WO2012070529A1 - 半導体封止用エポキシ樹脂組成物及び半導体装置 - Google Patents
半導体封止用エポキシ樹脂組成物及び半導体装置 Download PDFInfo
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- WO2012070529A1 WO2012070529A1 PCT/JP2011/076799 JP2011076799W WO2012070529A1 WO 2012070529 A1 WO2012070529 A1 WO 2012070529A1 JP 2011076799 W JP2011076799 W JP 2011076799W WO 2012070529 A1 WO2012070529 A1 WO 2012070529A1
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- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
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- 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
- H01L2924/01—Chemical elements
- H01L2924/01015—Phosphorus [P]
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- 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
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/14—Integrated circuits
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- 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
Definitions
- the present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device sealed with the same.
- This application claims priority based on Japanese Patent Application No. 2010-260913 for which it applied to Japan on November 24, 2010, and uses the content here.
- an epoxy resin composition excellent in heat resistance and moisture resistance which contains an epoxy resin, a phenol resin-based curing agent, and an inorganic filler such as fused silica or crystalline silica.
- an epoxy resin composition excellent in heat resistance and moisture resistance which contains an epoxy resin, a phenol resin-based curing agent, and an inorganic filler such as fused silica or crystalline silica.
- Patent Document 1 discloses a bonding wire having a core material mainly composed of copper, and an outer skin layer containing conductive metal and copper different in one or both of components and compositions from the core material on the core material. Is described.
- this bonding wire when the thickness of the outer skin layer is 0.001 to 0.02 ⁇ m, the material cost is low, the ball bonding property, the wire bonding property, etc. are excellent, the loop forming property is also good, and the narrow pitch It is described that it becomes possible to provide a copper-based bonding wire that can be adapted for thinning a wire and increasing the diameter of a power IC.
- the moisture resistance reliability (HAST) of the semiconductor device may be lowered.
- HAST moisture resistance reliability
- the epoxy resin composition for semiconductor encapsulation according to any one of [1] to [4], wherein the epoxy resin (A) includes an epoxy resin represented by the following general formula (1): Is provided.
- a plurality of R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n represents a degree of polymerization, and an average value thereof is a positive number of 0 to 4. is there.
- the epoxy resin composition for semiconductor encapsulation of the present invention is A semiconductor element mounted on a lead frame or circuit board having a die pad portion; A metal wire for electrically joining an electrical joint provided on the lead frame or the circuit board and an electrode pad provided on the semiconductor element; A semiconductor sealing epoxy resin composition used for manufacturing a semiconductor device by sealing an epoxy resin (A), a curing agent (B), an inorganic resin. Containing a filler (C),
- the epoxy resin (A) is characterized in that the area of the main peak in the measurement by an area method of gel permeation chromatography is 90% or more with respect to the total area of all peaks.
- the epoxy resin composition for semiconductor encapsulation of the present invention contains an epoxy resin (A).
- the epoxy resin (A) is a monomer, oligomer, or polymer in general having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited.
- epoxy resin (A) examples include biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol type epoxy resin such as tetramethylbisphenol F type epoxy resin, stilbene type epoxy resin; phenol novolac type epoxy Resin, novolak type epoxy resin such as cresol novolac type epoxy resin; polyfunctional epoxy resin such as triphenolmethane type epoxy resin and alkyl-modified triphenolmethane type epoxy resin; phenol aralkyl type epoxy resin having phenylene skeleton, phenylene skeleton Aralkyl-type epoxy resins such as naphthol aralkyl-type epoxy resins and phenol-aralkyl-type epoxy resins having a biphenylene skeleton; dihydroanthracenediol Type epoxy resin; naphthol type epoxy resin such as epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene dimer; triazine nucleus-containing epoxy resin such as triglycidyl
- biphenyl type epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, stilbene type epoxy resin, etc. have the property of expressing high crystallinity by selection and purification of synthesis methods.
- the epoxy resin (A) used in the present invention is characterized in that the area of the main peak in the measurement by the area method of gel permeation chromatography is 90% or more with respect to the total area of all peaks. More preferably, the area of the main peak is 92% or more with respect to the total area of all peaks. Particularly preferably, the area of the main peak is 95% or more with respect to the total area of all the peaks.
- the main peak in the measurement by the area method of the gel permeation chromatograph of the epoxy resin (A) is a peak having the maximum area in each peak of the gel permeation chromatograph, and the purity of the epoxy resin It can be used as an index. And since the epoxy resin (A) whose area of the said main peak is in the said range with respect to the total area of all the peaks has few by-products containing chlorine, the epoxy resin composition with few corrosive impurities is obtained. be able to.
- an epoxy metal precursor such as a phenol resin is dissolved in an excess of epihalohydrin such as epichlorohydrin, and then an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. And a method of reacting at 50 to 150 ° C., preferably 60 to 120 ° C. for 1 to 10 hours. After completion of the reaction, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain an epoxy resin. Can be obtained.
- epihalohydrin such as epichlorohydrin
- an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
- a method of reacting at 50 to 150 ° C., preferably 60 to 120 ° C. for 1 to 10 hours. After completion of the reaction, excess epichlorohydrin is distilled off, and
- the amount of epihalohydrin is reduced within a range not to increase the molecular weight by self-polymerization at the time of synthesis, or the halogen adduct in the epoxy resin or the like.
- a technique such as reducing the blending amount and blending concentration of the alkali metal hydroxide within a range in which the ring-closing epoxy group does not become excessive can be applied.
- specific epoxy resins specified in the present invention can be prepared by appropriately combining known purification methods such as column chromatography fractionation, molecular distillation, recrystallization, etc. with epoxy resins that are synthesized by known methods or are commercially available. Also good.
- a commercially available epoxy resin prepared in this way can also be used. Examples of commercially available products include “YX4000UH” manufactured by Mitsubishi Chemical Corporation and “YL7684” manufactured by Mitsubishi Chemical Corporation.
- GPC gel permeation chromatography
- the GPC apparatus is composed of a pump, an injector, a guard column, a column, and a detector, and tetrahydrofuran (THF) is used as a solvent.
- the measurement is performed at a pump flow rate of 0.5 ml / min. A flow rate higher than this is not preferable because the detection accuracy of the target molecular weight is lowered.
- the flow rate accuracy is preferably 0.10% or less.
- a commercially available guard column for example, TSK GUARDCOLUMN HHR-L: diameter 6.0 mm, tube length 40 mm
- TSK-GEL GMHHR- manufactured by Tosoh Corporation a commercially available polystyrene gel column
- L diameter 7.8 mm, tube length 30 mm
- RI detector for example, a differential refractive index (RI) detector W2414 manufactured by WATERS
- WATERS differential refractive index
- the epoxy resin (A) used in the present invention preferably has a total chlorine content of 300 ppm or less and a hydrolyzable chlorine content of 150 ppm or less. More preferably, the total chlorine content is 200 ppm or less, and the hydrolyzable chlorine content is 100 ppm or less. Particularly preferably, the total chlorine content is 50 ppm or less, and the hydrolyzable chlorine content is 30 ppm or less.
- a semiconductor device with high moisture resistance reliability can be obtained. Chlorine ions are corrosive to metals and corrode aluminum wiring parts such as electrode pads of semiconductor elements.
- Chlorine in the epoxy resin composition for semiconductor encapsulation is derived from the epoxy resin. Since an epoxy resin is synthesized using epichlorohydrin containing chlorine, even if it is a high-purity epoxy resin for use in electronic materials, the total chlorine content is usually 600 ppm or more. At least 50% of the chlorine contained in the epoxy exhibits hydrolyzability and is easily desorbed as chlorine ions. If the total chlorine amount and hydrolyzable chlorine amount in the epoxy resin are within the above ranges, the moisture resistance reliability of the semiconductor device is greatly improved.
- Chlorine is contained in a large amount in the high molecular weight component of the epoxy resin, and is small in the main peak portion which is the lowest molecule (when n is 0 in the following general formula (1)). That is, the main peak portion is on the low molecular side, and the amount of chlorine contained in the epoxy resin on the low molecular side decreases. If it is an epoxy resin whose area of the main peak is within the above range with respect to the total area of all peaks as measured by the area method of gel permeation chromatography, the total chlorine amount and hydrolyzable chlorine amount are within the above range. By using such an epoxy resin, it is possible to obtain a resin composition for encapsulating a semiconductor having a remarkably low chlorine content.
- the total chlorine content of the epoxy resin can be measured by JIS K7229 (quantitative determination method of chlorine in the chlorine-containing resin), and the hydrolyzable chlorine can be measured by JIS K6755 (easily saponifiable chlorine content test method in the epoxy resin).
- an epoxy resin (A) what contains the epoxy resin represented by following General formula (1) can be used as an epoxy resin (A). Since the epoxy resin represented by the general formula (1) is a crystalline epoxy resin, by performing purification by recrystallization, the area of the main peak is the sum of all peaks as measured by the gel permeation chromatograph area method. An epoxy resin that is 90% or more based on the area can be obtained relatively easily.
- a plurality of R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n represents a degree of polymerization, and an average value thereof is a positive number of 0 to 4. is there.
- n is preferably 0 to 3, more preferably 0 to 2, and most preferably 0.
- the compounding ratio of an epoxy resin (A) is not specifically limited, It is preferable that it is 3 to 20 mass% with respect to the whole epoxy resin composition for semiconductor sealing, and is 5 to 18 mass%. More preferably. Although it does not specifically limit as a lower limit of the compounding ratio of an epoxy resin (A), It is preferable that it is 3 mass% or more with respect to the whole epoxy resin composition for semiconductor sealing, and it is more preferable that it is 5 mass% or more. preferable. The reason is that when the lower limit value of the blending ratio of the epoxy resin (A) is within the above range, there is little possibility of causing wire breakage due to an increase in viscosity.
- the upper limit of the blending ratio of the epoxy resin (A) is not particularly limited, but is preferably 20% by mass or less, and 18% by mass or less with respect to the entire epoxy resin composition for semiconductor encapsulation. Is more preferable. The reason is that when the upper limit value of the blending ratio of the epoxy resin (A) is within the above range, there is little possibility of causing a decrease in moisture resistance reliability due to an increase in water absorption.
- curing agent (B) used for the epoxy resin composition for semiconductor sealing of this invention it divides roughly into three types, for example, a polyaddition type hardening
- polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylene diamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylenediamine (MPDA).
- DETA diethylenetriamine
- TETA triethylenetetramine
- MXDA metaxylylene diamine
- DDM diaminodiphenylmethane
- MPDA m-phenylenediamine
- aromatic polyamines such as diaminodiphenylsulfone (DDS), polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, and the like; alicyclics such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides, including acid anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), aromatic anhydrides such as benzophenone tetracarboxylic acid (BTDA); Polyphenol compounds such as phenol resins typified by condensation of phenols such as alcohol and naphthol with ketones and aldehydes, and phenol polymers typified by polyvinylphenol; Polymercaptan compounds such as polysulfide, thioester and thioether; Examples thereof include isocyanate compounds such as polymers and blocked isocyanates; and organic acids such as carboxylic acid-containing polyester
- catalyst-type curing agent examples include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4 -Imidazole compounds such as methylimidazole (EMI24); Lewis acids such as BF3 complexes.
- BDMA benzyldimethylamine
- DMP-30 2,4,6-trisdimethylaminomethylphenol
- 2-methylimidazole, 2-ethyl-4 -Imidazole compounds such as methylimidazole (EMI24)
- Lewis acids such as BF3 complexes.
- condensation type curing agent examples include phenol resin-based curing agents such as resol type phenol resins; urea resins such as methylol group-containing urea resins; melamine resins such as methylol group-containing melamine resins.
- a phenol resin-based curing agent is preferable from the viewpoint of balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like.
- the phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure are not particularly limited.
- novolak type resins such as phenol novolak resin, cresol novolak resin, bisphenol novolak; polyfunctional phenol resins such as triphenolmethane type phenol resin; modified phenol resins such as terpene modified phenol resin and dicyclopentadiene modified phenol resin; phenylene Aralkyl type resins such as a phenol aralkyl resin having a skeleton and / or a biphenylene skeleton, a naphthol aralkyl resin having a phenylene and / or a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F, and the like. Two or more types may be used in combination. Two or more types may be used in combination.
- curing agent (B) is not specifically limited, It is preferable that it is 0.8 mass% or more and 16 mass% or less with respect to the whole epoxy resin composition for semiconductor sealing, and 1.5 mass% or more and 14 It is more preferable that the amount is not more than mass%. Although it does not specifically limit about the lower limit of the mixture ratio of a hardening
- the upper limit of the blending ratio of the curing agent (B) is not particularly limited, but is preferably 16% by mass or less, and 14% by mass or less with respect to the entire epoxy resin composition for semiconductor encapsulation. It is more preferable. The reason is that when the upper limit value of the blending ratio is within the above range, there is little possibility of causing a decrease in moisture resistance reliability due to an increase in water absorption.
- the number of epoxy groups (EP) of all epoxy resins and the phenol of all phenol resin-based curing agents is 0.8 or more and 1.3 or less.
- the equivalent ratio (EP) / (OH) to the number of functional hydroxyl groups (OH) is 0.8 or more and 1.3 or less.
- the inorganic filler (C) used in the epoxy resin composition for semiconductor encapsulation of the present invention those used in general epoxy resin compositions for semiconductor encapsulation can be used.
- fused spherical silica, fused crushed silica, crystalline silica, talc, alumina, titanium white, silicon nitride and the like can be mentioned, among which fused spherical silica is particularly preferable.
- These inorganic fillers may be used alone or in combination of two or more.
- the shape of the inorganic filler (C) is as spherical as possible in order to suppress an increase in melt viscosity of the epoxy resin composition for semiconductor encapsulation and further increase the content of the inorganic filler, and the particle size The distribution is preferably broad.
- the inorganic filler (C) may be surface-treated with a coupling agent. Further, if necessary, the inorganic filler (C) may be pretreated with an epoxy resin or a phenol resin. Examples of the treatment method include a method of removing the solvent after mixing using a solvent, a method of directly adding to the inorganic filler (C), and a mixing treatment using a mixer.
- the content rate of an inorganic filler (C) is not specifically limited, It is preferable that it is 60 to 92 mass% with respect to the whole epoxy resin composition for semiconductor sealing, and 65 to 89 mass% is preferable. It is more preferable that The lower limit of the content ratio of the inorganic filler (C) is not particularly limited, but considering the filling property of the epoxy resin composition for semiconductor encapsulation and the reliability of the semiconductor device, the entire epoxy resin composition for semiconductor encapsulation is considered as a whole. Thus, it is preferably 60% by mass or more, and more preferably 65% by mass or more.
- the upper limit of the content ratio of the inorganic filler is preferably 92% by mass or less, and preferably 89% by mass or less, with respect to the entire epoxy resin composition for semiconductor encapsulation, in view of moldability. More preferred. The reason for this is that, if the upper limit is not exceeded, fluidity is reduced and there is little risk of inadequate filling during molding, or inconvenience such as wire flow in the semiconductor device due to increased viscosity. It is.
- a curing accelerator can further be used in the epoxy resin composition for semiconductor encapsulation of the present invention.
- the curing accelerator include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; -Amidines and tertiary amines exemplified by diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole and the like, and further nitrogen-containing compounds such as the quaternary salts of amidines and amines mentioned above Of these, one or two or more of these can be used in combination.
- a phosphorus atom-containing compound is preferable from the viewpoint of curability, and an adduct of a phosphobetaine compound and a phosphine compound and a quinone compound is particularly preferable from the viewpoint of solder resistance and fluidity.
- phosphorus-containing compounds such as tetra-substituted phosphonium compounds and adducts of phosphonium compounds and silane compounds are particularly preferred.
- Examples of the organic phosphine that can be used in the resin composition include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; a trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine. Tertiary phosphine.
- Examples of the tetra-substituted phosphonium compound that can be used in the resin composition include compounds represented by the following general formula (2).
- P represents a phosphorus atom.
- R8, R9, R10, and R11 represent an aromatic group or an alkyl group.
- A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group.
- X and y are integers of 1 to 3
- z is an integer of 0 to 3
- x y.
- the compound represented by the general formula (2) is obtained, for example, as follows, but is not limited thereto. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Subsequently, when water is added, the compound represented by the general formula (2) can be precipitated.
- R7, R8, R9 and R10 bonded to the phosphorus atom are preferably phenyl groups
- AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols.
- A is an anion of the phenol.
- phenols in the present invention include monocyclic phenols such as phenol, cresol, resorcin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, bisphenol A, bisphenol F, and bisphenol S.
- monocyclic phenols such as phenol, cresol, resorcin, and catechol
- condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol
- bisphenol A bisphenol F
- bisphenol S bisphenol S
- polycyclic phenols such as bisphenols, phenylphenol, and biphenol.
- Examples of the phosphobetaine compound include compounds represented by the following general formula (3).
- X1 represents an alkyl group having 1 to 3 carbon atoms
- Y1 represents a hydroxyl group
- e is an integer of 0 to 5
- f is an integer of 0 to 3.
- the compound represented by the general formula (3) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt.
- a triaromatic substituted phosphine which is a third phosphine
- the present invention is not limited to this.
- Examples of the adduct of a phosphine compound and a quinone compound include compounds represented by the following general formula (4).
- R12, R13 and R14 each represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same as each other
- R15, R16 and R17 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R15 and R16 are bonded to form a cyclic structure. May be.
- Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine.
- aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine.
- Those having a substituent or a substituent such as an alkyl group or an alkoxyl group are preferred.
- Examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, tripheny
- examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone and anthraquinones, and among them, p-benzoquinone is preferable from the viewpoint of storage stability.
- the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone.
- the solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct.
- the present invention is not limited to this.
- R11, R12 and R13 bonded to the phosphorus atom are phenyl groups, and R14, R15 and R16 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl
- R11, R12 and R13 bonded to the phosphorus atom are phenyl groups
- R14, R15 and R16 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl
- a compound to which phosphine is added is preferable in that it reduces the thermal elastic modulus of the cured product of the resin composition.
- Examples of the adduct of the phosphonium compound and the silane compound include compounds represented by the following general formula (5).
- P represents a phosphorus atom and Si represents a silicon atom.
- R18, R19, R20 and R21 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.
- X2 is an organic group bonded to the groups Y2 and Y3, where X3 is an organic group bonded to the groups Y4 and Y5.
- Y3 represent a group formed by releasing a proton from a proton donating group, and groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate structure.
- Y4 and Y5 are proton donating groups.
- the group represents a group formed by releasing a proton, and the groups Y4 and Y5 in the same molecule are bonded to a silicon atom to form a chelate structure.
- X2 and X3 may be the same or different from each other. Even if well, Y2, Y3, Y4, and Y5 is .Z1 may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.
- R18, R19, R20 and R21 for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, and the like.
- an aromatic group having a substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, or the like
- a substituted aromatic group is more preferred.
- X2 is an organic group bonded to Y2 and Y3.
- X3 is an organic group that binds to groups Y4 and Y5.
- Y2 and Y3 are groups formed by proton-donating groups releasing protons, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure.
- Y4 and Y5 are groups formed by proton-donating groups releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure.
- the groups X2 and X3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other.
- the groups represented by -Y2-X2-Y3- and -Y4-X3-Y5- in general formula (5) are constituted by groups in which the proton donor releases two protons. Is.
- the proton donor is preferably an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule. Further, an aromatic compound having at least two total carboxyl groups or hydroxyl groups on adjacent carbons constituting the aromatic ring is preferable, and among them, an aromatic compound having at least two total hydroxyl groups on the carbon constituting the aromatic ring is more preferable. .
- catechol pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3 -Hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin and the like.
- catechol 1,2 -Dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferred.
- Z1 represents an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.
- aliphatic hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and octyl group
- aromatic groups such as phenyl group, benzyl group, naphthyl group and biphenyl group.
- Reactive substituents such as hydrocarbon group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group can be mentioned.
- methyl group, ethyl group, phenyl group, naphthyl group and biphenyl group are included. From the viewpoint of thermal stability, it is more preferable.
- a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol, and then dissolved.
- Sodium methoxide-methanol solution is added dropwise with stirring.
- crystals are deposited. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound.
- the manufacturing method is not limited to this.
- the blending ratio of the curing accelerator is not particularly limited, but is preferably 0.05% by mass or more and 1% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass with respect to the entire epoxy resin composition for semiconductor encapsulation. It is more preferable that the amount is not more than mass%. Although it does not specifically limit as a lower limit of the mixture ratio of a hardening accelerator, It is preferable that it is 0.05 mass% or more with respect to the whole epoxy resin composition for semiconductor sealing, and it is 0.1 mass% or more. Is more preferable. The reason is that when the lower limit of the blending ratio of the curing accelerator is within the above range, there is little possibility of causing a decrease in curability.
- the upper limit of the blending ratio of the curing accelerator is not particularly limited, but it is preferably 1% by mass or less, and 0.5% by mass or less with respect to the entire epoxy resin composition for semiconductor encapsulation. Is more preferable. The reason is that when the upper limit of the blending ratio of the curing accelerator is within the above range, there is little possibility of causing a decrease in fluidity.
- the epoxy resin composition for semiconductor encapsulation of the present invention further includes a corrosion inhibitor such as hydrotalcite and zirconium hydroxide; an inorganic ion exchanger such as bismuth oxide hydrate; and ⁇ -glycidoxy Coupling agents such as propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane; colorants such as carbon black and bengara; low stress components such as silicone rubber; natural waxes such as carnauba wax; Synthetic waxes, higher fatty acids such as zinc stearate and metal salts thereof or mold release agents such as paraffin; various additives such as antioxidants may be appropriately blended.
- a corrosion inhibitor such as hydrotalcite and zirconium hydroxide
- an inorganic ion exchanger such as bismuth oxide hydrate
- ⁇ -glycidoxy Coupling agents such as propyltrimethoxysilane, 3-mercaptopropyl
- the epoxy resin composition for semiconductor encapsulation used in the semiconductor device of the present invention can be prepared by mixing the above-described components at 15 ° C. to 28 ° C. using a mixer or the like, and then using a roll.
- a kneaded or kneaded machine such as a kneader, melt kneaded, cooled and pulverized may be used.
- the cured product of the epoxy resin composition for semiconductor encapsulation of the present invention can be obtained by molding and curing the above epoxy resin composition by a conventional molding method such as transfer molding, compression molding, injection molding or the like.
- the cured product of the epoxy resin composition molded and cured by a molding method such as transfer mold is completely cured at a temperature of about 80 ° C. to 200 ° C. for 10 minutes to 10 hours as necessary. It can also be obtained.
- the epoxy resin composition for semiconductor encapsulation of the present invention has a small amount of total chlorine and hydrolyzable chlorine contained in the epoxy resin (A), even when a copper wire is used as the metal wire, Corrosion hardly occurs at the joint with the electrode pad, and a highly reliable semiconductor device can be manufactured at low cost.
- the semiconductor device of the present invention is A semiconductor element mounted on a lead frame or circuit board having a die pad portion; Curing of the epoxy resin composition for sealing a semiconductor according to the present invention, wherein the metal wire for electrically bonding the electrical joint provided on the lead frame or the circuit board and the electrode pad provided on the semiconductor element It is characterized by being sealed with an object.
- Examples of the metal wire that is used in the semiconductor device of the present invention to electrically join an electrical joint provided on a lead frame or a circuit board and an electrode pad provided on a semiconductor element include, for example, a gold wire and a copper wire And aluminum wire.
- the semiconductor device of the present invention to which the epoxy resin composition for semiconductor encapsulation of the present invention is applied even when a low-cost copper wire is applied, corrosion at the junction with the electrode pad on the semiconductor element In addition to being able to provide a highly reliable semiconductor device, electrical characteristics of the semiconductor device such as reduction in electrical resistance can be improved.
- the semiconductor device of the present invention shown in FIG. 1 includes a lead frame 3 having a die pad portion 3a, a semiconductor element 1 mounted on the die pad portion 3a, and the lead frame 3 and the semiconductor element 1 electrically connected. And a sealing resin 5 that is made of a cured product of the above-described epoxy resin composition for semiconductor sealing and seals the semiconductor element 1 and the metal wire 4.
- the semiconductor element 1 is not particularly limited, and examples thereof include an integrated circuit, a large-scale integrated circuit, a solid-state imaging element, a semiconductor element using SiC, a power semiconductor such as a power transistor, an in-vehicle electronic component, and the like. It is done.
- the lead frame 3 used in the present invention is not particularly limited, and a circuit board may be used instead of the lead frame 3.
- a circuit board may be used instead of the lead frame 3.
- DIP Dual Inline Package
- PLCC Plastic Leaded Chip Carrier
- QFP Quad Flat Package
- LQFP Low Profile Quad Flat Package
- SOJ Small Outline ⁇ J lead package
- TSOP thin small outline package
- TQFP tape carrier package
- BGA ball grid array
- CSP Chip size ⁇ Package
- QFN Quad Flat Non-Leaded Package
- SON Small Outline Non-Leaded Package
- Leadframe BGA LF-BGA
- Mold Array Package It can be used a lead frame or a circuit board used in the conventional semiconductor device, such as a BGA (MAP-BGA) of Jitaipu.
- the semiconductor element 1 may be a stack of a plurality of semiconductor elements.
- the first-stage semiconductor element is bonded to the die pad portion 3a via a die bond material cured body 2 such as a film adhesive or a thermosetting adhesive.
- the semiconductor elements in the second and subsequent stages can be sequentially laminated with an insulating film adhesive.
- electrode pads 6 are formed on appropriate layers such as the uppermost layer.
- the electrode pad 6 is mainly composed of aluminum. Although it does not specifically limit as the purity of the aluminum used for the electrode pad 6, 99.5 mass% or more is preferable.
- the electrode pad 6 is formed by forming a general titanium barrier layer on the surface of the lower copper circuit terminal, and applying a general method for forming an electrode pad of a semiconductor element such as vapor deposition, sputtering, and electroless plating of aluminum. Can be produced.
- the metal wire 4 is used to electrically connect an electrical joint provided on the lead frame 3 and an electrode pad provided on the semiconductor element 1 mounted on the die pad portion 3 a of the lead frame 3. .
- An oxide film is naturally or unavoidably formed on the surface of the metal wire 4 depending on the type of the metal wire.
- the metal wire 4 includes those having an oxide film formed on the surface of the wire in this way.
- the wire diameter of the metal wire is 30 ⁇ m or less, more preferably 25 ⁇ m or less, and preferably 15 ⁇ m or more. If it is this range, the ball
- a copper wire As a metal wire, it is preferable that it is 99.9 mass% or more of copper purity, and it is more preferable that it is 99.99 mass% or more.
- various elements dopants
- the ball side shape at the tip of the copper wire at the time of bonding can be stabilized.
- the wire When the ball portion is hardened at the time of bonding, damage may be caused to the electrode pad 6 side of the semiconductor element 1, which may cause problems such as a decrease in moisture resistance reliability due to insufficient bonding, a decrease in high-temperature storage characteristics, and an increase in electric resistance value. .
- the copper wire has a copper purity of 99.9% by mass or more, the ball portion has sufficient flexibility, and there is no fear of damaging the electrode pad side during bonding.
- the copper wire that can be used in the semiconductor device of the present invention is further obtained by doping 0.001% by mass to 0.003% by mass of Ba, Ca, Sr, Be, Al, or rare earth metal into copper as the core wire. Ball shape and joint strength are improved.
- the coating layer comprised with the metal material containing palladium on the surface.
- tip is stabilized, and the connection reliability of a junction part can be improved.
- the effect which prevents the oxidation deterioration of copper which is a core wire is also acquired, and the high temperature storage characteristic of a junction part can be improved.
- the thickness of the coating layer made of a metal material containing palladium in the copper wire is preferably 0.001 ⁇ m to 0.02 ⁇ m, and more preferably 0.005 ⁇ m to 0.015 ⁇ m.
- Copper wire is obtained by casting a copper alloy in a melting furnace, rolling and rolling the ingot, further drawing with a die, heating while continuously sweeping the wire, and then performing heat treatment Can do.
- the coating layer comprised from the metal material containing palladium in the copper wire which can be used with the semiconductor device of this invention prepares the wire of the target wire diameter previously, and this is made into the electrolytic solution or electroless containing palladium
- the coating layer can be formed by dipping in a solution and continuously sweeping and plating. In this case, the thickness of the coating can be adjusted by the sweep rate.
- prepare a wire thicker than the target wire diameter immerse it in an electrolytic solution or electroless solution, continuously sweep it to form a coating layer, and then draw the wire until it reaches a predetermined diameter Can also be adopted.
- the electrical joint (lead part) 3b of the lead frame 3 and the electrode pad 6 provided on the semiconductor element 1 may be joined by a reverse bond of a wire.
- a ball formed at the tip of the metal wire 4 is first bonded to the electrode pad 6 of the semiconductor element 1, and the metal wire 4 is cut to form a bump for stitch bonding.
- a ball formed at the tip of the wire is bonded to the metal-plated lead portion 3 b of the lead frame 3, and stitch-bonded to the bump of the semiconductor element 1.
- the height of the wire on the semiconductor element 1 can be made lower than that in the positive bonding, so that the bonding height of the semiconductor element 1 can be reduced.
- the semiconductor device of the present invention seals an electronic component such as a semiconductor element using an epoxy resin composition for semiconductor encapsulation, and is cured and molded by a conventional molding method such as a transfer mold, a compression mold, or an injection mold. can get.
- a semiconductor device sealed by a molding method such as a transfer mold is completely cured at a temperature of about 80 ° C. to 200 ° C. for 10 minutes to 10 hours and then mounted on an electronic device or the like. Is done.
- Sealing resin 5 is a cured product of the epoxy resin composition for semiconductor sealing of the present invention described above.
- the semiconductor device according to the present invention is provided in the semiconductor element mounted on the lead frame or the circuit board having the die pad part, the electrical junction provided in the lead frame or the circuit board, and the semiconductor element.
- a metal wire for electrically joining the electrode pad is sealed with a cured product of the epoxy resin composition for semiconductor sealing of the present invention, and an epoxy for semiconductor sealing Since the epoxy resin (A) used in the resin composition has a main peak area of 90% or more with respect to the total area of all peaks in the measurement by the gel permeation chromatographic area method, the copper wire is low in cost. Even when applied, corrosion at the junction with the electrode pad on the semiconductor element can be reduced, resulting in an increase in electrical resistance at the junction or disconnection at the junction. It can be achieved Rinikui highly reliable semiconductor device.
- the copper wire When a copper wire is used as the metal wire, the copper wire is useful for reducing the cost of the semiconductor device because it is inexpensive. However, when the semiconductor element 1 connected to the copper wire is encapsulated with a conventional epoxy resin composition for encapsulating a semiconductor, the moisture resistance reliability may be lowered.
- the mechanism of corrosion at the joint between the copper wire and the aluminum electrode pad 6 of the semiconductor element 1 is considered as follows.
- a copper aluminum alloy is formed at the bonding interface between the copper wire and the aluminum electrode pad 6 of the semiconductor element 1. Since copper aluminum alloy forms a galvanic pair, it has high electrochemical activity and low corrosion resistance. Under high temperature and high humidity, chlorine ions are generated by hydrolysis from a cured product of the epoxy resin composition for semiconductor encapsulation constituting the sealing resin 5. This chlorine ion corrodes the copper aluminum alloy layer having low corrosion resistance, resulting in an increase in electrical resistance and disconnection at the joint.
- the epoxy resin (A) having a low chlorine content the amount of corrosive chlorine ions generated from the sealing resin 5 is reduced when the semiconductor device is treated at high temperature and high humidity. By doing so, corrosion of the joint between the copper wire and the aluminum electrode pad 6 of the semiconductor element 1 can be prevented. Thereby, even when a copper wire is applied as the metal wire, the semiconductor device of the present invention can be excellent in moisture resistance reliability.
- a semiconductor device according to the present invention is HAST-processed (130 ° C. and 85% RH 20 V)
- a semiconductor device in which the value of the electrical resistance value between wirings is increased by 20% relative to the initial value is determined to be defective. It is desirable that no defects occur even after time processing.
- a semiconductor device is required to have a resistance of 96 hours by HAST processing (130 ° C., 85% RH 20 V). Therefore, sufficient reliability can be ensured if no defect occurs over 192 hours in the HAST process (130 ° C., 85% RH 20 V).
- the epoxy resin (A), the curing agent (B), and the inorganic filler (C) are contained, and the epoxy resin (A) has a total area of the main peak in the measurement by the gel permeation chromatograph area method.
- the epoxy resin composition for encapsulating a semiconductor of the present invention that is 90% or more with respect to the total area of the peak, it is possible to realize the semiconductor device of the present invention that is resistant to disconnection and has high moisture resistance reliability.
- Curing agent A Phenol aralkyl resin, manufactured by Mitsui Chemicals, Inc., XLC-2L, hydroxyl equivalent 175, melt viscosity of 360 mPa ⁇ s at 150 ° C.
- Curing agent B phenol novolak resin, manufactured by Sumitomo Bakelite Co., Ltd., PR-HF-3 softening point 80 ° C., hydroxyl group equivalent 104.
- ⁇ Filler> Fused spherical silica (average particle size 26.5 ⁇ m, particles of 105 ⁇ m or more, 1% by weight or less, “FB-820” manufactured by Denki Kagaku Kogyo Co., Ltd.)
- Curing accelerator 1,4-benzoquinone adduct of triphenylphosphine (TPP, “PP360” manufactured by Kay Kasei Co., Ltd.)
- Coupling agent ⁇ -glycidoxypropyltrimethoxysilane
- carbon black was used as a colorant and carnauba wax was used as a mold release agent.
- Example 1 Epoxy resin B (6.55 parts by mass), curing agent A (6.20 parts by mass), fused spherical silica (86.00 parts by mass) as a filler, and a curing accelerator (0.20 parts by mass) , Coupling agent (0.25 parts by mass), carbon black (0.30 parts by mass) as a colorant, and carnauba wax (0.50 parts by mass) as a release agent, using a mixer. The mixture was mixed at a temperature of 70 ° C. and then roll kneaded at 70 ° C. to 100 ° C. After cooling, it was pulverized to obtain an epoxy resin composition.
- Examples 2 to 4 Comparative Examples 1 and 2 According to the composition of the epoxy resin composition for semiconductor encapsulation described in Table 1, an epoxy resin composition for semiconductor encapsulation was obtained in the same manner as in Example 1. All the formulations shown in Table 1 are parts by mass.
- TEG TEST ELEMENT GROUP
- chip 3.5 mm x 3.5 mm
- aluminum electrode pads is a 352-pin BGA (substrate thickness is 0.56 mm, bismaleimide / triazine resin / glass cloth substrate, package size is 30 mm x 30mm, 1.17mm thick) using a copper wire 4N (copper purity 99.99 mass%) so that the aluminum electrode pad of the TEG chip and the electrode pad of the substrate are connected in a daisy chain. Then, wire bonding was performed at a wire pitch of 80 ⁇ m.
- Examples 1 to 4 or Comparative Examples 1 to 2 were set under the conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 2 minutes.
- a 352-pin BGA package was produced by sealing with any one of the epoxy resin compositions for semiconductor encapsulation. This package was post-cured at 175 ° C. for 4 hours to obtain a semiconductor device.
- HAST Highly Accelerated Temperature and Humidity Stress Test
- the epoxy resin composition for semiconductor encapsulation of the present invention is provided in a semiconductor element mounted on a lead frame or a circuit board having a die pad portion, and an electrical junction provided in the lead frame or circuit board and the semiconductor element.
- copper wire is used as the metal wire to electrically bond to the electrode pad, it is possible to suppress the corrosion under high temperature and high humidity in the bonded structure of the electrode pad and copper wire on the semiconductor element. It can be suitably used to manufacture a low-cost semiconductor device with improved resistance.
- SYMBOLS 1 Semiconductor element 2 Die-bonding material hardening body 3 Lead frame 3a Die pad part 3b Electrical junction (lead part) of lead frame 4 Metal wire (copper wire) 5 Sealing resin 6 Electrode pad
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Abstract
Description
本願は、2010年11月24日に日本に出願された特願2010-260913号に基づき優先権を主張し、その内容をここに援用する。
一方、半導体装置に対するコストダウンの要求も激しく、従来の金線接合ではコストが高いため、近年、金線に代わる安価なボンディングワイヤとして、銅ワイヤが提案されている。
本発明者の知見によれば、耐湿信頼性が低い半導体装置では、半導体素子上の電極パッドと銅ワイヤとの接合部における腐食によって、接合部の電気抵抗の上昇又は接合部の断線が発生していた。したがって、このような接合部の電気抵抗の上昇又は接合部の断線を防止できれば、半導体装置の耐湿信頼性を向上できることが期待された。
ダイパッド部を有するリードフレーム又は回路基板上に搭載された半導体素子と、
前記リードフレーム又は回路基板に設けられた電気的接合部と前記半導体素子に設けられた電極パッドとを電気的に接合する金属ワイヤと、
を封止して半導体装置を製造するのに用いられる半導体封止用エポキシ樹脂組成物であって、前記半導体封止用エポキシ樹脂組成物は、エポキシ樹脂(A)、硬化剤(B)、無機充填材(C)を含有し、
前記エポキシ樹脂(A)が、ゲルパーミエーションクロマトグラフの面積法による測定における主ピークの面積が全ピークの合計面積に対して90%以上であることを特徴とする半導体封止用エポキシ樹脂組成物、
が提供される。
前記エポキシ樹脂(A)が、ゲルパーミエーションクロマトグラフの面積法による測定における主ピークの面積が全ピークの合計面積に対して92%以上である前記[1]項に記載の半導体封止用エポキシ樹脂組成物、
が提供される。
前記エポキシ樹脂(A)が、含有される全塩素量が300ppm以下であり、加水分解性塩素量が150ppm以下である前記[1]項または[2]項に記載の半導体封止用エポキシ樹脂組成物、
が提供される。
前記エポキシ樹脂(A)が、含有される全塩素量が200ppm以下であり、加水分解性塩素量が100ppm以下である前記[1]項または[2]項のいずれか1項に記載の半導体封止用エポキシ樹脂組成物、
が提供される。
前記エポキシ樹脂(A)が下記一般式(1)で表されるエポキシ樹脂を含むものである、前記[1]項ないし[4]項のいずれか1項に記載の半導体封止用エポキシ樹脂組成物、
が提供される。
前記エポキシ樹脂(A)の配合割合が、前記半導体封止用エポキシ樹脂組成物全体に対して3質量%以上20質量%以下である、前記[1]項ないし[5]項のいずれか1項に記載の半導体封止用エポキシ樹脂組成物、
が提供される。
前記金属ワイヤが、銅ワイヤである、前記[1]項ないし[6]項のいずれか1項に記載の半導体封止用エポキシ樹脂組成物、
が提供される。
前記銅ワイヤの銅に対して0.1質量%以下のドーパントが添加されており、前記銅ワイヤの銅純度が99.9質量%以上である前記[7]項に記載の半導体封止用エポキシ樹脂組成物、
が提供される。
ダイパッド部を有するリードフレーム又は回路基板上に搭載された半導体素子と、
前記リードフレーム又は回路基板に設けられた電気的接合部と前記半導体素子に設けられた電極パッドとを電気的に接合する金属ワイヤと、
が、前記[1]項ないし[8]項のいずれか1項に記載の半導体封止用エポキシ樹脂組成物の硬化物により封止されていることを特徴とする半導体装置、
が提供される。
前記金属ワイヤが、銅ワイヤである、前記[9]項に記載の半導体装置、
が提供される。
ダイパッド部を有するリードフレーム又は回路基板上に搭載された半導体素子と、
前記リードフレーム又は回路基板に設けられた電気的接合部と前記半導体素子に設けられた電極パッドとを電気的に接合する金属ワイヤと、
を封止して半導体装置を製造するのに用いられる半導体封止用エポキシ樹脂組成物であって、前記半導体封止用エポキシ樹脂組成物は、エポキシ樹脂(A)、硬化剤(B)、無機充填材(C)を含有し、
前記エポキシ樹脂(A)が、ゲルパーミエーションクロマトグラフの面積法による測定における主ピークの面積が全ピークの合計面積に対して90%以上であることを特徴とする。
エポキシ樹脂(A)は、1分子内にエポキシ基を2個以上有するモノマー、オリゴマー、ポリマー全般であり、その分子量、分子構造は特に限定されない。エポキシ樹脂(A)としては、例えば、ビフェニル型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、テトラメチルビスフェノールF型エポキシ樹脂などのビスフェノール型エポキシ樹脂、スチルベン型エポキシ樹脂;フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂;トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂等の多官能エポキシ樹脂;フェニレン骨格を有するフェノールアラルキル型エポキシ樹脂、フェニレン骨格を有するナフトールアラルキル型エポキシ樹脂、ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂等のアラルキル型エポキシ樹脂;ジヒドロアントラセンジオール型エポキシ樹脂;ジヒドロキシナフタレンの2量体をグリシジルエーテル化して得られるエポキシ樹脂等のナフトール型エポキシ樹脂;トリグリシジルイソシアヌレート、モノアリルジグリシジルイソシアヌレート等のトリアジン核含有エポキシ樹脂;ジシクロペンタジエン変性フェノール型エポキシ樹脂等の有橋環状炭化水素化合物変性フェノール型エポキシ樹脂等が挙げられ、これらは1種類を単独で用いても2種類以上を併用してもよい。
これらの中でも、ビフェニル型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、テトラメチルビスフェノールF型エポキシ樹脂、スチルベン型エポキシ樹脂など、合成法の選択や精製によって高い結晶性を発現する性質を有するエポキシ樹脂がより好ましい。
ここで、エポキシ樹脂(A)のゲルパーミエーションクロマトグラフの面積法による測定における主ピークとは、ゲルパーミエーションクロマトグラフの各ピーク中で、最大面積を有するピークのことであり、エポキシ樹脂の純度の指標とすることができるものである。
そして、上記主ピークの面積が全ピークの合計面積に対して上記範囲内であるエポキシ樹脂(A)は塩素を含有する副生成物が少ないことから、腐食性不純物の少ないエポキシ樹脂組成物を得ることができる。
反応終了後、過剰のエピクロルヒドリンを留去し、残留物をトルエン、メチルイソブチルケトン等の溶剤に溶解し、濾過し、水洗して無機塩を除去し、次いで溶剤を留去することにより、エポキシ樹脂を得ることができる。
また、公知の方法で合成、または市販されるエポキシ樹脂にカラムクロマトグラフィー分別、分子蒸留、再結晶などの公知の精製手法を適宜組み合わせることによって、本発明で規定する特定のエポキシ樹脂を調製してもよい。
あるいは、このように調製された市販品のエポキシ樹脂を用いることもできる。市販品としては例えば、三菱化学(株)製「YX4000UH」、三菱化学(株)製「YL7684」などを挙げることができる。
GPC装置は、ポンプ、インジェクター、ガードカラム、カラムおよび検出器から構成され、溶媒にはテトラヒドロフラン(THF)を用いる。ポンプの流速は0.5ml/分として測定を行う。これよりも高い流速では目的の分子量の検出精度が低くなるため好ましくない。前記の流速で精度よく測定を行うためには流量精度の良いポンプを使用することが必要であり、流量精度は0.10%以下が好ましい。ガードカラムには市販のガードカラム(例えば、東ソー(株)製TSK GUARDCOLUMN HHR-L:径6.0mm、管長40mm)、カラムには市販のポリスチレンジェルカラム(東ソー(株)製TSK-GEL GMHHR-L:径7.8mm、管長30mm)を複数本直列接続させる。検出器には示差屈折率計(RI検出器。例えば、WATERS社製示差屈折率(RI)検出器W2414)を用いる。測定に先立ち、ガードカラム、カラムおよび検出器内部は40℃に安定させておく。試料には、濃度3~4mg/mlに調整したエポキシ樹脂(A)のTHF溶液を用意し、これを約50~150μlインジェクターにより注入して測定を行う。
さらに好ましくは、全塩素量が200ppm以下であり、加水分解性塩素量が100ppm以下である。
特に好ましくは、全塩素量が50ppm以下であり、加水分解性塩素量が30ppm以下である。
このようなエポキシ樹脂(A)を用いることにより、耐湿信頼性の高い半導体装置を得ることができる。
塩素イオンは金属の腐食性を有し、半導体素子の電極パッドなどアルミ配線部分を腐食する。半導体素子の電気接合に金属ワイヤとして銅ワイヤを使用した場合、接合部分にアルミニウムと銅の合金が生成する。この合金はガルバニック対となるため、塩素による腐食を特に受けやすく、さらには耐湿信頼性が低下する。半導体装置の耐湿信頼性向上には半導体封止用エポキシ樹脂組成物中の塩素量低減が必要である。
一般式(1)で表されるエポキシ樹脂は結晶性エポキシ樹脂であることから、再結晶による精製を行うことにより、ゲルパーミエーションクロマトグラフの面積法による測定で主ピークの面積が全ピークの合計面積に対して90%以上であるエポキシ樹脂を比較的容易に得ることができる。
特に、一般式(1)で表されるエポキシ樹脂を半導体封止用として用いるために、nは0~3が望ましく、0~2がより望ましく、0が最も望ましい。
フェノール樹脂系硬化剤は、一分子内にフェノール性水酸基を2個以上有するモノマー、オリゴマー、ポリマー全般であり、その分子量、分子構造は特に限定されない。例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールノボラック等のノボラック型樹脂;トリフェノールメタン型フェノール樹脂等の多官能型フェノール樹脂;テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂等の変性フェノール樹脂;フェニレン骨格及び/又はビフェニレン骨格を有するフェノールアラルキル樹脂、フェニレン及び/又はビフェニレン骨格を有するナフトールアラルキル樹脂等のアラルキル型樹脂;ビスフェノールA、ビスフェノールF等のビスフェノール化合物等が挙げられ、これらは1種類を単独で用いても2種類以上を併用してもよい。
硬化促進剤の具体例としては、有機ホスフィン、テトラ置換ホスホニウム化合物、ホスホベタイン化合物、ホスフィン化合物とキノン化合物との付加物、ホスホニウム化合物とシラン化合物との付加物等のリン原子含有化合物;1,8-ジアザビシクロ(5,4,0)ウンデセン-7、ベンジルジメチルアミン、2-メチルイミダゾール等が例示されるアミジンや3級アミン、さらには前記アミジン、アミンの4級塩等の窒素原子含有化合物が挙げられ、これらのうちの1種または2種以上を組み合わせて用いることができる。これらのうち、硬化性の観点からはリン原子含有化合物が好ましく、また耐半田性と流動性の観点では、ホスホベタイン化合物、ホスフィン化合物とキノン化合物との付加物が特に好ましく、連続成形における金型の汚染が軽度である点では、テトラ置換ホスホニウム化合物、ホスホニウム化合物とシラン化合物との付加物等のリン原子含有化合物が特に好ましい。
本発明の半導体装置は、
ダイパッド部を有するリードフレーム又は回路基板上に搭載された半導体素子と、
前記リードフレーム又は回路基板に設けられた電気的接合部と前記半導体素子に設けられた電極パッドとを電気的に接合する金属ワイヤとが、上記本発明の半導体封止用エポキシ樹脂組成物の硬化物により封止されていることを特徴とするものである。
これらの中でも、本発明の半導体封止用エポキシ樹脂組成物を適用する本発明の半導体装置においては、低コストである銅ワイヤを適用した場合でも、半導体素子上の電極パッドとの接合部における腐食が発生しにくく、高い信頼性を有する半導体装置とすることができるとともに、電気抵抗の低減など半導体装置の電気特性を向上させることができる。
図1に示された本発明の半導体装置は、ダイパッド部3aを有するリードフレーム3と、ダイパッド部3aに搭載された半導体素子1と、リードフレーム3と半導体素子1とを電気的に接続している金属ワイヤ4と、上記の半導体封止用エポキシ樹脂組成物の硬化物からなり、半導体素子1と金属ワイヤ4とを封止している、封止樹脂5と、を有する。
これに対し、銅純度99.9質量%以上の銅ワイヤであれば、ボール部分は充分な柔軟性を有しているため、接合時に電極パッド側にダメージを与える恐れがない。
尚、本発明の半導体装置で用いることができる銅ワイヤは、芯線である銅にBa、Ca、Sr、Be、Al又は希土類金属を0.001質量%~0.003質量%ドープすることでさらにボール形状と接合強度が改善される。
銅ワイヤにおけるパラジウムを含む金属材料から構成された被覆層の厚みとしては、0.001μm~0.02μmであることが好ましく、0.005μm~0.015μmであることがより好ましい。上記上限値を超えると、ワイヤボンド時に芯線である銅と被覆材のパラジウムを含む金属材料とが十分に溶けずボール形状が不安定になり、接合部分の耐湿性、高温保管特性が低下する恐れがある。また、上記下限値を下回ると、芯線の銅の酸化劣化を十分に防止できず、同様に接合部分の耐湿性、高温保管特性が低下する恐れがある。
銅ワイヤと半導体素子1のアルミニウム製電極パッド6の接合界面には銅アルミニウム合金が形成される。銅アルミニウム合金はガルバニック対を形成するため、電気化学的活性が高く腐食耐性が低い。高温高湿下では、封止樹脂5を構成する半導体封止用エポキシ樹脂組成物の硬化物から加水分解により塩素イオンが発生する。この塩素イオンにより腐食耐性が低い銅アルミニウム合金層が腐食し、接合部の電気抵抗の上昇や断線が生じる。
例えば、本発明の半導体装置をHAST処理(130℃85%RH20V)したときに、配線間の電気抵抗値の値が初期値に対して20%増加した半導体装置を不良と判定する場合において、192時間処理しても不良が発生しないことが望ましい。
通常、半導体装置は、HAST処理(130℃85%RH20V)で96時間の耐性が必要とされる。このため、HAST処理(130℃85%RH20V)で192時間にわたって不良が発生しなければ、十分な信頼性を確保することができる。
エポキシ樹脂A:ビフェニル型エポキシ樹脂(上記一般式(1)において、3位,3’位及び5位,5’位のRがメチル基、2位,2’位及び6位,6’位のRが水素原子であるエポキシ樹脂、三菱化学(株)製「YX4000H」、エポキシ当量193、全塩素量400ppm、加水分解塩素量150ppm、ゲルパーミエーションクロマトグラフの面積法:主ピークの面積/全ピークの合計面積=83.7%)。
エポキシ樹脂B:ビフェニル型エポキシ樹脂(上記一般式(1)において、3位,3’位及び5位,5’位のRがメチル基、2位,2’位及び6位,6’位のRが水素原子であるエポキシ樹脂、三菱化学(株)製「YL7684」、エポキシ当量184、全塩素量158ppm、加水分解塩素量80ppm、ゲルパーミエーションクロマトグラフの面積法:主ピークの面積/全ピークの合計面積=92.4%)。
エポキシ樹脂C:ビフェニル型エポキシ樹脂(上記一般式(1)において、3位,3’位及び5位,5’位のRがメチル基、2位,2’位及び6位,6’位のRが水素原子であるエポキシ樹脂、三菱化学(株)製「YX4000UH」、エポキシ当量177、全塩素量15ppm、加水分解塩素量<10ppm、ゲルパーミエーションクロマトグラフの面積法:主ピークの面積/全ピークの合計面積=99.7%)。
硬化剤A:フェノールアラルキル樹脂、三井化学(株)製、XLC-2L、水酸基当量175、150℃の溶融粘度360mPa・s。
硬化剤B:フェノールノボラック樹脂、住友ベークライト(株)製、PR-HF-3軟化点80℃、水酸基当量104。
溶融球状シリカ(平均粒径26.5μm、105μm以上の粒子が1重量%以下、電気化学工業(株)製「FB-820」)
硬化促進剤:トリフェニルホスフィン(TPP、ケイ・アイ化成(株)製「PP360」)の1,4-ベンゾキノン付加物
カップリング剤:γ-グリシドキプロピルトリメトキシシラン
(実施例1)
エポキシ樹脂B(6.55質量部)と、硬化剤A(6.20質量部)と、充填材として溶融球状シリカ(86.00質量部)と、硬化促進剤(0.20質量部)と、カップリング剤(0.25質量部)と、着色剤としてカーボンブラック(0.30質量部)と、離型剤としてカルナバワックス(0.50質量部)とを、ミキサーを用いて15~28℃で混合し、次いで70℃~100℃でロール混練した。冷却後、粉砕してエポキシ樹脂組成物を得た。
表1に記載の半導体封止用エポキシ樹脂組成物配合に従い、実施例1と同様にして半導体封止用エポキシ樹脂組成物を得た。表1に示された配合は全て質量部である。
アルミニウム製電極パッドを備えるTEG(TEST ELEMENT GROUP)チップ(3.5mm×3.5mm)を352ピンBGA(基板は厚さ0.56mm、ビスマレイミド・トリアジン樹脂/ガラスクロス基板、パッケージサイズは30mm×30mm、厚さ1.17mm)のダイパッド部に接着し、TEGチップのアルミニウム製電極パッドと基板の電極パッドとをデイジーチェーン接続となるように銅ワイヤ4N(銅純度99.99質量%)を用いてワイヤピッチ80μmでワイヤボンディングした。これを、低圧トランスファー成形機(TOWA製「Yシリーズ」)を用いて、金型温度175℃、注入圧力6.9MPa、硬化時間2分間の条件で実施例1~4又は比較例1~2のいずれかの半導体封止用エポキシ樹脂組成物により封止成形して、352ピンBGAパッケージを作製した。このパッケージを175℃、4時間の条件で後硬化して半導体装置を得た。
(1)エポキシ樹脂組成物の物性評価
得られたエポキシ樹脂組成物の物性を以下の方法により測定した。その結果を表1に示す。
低圧トランスファー成形機(コータキ精機(株)製「KTS-15」)を用いて、EMMI-1-66に準じたスパイラルフロー測定用の金型に、金型温度175℃、注入圧力6.9MPa、硬化時間120秒間の条件で、実施例1~4、比較例1~2の半導体封止用エポキシ樹脂組成物をそれぞれ注入し、流動長(単位:cm)を測定した。60cm以下であるとパッケージ未充填などの成形不良が生じる場合がある。
175℃に加熱した熱板上で実施例1~4、比較例1~2の半導体封止用エポキシ樹脂組成物をそれぞれ溶融後、へらで練りながら硬化するまでの時間を測定した。
作製した352ピンBGA半導体装置の耐湿信頼性(HAST)を以下の方法により測定した。その結果を表1に示す。
352ピンBGAパッケージを使用し、IEC68-2-66に準拠しHAST(Highly Accelerated temperature and humidity Stress Test)試験を行った。試験条件は130℃85%RH20V印加、96時間、192時間及び1008時間処理をして回路のオープン不良有無を測定した。1パッケージあたり4端子を持ち5パッケージで計20回路を評価に用いた。単位は不良回路の個数。
HASTにおいて、1008時間処理をしても不良が発生しない場合を◎、192時間処理しても不良が発生しない場合を○と判定し、それ以外を×と判定した。
2 ダイボンド材硬化体
3 リードフレーム
3a ダイパッド部
3b リードフレームの電気的接合部(リード部)
4 金属ワイヤ(銅ワイヤ)
5 封止樹脂
6 電極パッド
Claims (10)
- ダイパッド部を有するリードフレーム又は回路基板上に搭載された半導体素子と、
前記リードフレーム又は回路基板に設けられた電気的接合部と前記半導体素子に設けられた電極パッドとを電気的に接合する金属ワイヤと、
を封止して半導体装置を製造するのに用いられる半導体封止用エポキシ樹脂組成物であって、前記半導体封止用エポキシ樹脂組成物は、エポキシ樹脂(A)、硬化剤(B)、無機充填材(C)を含有し、
前記エポキシ樹脂(A)が、ゲルパーミエーションクロマトグラフの面積法による測定における主ピークの面積が全ピークの合計面積に対して90%以上であることを特徴とする半導体封止用エポキシ樹脂組成物。 - 前記エポキシ樹脂(A)が、ゲルパーミエーションクロマトグラフの面積法による測定における主ピークの面積が全ピークの合計面積に対して92%以上である請求項1に記載の半導体封止用エポキシ樹脂組成物。
- 前記エポキシ樹脂(A)が、含有される全塩素量が300ppm以下であり、加水分解性塩素量が150ppm以下である請求項1または2に記載の半導体封止用エポキシ樹脂組成物。
- 前記エポキシ樹脂(A)が、含有される全塩素量が200ppm以下であり、加水分解性塩素量が100ppm以下である請求項1または2のいずれか1項に記載の半導体封止用エポキシ樹脂組成物。
- 前記エポキシ樹脂(A)の配合割合が、前記半導体封止用エポキシ樹脂組成物全体に対して3質量%以上20質量%以下である、請求項1ないし5のいずれか1項に記載の半導体封止用エポキシ樹脂組成物。
- 前記金属ワイヤが、銅ワイヤである、請求項1ないし6のいずれか1項に記載の半導体封止用エポキシ樹脂組成物。
- 前記銅ワイヤの銅に対して0.1質量%以下のドーパントが添加されており、前記銅ワイヤの銅純度が99.9質量%以上である請求項7に記載の半導体封止用エポキシ樹脂組成物。
- ダイパッド部を有するリードフレーム又は回路基板上に搭載された半導体素子と、
前記リードフレーム又は回路基板に設けられた電気的接合部と前記半導体素子に設けられた電極パッドとを電気的に接合する金属ワイヤと、
が、請求項1ないし8のいずれか1項に記載の半導体封止用エポキシ樹脂組成物の硬化物により封止されていることを特徴とする半導体装置。 - 前記金属ワイヤが、銅ワイヤである、請求項9に記載の半導体装置。
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- 2011-11-21 SG SG2013039623A patent/SG190864A1/en unknown
- 2011-11-21 CN CN2011800561231A patent/CN103221480A/zh active Pending
- 2011-11-21 JP JP2012545740A patent/JPWO2012070529A1/ja active Pending
- 2011-11-21 TW TW100142521A patent/TW201221536A/zh unknown
- 2011-11-21 KR KR1020137013621A patent/KR20130141557A/ko not_active Application Discontinuation
- 2011-11-21 US US13/988,534 patent/US20130256863A1/en not_active Abandoned
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WO2015005275A1 (ja) * | 2013-07-11 | 2015-01-15 | 住友ベークライト株式会社 | 半導体装置の製造方法および半導体装置 |
JPWO2015005275A1 (ja) * | 2013-07-11 | 2017-03-02 | 住友ベークライト株式会社 | 半導体装置の製造方法および半導体装置 |
JP2015098521A (ja) * | 2013-11-19 | 2015-05-28 | 住友ベークライト株式会社 | 封止用樹脂組成物及び電子部品装置 |
JP2018115339A (ja) * | 2018-04-12 | 2018-07-26 | 住友ベークライト株式会社 | 封止用樹脂組成物及び電子部品装置 |
Also Published As
Publication number | Publication date |
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KR20130141557A (ko) | 2013-12-26 |
CN103221480A (zh) | 2013-07-24 |
JPWO2012070529A1 (ja) | 2014-05-19 |
US20130256863A1 (en) | 2013-10-03 |
TW201221536A (en) | 2012-06-01 |
SG190864A1 (en) | 2013-07-31 |
US20130243715A1 (en) | 2013-09-19 |
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