JPS6333412A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

PURPOSE:To provide the titled resin composition containing a polyfunctional epoxy compound and a specific phthalocyanine tetramine compound, giving a cured material having excellent heat-resistance, moisture-resistance and corrosion resistance and suitable for semiconductor device. CONSTITUTION:The objective composition contains (A) a polyfunctional epoxy compound (e.g. bisphenol A diglycidyl ether) and (B) a 4,4',4'',4'''-phthalocyanine tetramine compound of formula (M is none, Cu, Pb, Fe, Ni or Co) (e.g. 4,4',4'',4'''-phthalocyanine tetramine copper). A semiconductor device is produced by sealing or covering at least a part of a semiconductor element with the composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides an epoxy resin composition that can provide a cured product with excellent heat resistance, moisture resistance, and corrosion resistance, and an epoxy resin composition that can provide a cured product with excellent heat resistance, moisture resistance, and corrosion resistance, and The present invention relates to coated semiconductor devices.

[Conventional technology]

Memory LSIs are trending toward higher density and higher integration, and there is an inevitable demand for improved reliability under high temperature conditions and high temperature and high humidity conditions. High temperature and high humidity conditions, e.g. 65℃, 9
If a semiconductor device is installed in an atmosphere such as 5% relative humidity, 85°C and 85% relative humidity, or 121°C and two-atmosphere supersaturated steam, the AQ wiring on the device will corrode and break. occurs, and this is a major factor in reducing reliability.

The major causes of corrosion and breakage of AQ wiring are moisture that has entered the inside of the package and ionic impurities contained in the resin composition, especially chlorine ions. However, for resin-sealed products, it is difficult to remove the pressure of moisture that permeates and absorbs moisture through the resin bulk and reaches the element surface.

Therefore, as a countermeasure to this problem, a method of removing ionic impurities (particularly chlorine ions) by purifying each material of the resin composition has been studied. However, the current situation is that even these methods cannot provide fundamental countermeasures in the case of materials containing hydrolyzable ionic compounds. (Unexamined Japanese Patent Publication No. 60-202117) [Problems to be Solved by the Invention] The above-mentioned conventional technology lacks consideration for the corrosion resistance of the resin composition against AQ, and improvements have been made from this point of view. I cannot say that.

An object of the present invention is to provide an epoxy resin composition that can provide a cured product with excellent heat resistance, moisture resistance, and corrosion resistance, and a semiconductor device sealed and coated with the resin composition.

[Means for solving problems]

The above object is achieved by employing the following technology. The gist is as follows: 1. At least a polyfunctional epoxy compound [A] and the general formula (1) % formula % [wherein M is none, Cu, Pb, Fe, Ni.

Either Co. ] 4゜47 , 4
#, 4L//-phthalocyaninetetramine compound.

2. At least a polyfunctional epoxy compound (A) and the general formula (1) [wherein M is no g Cu y P b + Fe +
Either N i *CO. ] A semiconductor device characterized in that at least a part of a semiconductor element is sealed and covered with an epoxy resin composition containing a 4゜4',4'',4-phthalocyaninetetramine-based compound represented by .

In the present invention, the polyfunctional epoxy compound (A) is, for example, diglycidyl ether of bisphenol A, butadiene dieboxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexanecarboxylate, vinylcyclohexane. Dioxide, 4,4'
-di(1,2-epoxyethyl)diphenyl ether,
4゜4'-(1,2-epoxyethyl)biphenyl,
2.2-bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(3,4-epoxycyclopentyl)ether, 2-( 3,4-epoxy)cyclohexane-5゜5-spiro(3,4-epoxy)-cyclohexane-m-dioxane, bis-(3,4-epoxy-6-methylcyclohexyl)adipate, NIN
Trifunctional epoxy compounds such as '-m-phenylenebis(4,5-epoxy1゜2-cyclohexane) dicarboximide, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3.5-
Tri(1,2-epoxyethyl)benzene, 2.2'
, 4.4'-tetraglycidoxybenzophenone, tetraglyside, xytetraphenylethane, polyglycidyl ether of phenolformaldehyde novolak, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, etc. used.

The above epoxy compounds can be used in combination of one or more types depending on the use and purpose.

Further, in the present invention, -form (II) [wherein M is Cu, Pb, Fe, or Ni+Go].

In the present invention, the 4゜4', 4', 4''-phthalocyanine tetramine compound represented by -form CI) Hz [wherein M is Mg, Al1.Ca, Ti, V, Cr.

Mn, Fe, Go, Ni, Cu, Zn, Sr.

Zr, Pd, Ag, Cd, Sn+ Sb+ Bi.

Pb, PL, Au, or any of these metals. ] 4, 4 /, 4 #,
Examples of 4''-phthalocyaninetetramine compounds include 4,4/, 4a, 4///-phthalocyaninetetraminemagnesium, 4.4', 4'
, 4”-phthalocyaninetetramine aluminum, 4
．． 4'.

4, , 4///-phthalocyanine tetramine calcium, 4, 4', 4 N, 4 #//-phthalocyanine tetramine iron, 414', 4 #
, 4///-phthalocyanine tetramine copper etc. 41
4', 4#, 4///-Metal salts of phthalocyanine tetramine, etc. 6 In the present invention, -format (1
) 4,4'.

4′,4“′-phthalocyaninetetramine compounds,
Furthermore, the following - format (n), [m)...[11
) and/or... [Summer ■] [In the formula, M is Mg, AQ, Ca, Ti, V, Cr.

Mn, Fe, Go, Ni, Cu, Zn, 5
rsZr, Pd, Ag+ Cd, Snt Sb, B
i.

It is one of Pb, Pt, and Au. ] It is also possible to use a phthalocyanine tetramine compound represented by the following.

A conventionally known curing agent may be used in combination with the epoxy resin composition of the present invention. They are written by Hiroshi Kakiuchi; Epoxy resin (
Published September 1970) pages 109-149, Lee,
Written by Nevilla; Epoxy Resins (M
c Gray-Hill Book Company
Ince New York (published in 1957) 63~
141 pages, by P.E. Brunis; Ep.
Oxy Re5ins Technology (In
tersciencePublishers New
York, 1968) pages 45 to 111, such as aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines, carboxylic acids, trimellitic acid triglyceride (Recaresin TMTA, etc.) ) carboxylic acid anhydrides,
Aliphatic and aromatic polyamide oligomers and polymers.

Examples include boron trifluoride-amine complexes, synthetic resin initial condensates such as phenol resin, melamine resin, urea resin, and urethane resin, as well as dicyandiamide, carboxylic acid hydrazide, and polyaminomaleimide.

One or more types of these curing agents can be used depending on the use and purpose.

In particular, phenol novolac resin is suitable as a curing agent component of a semiconductor encapsulation material, which is the main objective of the present invention, from the viewpoint of the adhesiveness of the cured resin to the metal insert and the workability during molding.

For the resin composition, a known catalyst known to be effective in accelerating the curing reaction between an epoxy compound and a novolac type phenol resin can be used.

This catalyst includes, for example, triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine,
Tertiary amines such as tetramethylhexanediamine, triethylenediamine and dimethylaniline, oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol, and amines such as tris(dimethylaminomethyl)phenol and methylmorpholine can be applied. can.

Or, for the same purpose, as a catalyst, for example, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, pendylmethylpalmitylammonium chloride, allyldodecyltrimethyl Quaternary ammonium salts such as ammonium bromide, benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride and benzyldimethyltetradecylammonium acetate can be applied, as well as 2-undecylimidazole, 2-methylimidazole, 2- Ethylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole.

Imidazole compounds such as 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole and 1-azine-2-undecylimidazole , or triphenylphosphine tetraphenylborate, toluethylamine tetraphenylborate, N-methylmorpholine tetraphenylborate, pyridine tetraphenylborate 2-ethyl-4-methylimidazole tetraphenylborate and 2-ethyl-1,4-dimethylimidazole Tetraphenylboron salts such as tetraphenylborate are useful.

Two or more of these catalysts can be used in combination, and the amount thereof is based on 100% of the polyfunctional epoxy compound (A).
It may be used in a weight ratio of 0.01 to 20.

The epoxy resin composition of the present invention may also include, for example, calcium carbonate, silica, alumina, titania, aluminum hydroxide, aluminum silicate, zirconium silicate, zircon, glass, talc, Mica, graphite.

Powders and short fibrous fillers such as aluminum, copper and iron, mold release agents such as fatty acids and waxes, coupling agents such as epoxy silane, vinyl silane, borane compounds and alkyl titanate compounds, and furthermore, antimony and phosphorus. Flame retardants such as compounds and halogen-containing compounds can be added.

<Examples 1 to 5. Comparative Example> As a polyfunctional epoxy compound, a tris(hydroxyphenyl)methane-based polyfunctional epoxy compound, XD-9
053 (epoxy equivalent, 225° manufactured by Dow Chemical Company)
100 parts by weight.

As curing agent: 4.4',4',4''-phthalocyaninetetramine, 4.4',4',4''-phthalocyaninetetramine calcium, 4.4'.

4',4''-phthalocyaninetetramine aluminum,
4.4',4',4-Phthalocyanine iron.

4. Predetermined blending amounts of five types of phthalocyanine tetramine compounds for 4', 4', 4-phthalocyanine steel and novolak type phenolic resin as shown in Table 1.

As a curing accelerator, 2 parts by weight of triphenylphosphine;
Epoxysilane KBM303 as a coupling agent
(manufactured by Shin-Etsu Chemical Co., Ltd.) double-layered part, 4 parts by weight of addition-type imide coated red phosphorus as a flame retardant, 1 part by weight of calcium stearate and Hoechst Wax E (manufactured by Hoechst Japan Co., Ltd.) as a mold release agent, parts by weight, As a filler, 75% of fused silica glass powder was added, and as a colorant, carbon black (manufactured by Cabot Corporation) was added and blended.

Next, the mixture was kneaded for a while using two 8-inch diameter rolls at 70 to 80°C, and then coarsely pulverized to obtain a resin composition for semiconductor encapsulation.

Next, the resin composition is applied to the IM bit D-RAM memory L.
180℃, 70kgf・cd, 1.5 using a transfer molding machine equipped with a mold filled with SI elements.
Molded under minute conditions.

The temperature of the obtained resin-sealed semiconductor device was 121°C.

After being placed in supersaturated steam (PCT) at 2 atm, the LSI was taken out at predetermined intervals to check whether the LSI's electrical operation was normal.

4.4',4''L,4-phthalocyaninetetramine compound and dialdehydes such as terephthalaldehyde and hydroxyterephthalaldehyde, or hydroxyaldehyde and dihydroxydialdehydes are reacted to form the following formula [wherein, XI * Xz is H, O
Any of H may be the same or different,
] A phthalocyanine Schiff-based polymer and/or a phthalocyanine hydroxy-Schiff-based polymer was obtained. This polymer has a conductivity of 1 to 1 without dopants.
Indicates 10-3Ω・pieces. It is effective for forming LSI circuits. Disconnection failures caused by corrosion, which occur in conventional AQ wiring, can be eliminated.

Claims (1)

[Claims] 1. At least a polyfunctional epoxy compound [A] and a general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] [In the formula, M is none, Cu, Pb, Fe, Ni, or Co. ] 4, 4', 4'', 4'''-
An epoxy resin composition comprising a phthalocyanine tetramine compound. 2. At least a polyfunctional epoxy compound [A] and a general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・〔I
] [In the formula, M is none, Cu, Pb, Fe, Ni, or Co. ] 4, 4', 4'', 4'''-
1. A semiconductor device characterized in that at least a part of a semiconductor element is sealed and coated with an epoxy resin composition containing a phthalocyanine tetramine compound.