CN111247206A - Resin composition for sealing and semiconductor device - Google Patents

Resin composition for sealing and semiconductor device Download PDF

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Publication number
CN111247206A
CN111247206A CN201880067422.7A CN201880067422A CN111247206A CN 111247206 A CN111247206 A CN 111247206A CN 201880067422 A CN201880067422 A CN 201880067422A CN 111247206 A CN111247206 A CN 111247206A
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China
Prior art keywords
resin composition
sealing
sealing resin
mass
semiconductor device
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CN201880067422.7A
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Chinese (zh)
Inventor
黑田洋史
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/484—Connecting portions
    • H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
    • H01L2224/48465—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area being a wedge bond, i.e. ball-to-wedge, regular stitch
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Abstract

The sealing resin composition contains a component (A): epoxy resin, component (B): inorganic filler and component (C): the content of S in a cured product of the resin composition for sealing is 10ppm or less based on the whole cured product.

Description

Resin composition for sealing and semiconductor device
Technical Field
The present invention relates to a sealing resin composition and a semiconductor device.
Background
As a technique for improving the electrical characteristics of a semiconductor package, there is a technique described in patent document 1 (japanese patent application laid-open No. 2007-161990). This document describes an epoxy resin molding material for sealing, which contains an epoxy resin, a curing agent, and a colorant resin mixture obtained by previously mixing a resin with a colorant having a specific resistivity within a specific range. According to this document, the encapsulating epoxy resin molding material is excellent in fluidity, curability and coloring property, and even when used as an encapsulating material in an electronic component device having a narrow distance between pads or between leads (wires), an electronic component device having excellent electrical characteristics can be obtained.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2007-161990
Disclosure of Invention
Technical problem to be solved by the invention
In a semiconductor package, an Au wire has been conventionally used for electrically connecting a chip and a lead frame, but in recent years, a Cu wire has been frequently used for cost reduction.
Although the Cu wire is less expensive than the Au wire, it is considered to have poor chemical stability and to be deteriorated by halogen ions, pH, and sulfur-based impurities contained in the sealing material. In particular, since the application range of semiconductor packages is expanded and the use thereof in a High temperature environment is increased, the deterioration of High Temperature Storage Life (HTSL) due to sulfur-based impurities during High temperature operation has been proposed as a technical problem in the case of using Cu wires.
Therefore, as a result of studies by the present inventors, there is room for improvement in the following points in the case of using a conventional sealing material: even when applied to a semiconductor device including a Cu wire, the obtained semiconductor device is excellent in HTSL characteristics and laser marking properties (laser marking performance).
Means for solving the problems
According to the present invention, there is provided a sealing resin composition comprising the following components (a) to (C):
(A) an epoxy resin;
(B) an inorganic filler material; and
(C) a black-based coloring agent, wherein,
the S content in a cured product of the sealing resin composition obtained by measuring a test piece obtained by the following production method by the following method is 10ppm or less with respect to the entire cured product.
(method of preparing sample)
A molded article having a diameter of 50mm and a thickness of 3mm was molded by a transfer molding machine at a mold temperature of 175 ℃ and an injection pressure of 7.4MPa for a curing time of 2 minutes, and post-cured at 175 ℃ for 4 hours to obtain a disc-shaped sample.
(method of measuring S content)
The sulfur concentration in the sample was measured by a wavelength dispersive X-ray fluorescence spectrometer (XRF-1800, manufactured by Shimadzu corporation) under conditions of a tube voltage of 40kV and a tube current of 95 mA.
According to the present invention, there is provided a semiconductor device obtained by sealing a semiconductor element using the sealing resin composition of the present invention.
Effects of the invention
According to the present invention, even when applied to a semiconductor device including a Cu wiring, a semiconductor device having excellent HTSL characteristics and excellent laser marking properties can be obtained.
Drawings
The above and other objects, features and advantages will become more apparent from the following description of the preferred embodiments and the accompanying drawings attached hereto.
Fig. 1 is a cross-sectional view showing the structure of a semiconductor device of this embodiment.
Detailed Description
Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted as appropriate. The drawings are schematic and do not necessarily correspond to actual dimensional ratios. Unless otherwise specified, the numerical range "a to B" means "a to B inclusive".
In the present embodiment, the sealing resin composition contains the following components (a) to (C):
(A) an epoxy resin;
(B) an inorganic filler material; and
(C) a black coloring agent.
The content of S (sulfur) in a cured product of the sealing resin composition obtained from the test piece obtained by the following production method was measured by the following method and was 10ppm or less based on the entire cured product.
(method of preparing sample)
A molded article having a diameter of 50mm and a thickness of 3mm was molded by a transfer molding machine at a mold temperature of 175 ℃ and an injection pressure of 7.4MPa for a curing time of 2 minutes, and post-cured at 175 ℃ for 4 hours to obtain a disc-shaped sample.
(method of measuring S content)
The sulfur concentration in the sample was measured by a wavelength dispersive X-ray fluorescence spectrometer (XRF-1800, manufactured by Shimadzu corporation) under conditions of a tube voltage of 40kV and a tube current of 95 mA.
In the present embodiment, the components (a) to (C) are used in combination in the sealing resin composition, and the S content in the cured product of the sealing resin composition is set to the above-specified range. By using the sealing resin composition, a semiconductor device having excellent HTSL characteristics and laser marking properties can be obtained even when the sealing resin composition is applied to a semiconductor device including a Cu wiring.
The sealing resin composition and the semiconductor device of the present embodiment will be described in further detail below.
The sealing resin composition is, for example, in the form of a pellet or a sheet.
Specific examples of the granular sealing resin composition include compositions in the form of tablets or granules. In the case where the sealing resin composition is in the form of a pig, the sealing resin composition can be molded by, for example, a transfer molding method. When the sealing resin composition is a powder or granule, the sealing resin composition can be molded by, for example, a compression molding method. Here, the term "the sealing resin composition is a powder or granule" means any of powder and granule.
The substrate is, for example, a circuit board such as an interposer (interposer) or a lead frame. The semiconductor element is electrically connected to the substrate by wire bonding, flip chip bonding, or the like.
The semiconductor device obtained by sealing a semiconductor element by seal molding using the sealing resin composition is not limited, and examples thereof include QFP (Quad Flat Package), SOP (Small Outline Package), BGA (Ball Grid Array), CSP (Chip size Package), QFN (Quad Flat Non-leaded Package), SON (Small Outline Non-leaded Package), LF-BGA (Lead Flat BGA; Lead Ball Grid Array), and the like.
In the present embodiment, the sealing resin composition can also be applied to a structure formed by MAP (Mold Array Package) molding, which has been frequently used for molding these packages in recent years. In this case, a package can be obtained by collectively sealing a plurality of semiconductor elements mounted on a base material with a sealing resin composition.
Examples of the semiconductor element include, but are not limited to, an integrated circuit, a large scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element. In the present embodiment, the semiconductor element to be sealed with the sealing resin composition is an element that does not involve the input and output of light, except for optical semiconductor elements such as a light receiving element and a light emitting element (such as a light emitting diode).
In the present embodiment, the S content in the cured product of the sealing resin composition is 10ppm or less, preferably 9ppm or less, more preferably 8.5ppm or less, and still more preferably 7.5ppm, with respect to the entire cured product, from the viewpoint of obtaining a semiconductor device excellent in HTSL characteristics and laser marking properties even when used together with a Cu wire.
The lower limit of the S content in the cured product is not less than 0ppm, and may be not less than a detection limit, specifically not less than 1 ppm.
In the present embodiment, the glass transition temperature (Tg) of a cured product of the sealing resin composition is preferably 110 ℃ or higher, more preferably 115 ℃ or higher, even more preferably 125 ℃ or higher, and even more preferably 135 ℃ or higher, from the viewpoint of improving the heat resistance of the cured product.
The upper limit of the glass transition temperature of the cured product is not limited, but is preferably 230 ℃ or lower, more preferably 200 ℃ or lower, and further preferably 180 ℃ or lower, from the viewpoint of improving the toughness of the cured product.
The glass transition temperature of the cured product was measured in a Thermal Mechanical Analysis (TMA) apparatus (TMA 100, manufactured by Seiko electronics Co., Ltd.) under conditions of a measurement temperature range of 0 ℃ to 320 ℃ and a temperature rise rate of 5 ℃/min. Further specific measurement methods of the glass transition temperature are described in the following examples.
In the present embodiment, the sealing resin composition contains the above components (a) to (C). The constituent components of the sealing resin composition will be described below.
(component (A): epoxy resin)
In the present embodiment, examples of the epoxy resin as the component (a) include biphenyl type epoxy resins; bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, and tetramethylbisphenol F epoxy resin; stilbene type epoxy resins; novolac type epoxy resins such as phenol novolac (phenol novolac) type epoxy resins and cresol novolac (cresol novolac) type epoxy resins; polyfunctional epoxy resins such as trisphenol methane type epoxy resins and alkyl-modified trisphenol methane type epoxy resins; phenol aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having 1 or 2 kinds of skeletons selected from phenylene skeletons and biphenylene skeletons and naphthol aralkyl type epoxy resins having 1 or 2 kinds of skeletons selected from phenylene skeletons and biphenylene skeletons; naphthol type epoxy resins such as dihydroxynaphthalene type epoxy resins and epoxy resins obtained by glycidyletherifying a dimer of dihydroxynaphthalene; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; the number of the bridged hydrocarbon compound-modified phenol epoxy resins such as dicyclopentadiene-modified phenol epoxy resin may be 1 or 2 or more.
From the viewpoint of improving the balance between the HTSL characteristics and the laser imprint properties of the semiconductor device, the epoxy resin is preferably 1 or 2 or more selected from the group consisting of a phenol aralkyl type epoxy resin containing a phenylene skeleton, an o-cresol novolac type epoxy resin, and a biphenyl type epoxy resin.
From the viewpoint of obtaining appropriate fluidity at the time of molding to improve filling property and moldability, the content of the component (a) in the sealing resin composition is preferably 2 mass% or more, more preferably 3 mass% or more, and further preferably 4 mass% or more, when the entire sealing resin composition is 100 mass%.
From the viewpoint of improving the HTSL properties of a semiconductor device having a sealing material formed using the sealing resin composition, the content of the component (a) in the sealing resin composition is preferably 40 mass% or less, more preferably 30 mass% or less, even more preferably 15 mass% or less, and even more preferably 10 mass% or less, when the entire sealing resin composition is 100 mass%.
(component (B): inorganic Filler)
In the present embodiment, as the inorganic filler of the component (B), an inorganic filler generally used in a resin composition for encapsulating a semiconductor can be used. Specific examples of the inorganic filler include silica such as fused silica and crystalline silica; alumina; talc; titanium oxide; silicon nitride; aluminum nitride. These inorganic fillers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Among these, silica is preferably used, and fused silica is more preferably used, from the viewpoint of excellent versatility. The shape of the silica is preferably spherical.
From the viewpoint of improving the low moisture absorption and low thermal expansion properties of the sealing material formed using the sealing resin composition and more effectively improving the moisture resistance reliability and reflow resistance of the obtained semiconductor device, the content of the component (B) in the sealing resin composition is preferably 50 mass% or more, more preferably 70 mass% or more, and still more preferably 80 mass% or more, when the entire sealing resin composition is taken as 100 mass%.
From the viewpoint of more effectively improving the flowability and filling property at the time of molding of the sealing resin composition, the content of the component (B) in the sealing resin composition is preferably 95% by mass or less, more preferably 93% by mass or less, and further preferably 90% by mass or less, when the entire sealing resin composition is taken as 100% by mass.
(component (C): Black colorant)
Specific examples of the black-based colorant of the component (C) include acetylene black, black titanium oxide (titanium black), and the like.
The black titanium oxide is TinO(2n-1)(n is a positive integer) is present. Black titanium oxide Ti used in the present embodimentnO(2n-1)Preferably, black titanium oxide having n of 4 to 6 is used. When n is 4 or more, the dispersibility of the black titanium oxide in the sealing resin composition can be improved. On the other hand, when n is 6 or less, the laser beam such as YAG laser beam can be improved in imprinting ability. Here, the black titanium oxide preferably contains Ti4O7、Ti5O9And Ti6O11At least one of (a). More preferably, the black titanium oxide is Ti4O7。
The component (C) preferably contains acetylene black, and more preferably contains acetylene black, from the viewpoint of obtaining a semiconductor device having excellent HTSL characteristics even when used together with a Cu wiring.
From the same viewpoint and from the viewpoint of reducing the content of sulfur derived from the raw material inevitably contained in the component (C) to further improve the HTSL characteristics of the semiconductor device including the Cu wiring, the sealing resin composition preferably contains substantially no furnace black, more preferably contains acetylene black and substantially no furnace black.
Here, the sealing resin composition does not substantially contain furnace black, which means that furnace black is not intentionally added to the sealing resin composition.
From the viewpoint of obtaining a preferable appearance of the sealing material, the content of acetylene black in the sealing resin composition is preferably 0.10% by mass or more, and more preferably 0.20% by mass or more, relative to the entire sealing resin composition. From the viewpoint of improving the insulation reliability of the semiconductor device, the content of acetylene black in the sealing resin composition is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.6% by mass or less, relative to the entire sealing resin composition.
From the viewpoint of obtaining a preferable appearance of the sealing material, the content of the component (C) in the sealing resin composition is preferably 0.10% by mass or more, and more preferably 0.20% by mass or more, relative to the entire sealing resin composition. From the viewpoint of improving the insulation reliability of the semiconductor device, the content of the component (C) in the sealing resin composition is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.6% by mass or less, relative to the entire sealing resin composition.
From the viewpoint of improving the laser marking property, the average particle diameter d50 of the 2-th order particles of acetylene black is preferably 1 μm or more, and more preferably 3 μm or more.
From the viewpoint of improving the laser inscribability, the average particle diameter d50 of the 2-th order particles of acetylene black is preferably 20 μm or less, and more preferably 10 μm or less.
Here, the average particle diameter d50 of the 2 nd order particles of acetylene black can be measured by a laser diffraction method.
In the present embodiment, the sealing resin composition may contain components other than the epoxy resin and the inorganic filler.
For example, the sealing resin composition may further contain a curing agent.
(curing agent)
The curing agent can be roughly classified into 3 types, for example, an addition polymerization type curing agent, a catalyst type curing agent, and a condensation type curing agent, and 1 or 2 or more of these can be used.
Examples of the addition polymerization type curing agent include: polyamine compounds including aliphatic polyamines such as Diethylenetriamine (DETA), triethylenetetramine (TETA), and m-xylylenediamine (MXDA), aromatic polyamines such as diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone (DDS), Dicyandiamide (DICY), and organic acid dihydrazide; acid anhydrides including alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), and aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA) and benzophenonetetracarboxylic acid (BTDA); phenolic resin curing agents such as novolak-type phenolic resins and polyvinyl phenols; polythiol compounds such as polysulfides, thioesters and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and organic acids such as carboxylic acid-containing polyester resins.
Examples of the catalyst-type curing agent include: tertiary amine compounds such as Benzyldimethylamine (BDMA) and 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30); imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI 24); lewis acids such as BF3 complex, etc.
Examples of the condensation type curing agent include: a phenolic resin; urea resins such as methylol group-containing urea resins; melamine resins such as methylol group-containing melamine resins, and the like.
Among these, a phenol resin curing agent is preferable from the viewpoint of improving the balance among flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like. As the phenolic resin curing agent, all monomers, oligomers, and polymers having 2 or more phenolic hydroxyl groups in one molecule can be used, and the molecular weight and the molecular structure thereof are not limited.
Examples of the phenolic resin curing agent used for the curing agent include: novolac-type phenol resins such as phenol novolac resins, cresol novolac resins, and bisphenol novolac resins; polyvinyl phenol; multifunctional phenol resins such as phenol/hydroxybenzaldehyde resins and triphenol methane type phenol resins; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; aralkyl type phenol resins such as phenol aralkyl resins having a phenylene skeleton and/or a biphenylene skeleton and naphthol aralkyl resins having a phenylene skeleton and/or a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F, and these may be used alone in 1 kind or in combination with 2 or more kinds. Of these, when applied to a semiconductor device including a Cu wiring, 1 or 2 or more selected from biphenyl aralkyl type phenol resins, novolac type phenol resins, and phenol aralkyl resins having a phenylene skeleton are more preferably used from the viewpoint of obtaining a semiconductor device excellent in HTSL characteristics and laser imprint properties.
In the present embodiment, as the combination of the component (a) and the phenol resin curing agent, a combination of biphenyl aralkyl type epoxy resin/biphenyl aralkyl type phenol resin, a combination of o-cresol novolac type epoxy resin/novolac type phenol resin, and a combination of biphenyl type epoxy resin/phenol aralkyl resin are preferable.
In the present embodiment, the content of the curing agent in the sealing resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, relative to the entire sealing resin composition, from the viewpoint of achieving excellent fluidity during molding and improving filling properties and moldability.
In the semiconductor device using the cured product of the sealing resin composition as the sealing material, the content of the curing agent in the sealing resin composition is preferably 25% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less with respect to the entire sealing resin composition, from the viewpoint of improving moisture resistance reliability and reflow resistance.
The sealing resin composition may contain components other than the above components, and for example, 1 or more of various additives such as a curing accelerator, a coupling agent, a release agent, an ion scavenger, a low-stress component, a flame retardant, and an antioxidant may be appropriately blended.
The curing accelerator may include, for example, a phosphorus atom-containing compound selected from organic phosphines, tetra-substituted phosphonium compounds, phosphate betaine compounds, adducts of phosphine compounds with quinone compounds, adducts of phosphonium compounds with silane compounds, and the like; 1, 8-diazabicyclo [5.4.0] undecene-7, benzyldimethylamine, amidine or tertiary amine exemplified by 2-methylimidazole, or a nitrogen atom-containing compound such as a quaternary salt of the amidine or amine. Among these, from the viewpoint of improving curability, a compound containing a phosphorus atom is more preferably contained. From the viewpoint of improving the balance between moldability and curability, compounds having latency such as tetra-substituted phosphonium compounds, phosphate betaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds are more preferable. From the same viewpoint, the curing accelerator more preferably contains triphenylphosphine.
From the viewpoint of improving the curing characteristics of the sealing resin composition, the content of the curing accelerator in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 2.0% by mass or less, more preferably 1.0% by mass or less, relative to the entire sealing resin composition.
The coupling agent may contain 1 or 2 or more kinds selected from known coupling agents such as, for example, aminosilanes such as epoxysilane, mercaptosilane and phenylaminosilane, various silane compounds such as alkylsilane, ureidosilane, vinylsilane and methacrylsilane, titanium compounds, aluminum chelates and aluminum/zirconium compounds. Among these, as a coupling agent which more effectively exhibits the effects of the present invention, it is more preferable to contain an epoxysilane or an aminosilane, and it is further preferable to contain a secondary aminosilane from the viewpoint of fluidity and the like. Specific examples of the secondary aminosilanes include N-phenyl-gamma-aminopropyltrimethoxysilane.
From the viewpoint of obtaining preferable fluidity at the time of molding of the sealing resin composition, the content of the coupling agent in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 2.0% by mass or less, more preferably 1.0% by mass or less, relative to the entire sealing resin composition.
The release agent may comprise, for example, a natural wax selected from carnauba wax; synthetic waxes such as oxidized polyethylene wax and montanic acid ester wax; higher fatty acids such as zinc stearate and metal salts thereof; and 1 or more than 2 kinds of paraffin.
From the viewpoint of obtaining preferable release characteristics of a cured product, the content of the release agent in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 2.0% by mass or less, more preferably 1.0% by mass or less, relative to the entire sealing resin composition.
The ion scavenger contains, for example, hydrotalcite.
From the viewpoint of improving the reliability of the semiconductor device, the content of the ion scavenger in the sealing resin composition is preferably 0.03 mass% or more, more preferably 0.05 mass% or more, and preferably 2.0 mass% or less, more preferably 1.0 mass% or less, with respect to the entire sealing resin composition.
Examples of the low-stress component include silicone oil, silicone rubber, and carboxyl-terminated butadiene acrylonitrile rubber.
From the viewpoint of improving the connection reliability of the semiconductor device, the content of the low-stress component in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and preferably 2.0% by mass or less, more preferably 1.0% by mass or less, relative to the entire sealing resin composition.
The flame retardant may contain, for example, 1 or 2 or more selected from aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene.
The antioxidant includes, for example, 1 or 2 or more selected from hindered phenol compounds, hindered amine compounds and thioether compounds.
(method for producing sealing resin composition)
Next, a method for producing the sealing resin composition will be described.
In the present embodiment, the sealing resin composition can be obtained, for example, by the following method: the above components are mixed by a known apparatus, and further melt-kneaded by a kneading machine such as a roll, kneader, or extruder, cooled, and then pulverized. If necessary, the resin composition for sealing in the form of particles can be obtained by crushing and then molding into a pellet form. The resin composition for sheet sealing can also be obtained by, for example, vacuum press molding or compression molding after pulverization in the above-mentioned method. The obtained resin composition for sealing can be appropriately adjusted in dispersibility, fluidity, and the like.
In the present embodiment, the S content in the cured product of the sealing resin composition in the above-described specific range can be obtained by adjusting the components and the blending (content) contained in the sealing resin composition.
The encapsulating resin composition obtained in the present embodiment contains the components (a) to (C), and the S content in the cured product is in a specific range, so that a semiconductor device having excellent HTSL properties and excellent laser marking properties can be obtained by using the encapsulating resin composition even when used in combination with a Cu wire.
(semiconductor device)
The semiconductor device of the present embodiment is obtained by sealing a semiconductor element using the sealing resin composition of the present embodiment.
Fig. 1 is a cross-sectional view showing an example of a semiconductor device 100 according to the present embodiment. Here, the substrate 30 is, for example, a lead frame.
The semiconductor device 100 of the present embodiment includes: a semiconductor element 20; a bonding wire 40 connected to the semiconductor element 20; and a sealing member 50, wherein the sealing member 50 is composed of a cured product of the sealing resin composition.
More specifically, the semiconductor element 20 is fixed to the base 30 via a die attach (die attach) material 10, and the semiconductor device 100 includes an external wire 34 connected from an electrode pad 22 provided on the semiconductor element 20 via a bonding wire 40. The bonding wire 40 may be set according to the semiconductor element 20 used, and for example, a Cu wire may be used.
The semiconductor element 20 can be fixed to the die pad 32 of the base 30 via the die bonding material 10.
In the present embodiment, the sealing member 50 is composed of a cured product of the sealing resin composition. Therefore, in the semiconductor device 100, even when the bonding wire 40 is made of a material containing Cu, excellent HTSL characteristics can be obtained, and the semiconductor device 100 is excellent in imprinting performance by a laser such as YAG laser. The seal member 50 may be formed, for example, as follows: the sealing resin composition is sealed and molded by a known method such as transfer molding or compression molding.
The upper surface of the sealing member 50 may be marked with a mark by a laser such as a YAG laser. The mark is constituted by at least 1 or more of characters, numbers, or symbols constituted by straight lines or curved lines, for example. The mark indicates, for example, a product name, a product number, a lot number, a manufacturer name, or the like of the semiconductor package. The label may be, for example, YVO4Laser, carbonic acid laser, etc.
Although the embodiments of the present invention have been described above, these are examples of the present invention, and various other embodiments than the above may be adopted.
[ examples ]
The present embodiment will be described in detail below with reference to examples and comparative examples. The present embodiment is not limited to the description of the examples.
Examples 1 to 5 and comparative examples 1 to 4
(preparation of sealing resin composition)
For each example and each comparative example, a resin composition for sealing was prepared in the following manner, respectively.
First, the components shown in table 1 were mixed by a mixer. Next, the obtained mixture was roll-kneaded, cooled, and pulverized to obtain a sealing resin composition as a powder or granule.
The details of each component in table 1 are as follows. The blending ratio of each component shown in table 1 represents the blending ratio (parts by mass) with respect to the whole resin composition.
(raw materials)
Filling material 1: fused spherical silica (FB-950 FC, manufactured by Denko Co., Ltd., average particle diameter d50 ═ 22 μm)
Filling material 2: synthetic spherical silica (SO-E2, average particle size d50 ═ 0.5 μm, manufactured by Admatechs Co., Ltd.)
Colorant 1: carbon black (Mitsubishi chemical corporation, MA-600)
Colorant 2: CARBON black (CARBON #5, Mitsubishi chemical corporation)
Colorant 3: black titanium oxide (Ti)4O7Volume resistivity of 7.3 × 104Ω·cm)
Colorant 4: acetylene black (Li-100, manufactured by electrochemical Co., Ltd., average particle diameter d50 of 2-th order particles: 8 μm)
Colorant 5: acetylene black (Li-400, manufactured by electrochemical Co., Ltd., average particle diameter d50 of 2-th order particles: 5 μm)
Coupling agent: n-phenyl-gamma-aminopropyltrimethoxysilane (CF-4083, manufactured by Dow Corning Dongli Co., Ltd.)
Epoxy resin 1: phenylaralkyloxy type epoxy resin having phenylene skeleton (NC-3000, made by Nippon Kagaku Co., Ltd.)
Epoxy resin 2: o-cresol novolac type epoxy resin (YDCN-800-70, made by Nissi iron Tokyo chemical Co., Ltd.)
Epoxy resin 3: biphenyl type epoxy resin (manufactured by Mitsubishi chemical corporation, YX4000HK)
Curing agent 1: biphenylalkyl phenol resin (GPH-65, made by Nippon Kabushiki Kaisha)
Curing agent 2: novolac type phenol resin (PR-HF-3, manufactured by Sumitomo Bakelite Co., Ltd.)
Curing agent 3: phenol aralkyl resin having a phenylene skeleton (XLC-4L, manufactured by Mitsui chemical Co., Ltd.)
Curing accelerator: triphenylphosphine (TPP)
Mold release agent 1: CARNAUBA wax (NIKKO CARNAUBA, manufactured by NIKKO RICA)
And (2) release agent: oxidized polyethylene wax (RICO WAXPED522, produced by Clariant Chemicals, Inc.)
An ion scavenger: hydrotalcite (DHT-4H, manufactured by Kyoho chemical industry Co., Ltd.)
Low-stress agent 1: silicone oil having a polyalkylene ether group, a methyl group, etc. (FZ-3730, manufactured by Dow Corning Dongli Co., Ltd.)
Low-stress agent 2: carboxyl-terminated butadiene acrylonitrile rubber (CTBN 1008SP, made by Yu Shih Kyoki Kaisha)
(evaluation)
The following evaluations were made with respect to the sealing resin compositions obtained in the respective examples or cured products thereof. The evaluation results are shown in table 1.
(quantity S: approximate fluorescence X-ray (ppm))
The sealing resin compositions obtained in the respective examples were molded into a molded article having a diameter of 50mm and a thickness of 3mm at a mold temperature of 175 ℃, an injection pressure of 7.4MPa, and a curing time of 2 minutes by a transfer molding machine, and post-cured at 175 ℃ for 4 hours to obtain disk-shaped samples.
The surface of the sample was scanned with X-rays (under conditions of a tube voltage of 40kV and a tube current of 95 mA) by a wavelength dispersive X-ray fluorescence analyzer (XRF-1800, manufactured by Shimadzu corporation) to measure the intensity of the X-rays. The sulfur concentration in the sample is calculated from a calibration curve of the amount of S and the intensity of fluorescent X-rays prepared from a standard sample having a known amount of S (1 to 50 ppm).
(Tg(℃))
Glass transition temperature the test piece obtained was post-cured at 175 ℃ for 4 hours, and then, from a graph obtained by measuring a temperature range of 0 ℃ to 320 ℃ at a temperature rise rate of 5 ℃/minute using a thermomechanical analyzer (TMA 100, manufactured by seiko electronics corporation), the linear expansion coefficient (α 1) of a region below the glass transition temperature and the linear expansion coefficient (α 2) corresponding to the rubber-like region were determined, and at this time, the intersection of the extension lines of α 1 and α 2 was set as the glass transition temperature (unit is shown in degrees centigrade).
(imprintability)
A molded article having a diameter of 50mm and a thickness of 3mm was molded by a transfer molding machine at a mold temperature of 175 ℃ and an injection pressure of 7.4MPa for a curing time of 2 minutes, and post-cured at 175 ℃ for 4 hours to obtain a disc-shaped sample. The disk was engraved (marked) by a mask type YAG laser marker (laser marker) manufactured by japan electric corporation (conditions of an applied voltage of 2.4kV, a pulse width of 120 μ s, 15A, 30kHz, 300 mm/sec).
The evaluation criteria are shown below.
OK: visibility (visibility) equal to or greater than that of comparative example 1
NG: the visibility was inferior to that of comparative example 1
(color tone)
The color tone of the sample used for evaluation of the imprint property in each example was evaluated visually by 1 evaluator.
The evaluation criteria are shown below.
OK: has a black color tone equivalent to that of comparative example 1
△ the hue was close to other colors as compared with comparative example 1
NG: the black color was pale as compared with comparative example 1, and was further close to other colors
The "OK" and "△" were evaluated as passed.
(HTSL：200℃、1500h)
[ production of semiconductor device ]
Semiconductor devices were fabricated as follows for examples 1 to 5 and comparative examples 1 to 4, respectively.
First, a TEG (Test Element Group) chip (3.5mm × 3.5mm) having an aluminum electrode pad was mounted on a die pad portion of a lead frame whose surface was Ag-plated. Next, electrode pads of the TEG chip (hereinafter also simply referred to as "electrode pads") and external lead portions of the lead frame were wire bonded at a lead pitch of 120 μm using bonding wires made of a metal material of cu99.9%. The structure thus obtained was subjected to sealing molding using a sealing resin composition under conditions of a mold temperature of 175 ℃, an injection pressure of 10.0MPa, and a curing time of 2 minutes by a low-pressure transfer molding machine to produce a semiconductor package. Thereafter, the obtained semiconductor was sealed at 175 ℃ for 4 hours and post-cured to obtain a semiconductor device.
[ high temperature storage characteristics ]
The obtained semiconductor device was subjected to HTSL (high temperature storage test) by the following method. Each semiconductor device was stored at a temperature of 200 ℃ for 1500 hours. The resistance between the lead and the electrode pad of the semiconductor device after storage was measured. The semiconductor devices showing a resistance value of less than 110% in the average value of the initial resistance values of the respective semiconductor devices were evaluated as OK, and the semiconductor devices showing a resistance value of 110% or more were evaluated as NG.
Figure BDA0002453205770000161
The present application claims priority based on Japanese application laid-open application No. 2017-200110 filed on 16.10.2017, the entire disclosure of which is incorporated herein by reference.

Claims (6)

1. A sealing resin composition comprising the following components (A) to (C):
(A) an epoxy resin;
(B) an inorganic filler material; and
(C) a black-based coloring agent, wherein,
the resin composition for sealing is characterized in that:
the S content in a cured product of the sealing resin composition obtained by measuring a test piece obtained by the following production method by the following method is 10ppm or less based on the whole cured product,
(method of preparing sample)
A molded article having a diameter of 50mm and a thickness of 3mm was molded by a transfer molding machine at a mold temperature of 175 ℃ under an injection pressure of 7.4MPa for a curing time of 2 minutes, and post-cured at 175 ℃ for 4 hours to obtain a disc-shaped sample,
(method of measuring S content)
The sulfur concentration in the sample was measured under conditions of a tube voltage of 40kV and a tube current of 95mA using a wavelength dispersive X-ray fluorescence analyzer XRF-1800 manufactured by Shimadzu corporation.
2. The resin composition for sealing according to claim 1, characterized in that:
the component (C) contains acetylene black.
3. The resin composition for sealing according to claim 2, characterized in that:
the content of the acetylene black in the sealing resin composition is 0.10 mass% or more and 1.0 mass% or less with respect to the entire sealing resin composition.
4. The resin composition for sealing according to claim 2 or 3, characterized in that:
the average particle diameter d50 of the 2-order particles of acetylene black is 1-20 μm.
5. The resin composition for sealing according to any one of claims 1 to 4, characterized in that:
the sealing resin composition does not substantially contain furnace black.
6. A semiconductor device, characterized in that:
a semiconductor device sealed by using the sealing resin composition according to any one of claims 1 to 5.
CN201880067422.7A 2017-10-16 2018-10-04 Resin composition for sealing and semiconductor device Pending CN111247206A (en)

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