−ＣＨ_３で表されるアルキル基、又はアルコキシ基を表し、かつＲ^２、Ｒ^３及びＲ^４の少なくとも一つはメトキシ基を表し、ｍは０〜３の整数を表し、ｎは１〜６の整数を表す。］ ((C) component: compound represented by formula (1))
The component (c) is not particularly limited as long as it is a compound represented by the following formula (1).

In Expression (1), ^{R 1} represents a hydrogen atom, a methyl group or an ethyl ^group, R 2, ^{R 3} and ^{R 4} are each independently a hydrogen atom, _- represented by _(CH 2) m -CH ₃ It represents an alkyl group or an alkoxy group, and at least one of R ² , R ³ and R ⁴ represents a methoxy group, m represents an integer of 0 to 3, and n represents an integer of 1 to 6. ]

The compound represented by the formula (1) is acrylic silane when R ¹ is a hydrogen atom, methacryl silane when R ¹ is a methyl group, and ethacryl silane when R ¹ is an ethyl group. From the viewpoint of improvement, acrylic silane or methacrylic silane is preferable (that is, R ¹ is preferably a hydrogen atom or a methyl group).

  n is an integer of 1-6. There exists a possibility that the intensity | strength after hardening of an adhesive agent may fall that n is seven or more. n is preferably 2 or more, more preferably 3 or more, from the viewpoint of suppressing a decrease in reactivity and further improving the adhesive force.

R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group represented by — (CH ₂ ) _m —CH ₃ , or an alkoxy group, and at least one of R ² , R ³ and R ⁴ . One is a methoxy group. m is an integer of 0-3. The number of carbon atoms of the alkoxy group may be, for example, 1 to 3. In the case where at least one of R ² , R ³ and R ⁴ is a methoxy group, the reactivity is improved and the adhesive strength compared to the case where all of R ² , R ³ and R ⁴ are alkyl groups or ethoxy groups. Is further improved. From the viewpoint of further improving the adhesive strength, it is preferable that two of R ^2, R ³ and R ⁴ is a methoxy group, it is preferable that all of R ^2, R ³ and R ⁴ are methoxy groups.

  Specific examples of the component (c) include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxy. Examples thereof include propyldimethylmonomethoxysilane and 3-methacryloxypropyldimethylmonomethoxysilane.

  The content of the component (c) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and still more preferably 0. 0% by mass, based on the total amount of the adhesive, from the viewpoint of excellent adhesive strength. It is 5 to 3% by mass.

  The component (c) not only improves the wettability to the semiconductor chip and the semiconductor substrate and improves the adhesion, but also between the resin components (acrylic resin, etc.), between the inorganic components (filler, etc.), the resin component and the inorganic component. It plays the role of a binder between and improves the adhesive strength of the adhesive and the strength after curing.

((D) 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 (d), 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. The component (d) can be used as a single type or a mixture or copolymer of two or more types.

  The mass ratio of the component (d) and 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 (d) 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 (d) is preferably 10,000 or more, more preferably 30000 or more, further 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 resin filler include polyurethane and polyimide. 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 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 1-3 and Comparative Examples 1-3)
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)
-Component (b): Dicumyl peroxide (manufactured by NOF Corporation, Park Mill D)
-(C) component:
(C-1): 3-methacryloxypropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., Z-6030)
(C-2): 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503)
(C-3): 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-502)
Other coupling agent (x-1): 3-methacryloxypropyltriethoxyxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-503)
(X-2): 3-glycidoxypropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., Z-6040)
Component (d): Acrylic rubber (manufactured by Hitachi Chemical Co., Ltd., KH-CT865, Tg: 0 to 12 ° C., weight average molecular weight: 450,000 to 650000)
Filler (e-1): Silica filler (manufactured by Admatechs, SE2050, average particle size 0.5 μm)
(E-2): Methacrylic surface-treated nano silica filler (manufactured by Admatechs Co., Ltd., YA050C-SM, hereinafter referred to as SM nano silica, average particle diameter of about 50 nm)
(E-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 so that the component (a), the component (c), and the filler were NV 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). Thereafter, component (d) was added, and the mixture was again stirred for 30 minutes with a bead mill. After stirring, the component (b) 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) with a clean oven (manufactured by ESPEC) to obtain a film adhesive.

(1) Adhesive strength evaluation (260 ° C adhesive strength measurement after moisture absorption)
Cut out the film adhesive (5mm x 5mm x 0.045mm ^t ), paste it on the upper silicon chip (5mm x 5mm x 0.725mm ^t , nitride film coating) at 80 ° C, thermocompression testing machine (Hitachi Chemical Techno Plant Co., Ltd.) The product was pressure-bonded to a lower silicon chip (10 mm × 8 mm × 0.725 mm ^t , nitride film coating) using a company (compression condition: 130 ° C./1 s + 250 ° C./4 s, 0.5 MPa). Next, it was after-cured in a clean oven (manufactured by ESPEC) (175 ° C./2 h). Then, it is left for 48 hours in an 85 ° C./60% constant temperature and humidity chamber (manufactured by ESPEC, PR-2KP), taken out, and then taken out on a hot plate at 260 ° C. (adhesive bond tester DAGE 4000 type, manufactured by DAGE). Was used to measure the adhesive force under the conditions of a tool height of 0.05 mm from the substrate and a tool speed of 0.05 mm / s. The case where the adhesive strength is 15 kg or more is evaluated as A, the case where it is 10 kg or more and less than 15 kg is B, the case where it is 5 kg or more and less than 10 kg is C, and the case where it is less than 5 kg is evaluated as D. It was judged.

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

(3) Evaluation of voids The sample after crimping was taken with an ultrasonic diagnostic imaging apparatus (Insight-300, manufactured by Insight), and an external image was taken. The image of the layer was taken in, and the void portion was identified by color tone correction and two-gradation using the image processing software Adobe Photoshop, and the ratio of the void portion was calculated by the histogram. The area of the semiconductor adhesive portion on the chip was 100%. The case where the void generation rate was 10% or less was evaluated as A (good), and the case where the void generation rate exceeded 10% was evaluated as B (defective).

(4) 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).

(5) Evaluation of reflow resistance The package prepared in (2) was molded using a sealing material (CEL9750ZHF10, manufactured by Hitachi Chemical Co., Ltd.) (condition: 180 ° C./6.75 MPa / 90 s). Next, after-curing was performed at 175 ° C. for 5 hours in a clean oven (manufactured by ESPEC). Then, after high-temperature moisture absorption under JEDEC level 2, conditions for reflow (manufactured by FURUKAWA ELECTRIC, SALAMANDER) were evaluated (reflow furnace was passed 3 times). After reflow, a sample with good connection without peeling was evaluated as A, and a sample with peeling and poor connection was evaluated as B. Connection evaluation was performed in the same manner as in (4).

  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, a hardening | curing agent, and the compound represented by following formula (1).

In Expression (1), ^{R 1} represents a hydrogen atom, a methyl group or an ethyl ^group, R 2, ^{R 3} and ^{R 4} are each independently a hydrogen atom, _- represented by _(CH 2) m -CH ₃ It represents an alkyl group or an alkoxy group, and at least one of R ² , R ³ and R ⁴ represents a methoxy group, m represents an integer of 0 to 3, and n represents an integer of 1 to 6. ]   The adhesive for semiconductors of Claim 1 which further contains the high molecular compound whose weight average molecular weight is 10,000 or more.   The semiconductor adhesive according to claim 2, 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.   The adhesive for semiconductors as described in any one of Claims 1-3 which is a film form.   The adhesive for semiconductors as described in any one of Claims 1-4 whose said (meth) acryl compound is solid at 25 degreeC.   The adhesive for semiconductors as described in any one of Claims 1-5 whose said hardening | curing agent is a thermal radical generator.   The adhesive for semiconductors as described in any one of Claims 1-6 whose said hardening | curing agent is a peroxide.   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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