JPS6279654A - Semiconductor device - Google Patents

Abstract

PURPOSE:To protect a wiring on a semiconductor element from corrosion-caused disconnection and thereby to improve reliability by a method wherein a coating/ sealing layer is formed by using a treatment containing a compound based on zircoaluminate. CONSTITUTION:At least a part of a semiconductor device is provided with a coating/sealing layer formed by using a treatment containing a compound based on zircoaluminate. The compound based on zircoaluminate is an ether or ester compound containing zirconium and aluminum, equipped with such terminal groups as an amino group, carboxyl group, fatty acid group, or methacryloyloxy group. The conditions whereunder a coating resin composite is processed are not to be specified. Generally, a coating capable of desired performance may be produced after heat treatment at 100-300 deg.C for about 30sec-1hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a sealed semiconductor device having excellent moisture resistance and reliability, which is coated with a material for a semiconductor element and having excellent adhesion and adhesion.

[Background of the invention]

In resin-sealed semiconductor devices, higher density, higher reliability, and multifunctionality are being sought.

However, with the increasing density of semiconductors, soft errors (device damage due to alpha ray energy emitted from U and Th contained in the package material), corrosion and disconnection of At wiring under high temperature and high humidity conditions, and migration problems are occurring. Problems related to the interface between the element and the resin encapsulant, such as problems with dimensional accuracy and dimensional accuracy, have been attracting attention.

Under these circumstances, the quality of the peeling state at the interface between the element and the resin (substrate material, sealing material, etc.) has attracted attention as one of the major factors that influences the reliability of semiconductor devices, and various improvements have been made. Measures have been proposed.

For example, silane-based on the element, At-chelate yarn, A4-
These include improving the adhesion between the element and the resin by treatment with a coupling agent such as alkoxide thread, reducing the stress of the covering material or sealing material, and reducing the moisture absorption rate and moisture permeability rate. However, all of the above measures have their advantages and disadvantages, and there are currently no fundamental countermeasures in sight.

[Purpose of the invention]

The present invention was made in view of the above-mentioned situation, and its purpose is to prevent the occurrence of defects due to corrosion and disconnection of wiring (P, T, etc.) on semiconductor elements even if exposed to high temperature and high humidity for a long period of time. The purpose of the present invention is to provide a complete package of highly reliable sealed semiconductor devices with minimal oxidation.

[Summary of the invention]

To summarize the present invention, the present invention relates to a semiconductor device, and includes a coating and/or a sealing layer formed on at least a portion of the semiconductor device using a processing agent containing a zircoaluminate compound. It is characterized by containing.

In the present invention, the zircoaluminate compound is an ether or ester compound consisting of zirconium and aluminum, all of which have terminal groups such as amine groups, carboxyl groups, fatty acid groups, and methacryloyloxy groups.

As a specific example, the alcohol system of CAPCO MOD [0AVCOMOD], which is sold by Kusumoto F.Hiseisha, has A (amino group λ, C (carboxyl group J, C-1 (
carboxyl group>, "<mfat fI1.), M (methacryloyloxy group), M-1 (methacryloyloxy group and fatty acid'l, S (mercaptan group), and glycol type APG (amine group), 0PG (carboxyl basis)
, CPM (carboxyl group), FPM (fatty acid group, M
Examples include PG (methacryloyloxy group) and MPM (methacryloyloxy group). One or more of these can also be used in combination.

Moreover, in the non-invention, the above-mentioned zircoaluminate type 1
A mixture or reaction product of the compound 6 and an alkoxysilane compound and/or a titanate compound can be used.

Examples of alkoxysilane compounds include β-(5
,4-epoxycyclohexyl]ethyltrimethoxysilane (U, CoO A-186, etc.), γ-(glycidoxypropyl)) 1.1 Me)oxysilane (U
N-(β-aminoethyl) -γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM603, etc.), γ-mercagtobropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM805, etc.), γ-aminoglobiltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM805, etc.) IBM 905, etc.), γ-methacryloyloxyglobyltrimethoxysilane (Shin-Etsu Chemical, KBM505, etc.), γ-ureidopropyltriethoxysilane (U, 000, A-1160)
etc.) etc.

``1fC1 titanate yarn ratio compounds include tetrastearyl titanate, tetra-n-butyl titanate, tetra-stearyl titanate, tetra-2-ethylhexyl titanate, butyl titanate dimer, diisogropoxy titanium bis(acetylacetonate J, titanium Examples include octylene glycolate, butane triethanolaminate, polyhydroxy titanium stearate, polyisopropoxy titanium stearate, and one or more of the above may be used in combination.

The film-forming resin m paraboloid also contains aluminum, titanium,
Alcoholate compounds of at least 1fi1 metals selected from tin, zinc, lead and zirconium can be used as components. Examples of such alcoholate compounds include aluminum methylate, aluminum methylate, and aluminum-1-globulin.
aluminum-n-butyrate, mono-5ec-butoxyaluminum-di-1-propylate, ethylaluminum-dietherate, ethylaluminum-di-1-propylate, titanium-tetra-1-propylate, tin-tetra-1-propylate , zinc-di-1-propylate, lead-di-1-propylate, zirconium-tetra-1-propylate, etc., which can be used in one forest or two or more buildings, and some of them or It may be used as a prepolymer formed entirely by combining MWi, or it may be used after being mixed with a zircoaluminate compound and/or prepared as a copolymer.

1fcs In the present invention, at least one metal selected from aluminum, titanium, tin, zinc, lead, and zirconium and β
It is also possible to use a metal chelate compound consisting of a secondary ligand selected from -diketones and β-ketoyesters. For example, tris(2,4-pentanedionatonoaluminum, (2,4-pentanedionate 2bis(
Ethylacetoacetate dialuminum, tris(ethylacetoacetate) aluminum, bis(ethylacetoacetate) titanium, tetrakis(2,4-pentanedionato) titanium, dibutyl bis(2,4-pentanedionate) tin, Dimethylbis(ethylacetoacetatetin, bis(2,4-pentanedionate) MM
t, bis(ethyl acetoacetate) lead, tetrakis(
Examples include ethyl acetoacetate nozirconium.

In the present invention, the resin used for the coating! The 1N bottom item is
The treatment conditions are not particularly limited, but generally, by heat treatment at a temperature of about 100 to 300°C for about 30 seconds to 1 hour, a coating that exhibits the desired effect of the present invention can be formed. I can do it.

In the present invention, the zircoaluminate positive compound,
Alternatively, after coating the device with a coating mainly composed of a zircoaluminate compound, an alkoxysilane compound, and/or a titanate compound, a metal alcoholate compound, a β-diketone compound, etc., a heterocycle is added to the molecular skeleton. A protective film made of an organic polymer, a siloxane polymer, a perfluoropolymer, etc. may additionally be used. There is no problem in using such a polymer by internally adding the above-mentioned zircoaluminate compound. In this case, there is no particular restriction on the amount of the zircoaluminate compound added, and an appropriate amount may be used depending on the purpose and use, depending on the prefecture.

Examples of the organic polymer include polyimide, polybenzimidazole, polybenzoxazole, polybenzthiazole, polyoxathiazole, polyoxadiazole, polypyrazole, polyquinoxaline, polyquinazolinedione, polybenzoxazinone, and polyindolone. , polyquinazolone, polyindoxyl, etc.

The above-mentioned organic polymers also include protective coatings made of copolymers containing skeletons such as amide, ether, ester, siloxane, perfluoro, carborane, and phosphazene.

In the present invention, the semiconductor element coated with a required zircoaluminate compound or further protectively coated with an organic polymer and/or an inorganic polymer is then coated with an organic resin composition or other known material from the outside. It is preferable to further perform coating and/or sealing molding.

Usable resin compositions include, for example, epoxy resins, phenolic resins, unsaturated polyester resins, urethane resins, diallyl phthalate resins, jpolymer resins, melamine resins, addition type polyimide resins, polysulfide resins,
Examples include compositions containing polyetheretherketone resins, silicone resins, lactone-siloxane copolymers, fluorine fibers, and the like. Among these, resin compositions containing all epoxy resin components are particularly preferred.

In the present invention, examples of the polyfunctional epoxy compound used in the epoxy resin composition include diglycidyl ether of bisphenol A, 3,4-epoxycyclohexylmethyl-(5,4-epoxy)cyclohexanecarboxylate, vinylcyclohexane dioxide, 4.4'
-di(1゜2-epoxyethyl fudiphenyl ether,
4゜4'-(1,2-epoxyethyl)biphenyl, 2
゜2-bis(5,4-epoxycyclohexylunglopane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,5-epoxycyclobentyl) ether, 2- (5,4-epoxy)cyclohexane-5,5-spiro(5,4-epoxynocyclohexane-m-dioxane, bis-(5,4-epoxy-6-methylcyclohexyl adipe), N, 1J'
- bifunctional epoxy compounds such as -m-phenylenebis(4,5-epoxy-1,2-cyclohexane) dicarboximide, triglycidyl ether of (laminophenol), polyallyl glycidyl ether, 1,5.
5-tri(1,2-epoxyeternenpenzene, 2.2
: Epoxy compounds having trifunctionality or more are used, such as 4'-tetraglycidyl benzophenone, polyglycidyl ether of phenol formaldehyde novolac, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane.

One or more of the above compounds can also be used in combination. When using these epoxy compounds, a curing agent that causes a crosslinking reaction is also used. They are written by Hiroshi Kakiuchi: Eboxy Resin (September 1970, published by Shokodo) No. 10
pp. 9-149, Lee, Nevi
llJ) Author: Epoxy Resin (Epoxy Re5
ins) New York City, McGraw-Hill Book Company, Inc. (Me Gra
w-HllllBook Company Engineering nc) (19
[Published in 1957], pages 65 to 141, etc., such as aliphatic polyamines, aromatic polyamines,
and tertiary amines, carboxylic acids, carboxylic anhydrides, aliphatic and aromatic polyamide oligomers and polymers, boron trifluoride-amine complexes, phenolic resins, melamine resins, urea resins, Synthetic resin initial condensates such as urethane resin, etc.
Examples include dicyandiamide, carboxylic acid hydrazide, polyaminomaleimide, and imidazoles.

One or more of the above curing agents can be used in combination.

In particular, a phenol-formaldehyde initial condensate is suitable for exhibiting the effects of the present invention from the viewpoints of adhesion of the cured resin to the metal insert, workability during molding, and the like.

In the present invention, depending on the purpose and use of the resin composition,
Various solvents, inorganic substances, additives, etc. can be mixed and used.

Examples of solvents include alcohols such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, and methyl alcohol; ketones such as acetone and methyl ethyl ketone; cellosolves such as methyl cellosolve and ethyl cellosolve; and petroleum-based solvents such as benzene, toluene, and xylene. Solvents include chloroform, carbon tetrachloride, dimethyl sulfoxide, dimethylacetamide, N-methyl-2-pyrrolidone, etc., and when one or more of them are used in combination, it is often effective in terms of film forming properties, etc. .

In addition, inorganic substances such as zircon, silica, fused silica glass, alumina, water tR1R1 hyaluminum ramulus,
Quartz glass, calcium silicate, stone wax, calcium carbonate, magnesite, clay, kaolin, talc, iron powder,
Fillers such as copper powder, silver powder, mica, asbestos, silicon carbide, boron nitride, molybdenum disulfide, lead compounds, lead oxide, zinc white, titanium white, carbon black, or spherical styrene of 10 μm or less, or styrene Organic fine powder fillers such as acrylate copolymers, higher fatty acids, mold release agents such as waxes, epoxy silanes,
Contains coupling agents such as vinylsilane, aminosilane, acrylic silane, chlorosilane, mercaptosilane, maleimidosilane, borane compounds, alkoxy titanate compounds, and aluminum chelate compounds, as well as antimony compounds, phosphorus compounds, bromine and chlorine. Known flame retardants or thixotropic agents capable of imparting various thixotropic effects can be used.

The present invention can be applied not only to resin-sealed semiconductor devices but also to semiconductor devices using other types of sealing methods such as glass-fused ceramic sealing and solder-fused ceramic sealing.

In the present invention, there are no particular limitations on the method or apparatus for coating or sealing a semiconductor element. Known methods such as transfer molding and injection molding can be applied.

An example of the apparatus of the present invention is shown in FIG. In other words, Figure 1 is
1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention. In FIG. 1, numeral 1 is a lead wire, 2 is a semiconductor element, and 5 is a lead wire.
6 means a protective coating resin, and 6 means a molding resin.

In the present invention, in the resin 5 and/or 6, a zircoaluminate compound or, if necessary, an alkoxysilane compound and/or a titanate compound@
All coating and/or sealing is performed by containing

[Embodiments of the invention]

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.

Examples 1 to 7 Into five 50 [] Wt Erlenmeyer flasks, 250-g of Inglobil alcohol was taken, and separately, Cabcomorado AP()%C! Add PG and FPM (both manufactured by Kusumoto Kasokosha) and dissolve with stirring to prepare five types of zircoaluminate/inglobil alcohol solutions.

Next, in three 500- Erlenmeyer flasks, 125
Toluene of fRt Inglobil alcohol 125- was taken, and each of them was separately treated with Cabcomod AP.
Gi10me extraction, these, yupoxysilane KBM3
03 (manufactured by Shinetsu F Toji Co., Ltd.), titanium isoprobyl titanate) TPT (manufactured by Mitsubishi Gas Fhigaku Co., Ltd.), diisoglopoxy titanium pis (acetylacetonate), TAA (manufactured by Mitsubishi Gas Chemical Co., Ltd.) The mixture was added in batches and heated and stirred at 60 to 80°C for 50 minutes to obtain five types of treatment solutions.

First, in a separate 500- Erlenmeyer flask, add 250-N
-Take methylpyrrolidone and add Cabcomorad AP to it.
G 10 mA and a total of 50 parts by weight of the polyimide precursor (polyamic acid polymer consisting of biphenyltetracarboxylic acid and 4,4'-diaminodiphenyl ether) were added and dissolved with stirring to form a zircoaluminate-containing polyimide precursor solution. It was created.

Next, 256 bits D-RAM memory 1.8 units (
The solutions of the seven strains described above were separately dropped onto the elements and lead wires of 16 bottles]. After that, 100℃, 1 hour +15
Heat treatment was performed at 0°C for 1 hour.

The zircoaluminate-containing polyimide precursor solution was further subjected to a heat treatment of 200° C. for 1 hour + 300° C. for 1 hour.

Next, the memory LSI of type 7a was resin-sealed with a resin composition containing at least epoxy resin t-ff in a transfer bottom shape.

Transfer bottom shape conditions 11180℃, 70□'.

After molding for 1.5 minutes, after-cure was performed at 150° C. for 5 hours.

For each of the 100 LSIs, we left them in supersaturated water vapor (PC'R) at 121°C and 2 atm, and after a predetermined period of time, we electrically checked for corrosion and disconnection of the At wiring on the chips to evaluate their moisture resistance reliability. . The results are shown in Table 1. For comparison, the device was also sealed with an epoxy resin composition without being treated with a zircoaluminate compound.
It is also listed in Table 1.

[Blend composition of sealing resin composition (parts by weight)] Phenol novolak resin 55 Triethylamine tetraphenylborate 2
5-bath fused silica glass powder 49
Zero engineering poxysilane KBM 405 (Shin-Etsu Chemical) 1.0 Red phosphorus 5.0 Carbon black 2.
0 Example 8 [Sealing phase / String of synthetic resin crude product (parts by weight)] Phenol novolac m 60 Triethylamine tetraphenylborate A
O bath fused silica glass powder 490
Cap Komotsud APG (amino group Song end) 2.0 Red phosphorus 5.0 The resin composition for stinging of the present invention is prepared by applying the above-mentioned Formulation 1 to two rolls of 8 inch diameter at 75 to 85°C. After kneading for a minute, cool,
Prepared by coarse grinding.

Using the above composition, in the same manner as in Example 1, 256 bit-D-RAM memory L8 processing (no zirco aluminate treatment) was sealed with resin, and the moisture resistance reliability was evaluated.

As a result, no defects were observed after 2000 hours of PCT.

Example? Glycol-based zircoaluminate, Cab Comorado A
PG (manufactured by Kusumoto Kasei Co., Ltd.) was added to the polyimide precursor used in Examples 1 to 7 to prepare a 25% by weight zircoaluminate-containing polyimide precursor solution.

2 and 3 show device structures in which the molten g is used as a multilayer (two-layer) wiring insulating film. That is, ijl! 2 and 3 are partial cross-sectional views of the element portion of the semiconductor device according to the invention. 2 and 3, reference numeral 2 denotes a semiconductor element, 5-IFI first layer protective coating resin, 5-1 second layer protective plate type resin, 4-1 first layer wiring, 4-11 2nd layer wiring, 5 is polyimide resin,
7 means a thermally acidified film.

The device consists of an 81-layer substrate, a Sin layer, an insulating layer, a polysilicon layer, and a first layer of aluminum wiring (4-
After forming 1), the above resin coating material was applied (using a spinner) and baked (250°C, 60 minutes) (5
- After IJ, positive resist I was applied and the manhole was buttered. Next, plasma etching was performed using CF4-Oak reaction gas. Next, the positive resist was removed using a plasma asher using 02 as a reactive gas.

Next, after forming the second layer of aluminum wiring (4-■), the above resin liquid was further coated and baked (according to the conditions described above).(3-■1) Note that FIG. Polyimide resin (Hitachi Chemical mPIQ
) k used next case (JrgJJ gold showed.

In addition, the moisture resistance reliability data with and without treatment on the Capco Mod APG 'ft element is shown in the second section below.
Shown in the table.

Table 2 [Effects of the Invention] As explained above, the semiconductor device of the present invention has excellent moisture resistance and heat resistance, and has the remarkable effect of being able to operate with high reliability.

[Brief explanation of drawings]

FIG. 1 is a sectional view of a semiconductor device according to an embodiment of the present invention, FIG. 2, and FIG. ¥I is a partial cross-sectional view of an element portion of a semiconductor device according to the present invention. DESCRIPTION OF SYMBOLS 1...Lead wire, 2...Semiconductor element, 5...Protective coating front surface, 5-1...First layer protective coating a resin, 3-n...Second layer protective coating side surface, 4-1... 1st layer wiring, 4-11... 2nd layer wiring, 5... polyimide resin, 6... mold resin, 7... thermal oxide film

Claims (1)

Claims: 1. A semiconductor device characterized in that at least a portion of the semiconductor device has a coating and/or a sealing layer formed using a processing agent containing a zircoaluminate compound. 2. The semiconductor device according to claim 1, wherein the processing agent contains a mixture or reaction product of a zircoaluminate compound and an alkoxysilane compound and/or a titanate compound. 3. The semiconductor device according to claim 1 or 2, wherein the processing agent is a resin composition containing a zircoaluminate compound. 4. The resin composition contains polyimide, polyimide precursor,
Polyimide silicone, polyfluoroimide, polyamideimide, fluorine polymer, silicone polymer,
At least one of an epoxy resin and a phenolic resin
The semiconductor device according to claim 3, which is a composition containing seeds.