JP3200413B2 - Semiconductor device manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has excellent solder heat resistance, also relates to a method of manufacturing a semiconductor device which holds an excellent reliability in high-temperature atmosphere.

[0002]

2. Description of the Related Art Semiconductor devices such as transistors, ICs and LSIs are usually sealed with an epoxy resin composition to form semiconductor devices. A typical example of this type of package is a conventional dual in-line package (DI
P). This DIP is a pin insertion type,
A semiconductor device is mounted by inserting pins into a mounting board.

In recent years, the integration and speed of semiconductor devices such as LSI chips have been increasing, and the mounting density has been increasing due to the demand for smaller and more sophisticated electronic devices.
From such a viewpoint, a surface mount type package is becoming mainstream instead of a pin insertion type package such as DIP. In a semiconductor device using this type of package, pins are taken out in a plane, and the pins are directly fixed to the surface of a mounting board by soldering or the like. Such a surface-mount type semiconductor device has such an advantage that pins can be taken out in a plane, and has the advantages of being thin, light, and small, and therefore has the advantage of occupying a small area on the mounting board. Another advantage is that double-sided mounting on a substrate is also possible.

[0004]

However, if the package itself absorbs moisture before surface mounting in a semiconductor device using the above-described surface mounting type package, the package pressure is increased by the vapor pressure of moisture during solder mounting. There is a problem that cracks occur in the slab. That is, in the surface mount type semiconductor device as shown in FIG. 1, moisture penetrates into the package 3 through the sealing resin 1 as shown by an arrow A, and mainly the surface of the Si-chip 7 and the back surface of the die bond pad 4. Stagnant. And, when performing solder surface mounting such as vapor phase soldering, the accumulated water is vaporized by heating in the solder mounting, and due to its vapor pressure,
As shown in FIG. 2, the resin portion on the back surface of the die bond pad 4 is pushed downward to create a gap 5 therein and, at the same time, to generate a crack 6 in the package 3. 1 and 2
, 8 is a bonding wire.

[0005] As a solution to such a problem, there is a method of sealing a semiconductor element in a package and then packing the obtained semiconductor device in a moisture-proof package and opening it immediately before surface mounting. 100 ° C. above semiconductor device
For 24 hours, followed by solder mounting, which has already been implemented. However, according to such a pretreatment method, a manufacturing process becomes long, and
There is a problem that it takes time.

On the other hand, in order to improve the heat resistance of the sealing resin,
Conventionally, the flame retardancy of an epoxy resin used for sealing has been increased. That is, by combining the brominated epoxy resin and antimony oxide into the epoxy resin composition, the flame retardancy of the cured epoxy resin composition is increased, thereby improving the flame retardancy of the sealing resin. ing. The combination of the above brominated epoxy resin and antimony oxide shows good results in terms of flame retardancy. However, in recent years, semiconductor devices have been used in large quantities in many outdoor devices such as automobiles. Along with this, heat resistance higher than before, especially storage reliability at high temperatures which was not a problem in the past, has been required for semiconductor devices, and a combination of the above brominated epoxy resin and antimony oxide has been required. Then, a problem arises with respect to the storage stability at the high temperature. That is, in a high temperature state, hydrogen bromide is generated by the thermal decomposition of the brominated epoxy resin, and the hydrogen bromide reacts with the junction between the gold wire of the semiconductor element and the aluminum pad to promote the formation of an alloy,
This leads to an increase in the electric resistance value, resulting in poor conduction.

The present invention has been made in view of such circumstances, and has a low stress property capable of withstanding heating during solder mounting without requiring a pretreatment when mounted on an electronic device, and furthermore, a storage in a high temperature atmosphere. Produces semiconductor devices with excellent stability
Its purpose is to provide a method of manufacturing .

[0008]

In order to achieve the above-mentioned object, a method of manufacturing a semiconductor device according to the present invention comprises the following steps (A) to (A).
Prepare an epoxy resin composition containing the component (D)
And a step of sealing a semiconductor element using the epoxy resin composition . (A) An epoxy resin represented by the following general formula (1).

Embedded image (B) A phenol aralkyl resin represented by the following general formula (2).

Embedded image (C) Brominated epoxy resin. (D) At least one of the following components (d1) and (d2). (D1) A hydrotalcite compound represented by the following general formula (3).

Embedded image (D2) at least one compound selected from the group consisting of a bismuth hydroxide, a bismuth oxide, an aluminum hydroxide and an aluminum oxide, wherein the content of chlorine ion, bromide ion and nitrate ion is each Compounds of 5 ppm or less.

That is, the present inventors have conducted a series of studies to achieve the above object. As a result, it has been found that it is effective to use the epoxy resin having a special resin skeleton to prevent the occurrence of package cracks during mounting. In order to maintain the reliability when left at high temperature, the halogen compound gas generated when the brominated epoxy resin as the flame retardant is thermally decomposed is converted into a special hydrotalcite compound represented by the general formula (3). And Bi, A
Focusing on the effective capture and trapping of hydroxides and oxides, it was found that it was effective to use them.
Was. Then, such a semiconductor device is manufactured by the manufacturing method of the present invention.
According to this, it can be obtained easily .

The epoxy resin composition used in the present invention comprises:
The special epoxy resin (component A) represented by the general formula (1), the phenol aralkyl resin represented by the general formula (2), the brominated epoxy resin (component C), and the general formula (3) )), And Bi, in which the contents of chloride ion, bromide ion, and nitrate ion are set to specific values or less, respectively.
It is obtained by using one or both of the compound (d2) composed of Al hydroxide and oxide and is usually in the form of a powder or a tablet obtained by compressing the powder.

The special epoxy resin (component A) is a biphenyl type epoxy resin and is represented by the following general formula (1).

[0012]

Embedded image

As described above, by adding a lower alkyl group to a phenyl ring having a glycidyl group, the phenyl ring has water repellency. And the special epoxy resin (A
Component) alone may constitute the epoxy resin component, or may be used in combination with other commonly used epoxy resins. In the former case, the whole of the epoxy resin component is composed of the special epoxy resin (A component) of the above general formula (1), and in the latter case, a part of the epoxy resin component is part of the above general formula (1) It will be composed of a special epoxy resin (component A). Examples of the commonly used epoxy resin include various epoxy resins such as cresol novolak type, phenol novolak type, novolak bis A type and bisphenol A type. As the novolak type epoxy resin, usually, an epoxy equivalent of 150 to 250,
A resin having a softening point of 50 to 130 ° C. is used. As the cresol novolac type epoxy resin, an epoxy equivalent of 180 is used.
Those having a softening point of 60 to 110 ° C are generally used. When both are used in this manner, the epoxy resin (A component) represented by the above general formula (1) should be set to 20% by weight (hereinafter abbreviated as “%”) or more of the entire epoxy resin component. Preferably, it is particularly preferably at least 50%.

The above phenol aralkyl resin (component B)
Is represented by the following general formula (2).

[0015]

Embedded image

The specific phenol aralkyl resin represented by the general formula (2) serves as a curing agent for the special epoxy resin, and is obtained by reacting aralkyl ether and phenol with a Friedel-Crafts catalyst. can get. Generally, α, α'-dimethoxy-p-
A condensation polymerization compound of xylene and a phenol monomer is known. And as said phenol aralkyl resin, softening point 70-110 degreeC, hydroxyl equivalent 150-22.
It is preferable to use those having 0. Further, the phenol aralkyl resin may constitute the curing agent component by itself or may be used in combination with other commonly used phenol resins. In the former case, the entire curing agent component is composed of the phenol aralkyl resin (component B), and in the latter case, a part of the curing agent component is composed of the phenol aralkyl resin (component B). . As the phenol resin commonly used as described above,
Phenol novolak, cresol novolak and the like can be mentioned. These novolak resins have a softening point of 50.
It is desirable to use one having a hydroxyl group equivalent of 70 to 150 ° C and a hydroxyl equivalent of 70 to 150. When using the above phenol aralkyl resin and such a normal phenol resin in combination,
The phenol aralkyl resin (component B) is preferably set to a proportion of 50% or more of the entire curing agent component, particularly preferably 70% or more. The mixing ratio of the phenol aralkyl resin (including the phenol aralkyl resin when used in combination with a normal phenol resin) is determined by the special epoxy resin (A
It is preferable that the hydroxyl group in the phenol aralkyl resin is 0.7 to 1.3 equivalent per 1 equivalent of the epoxy group in the component). 0.9 to more preferred
1.1 equivalents.

The brominated epoxy resin (component C) used together with the special epoxy resin (component A) and the phenol aralkyl resin (component B) has an epoxy equivalent of 4
It is desirable to use 20 or more, preferably 420 to 550. In particular, using a brominated bisphenol-type epoxy resin gives good results. If the epoxy equivalent is less than 420, not only does the resin have a tendency to be inferior in heat resistance, but also a hydrogen halide gas is easily generated.

Such a brominated epoxy resin (component C)
Is used in the resin component (A + B +) of the epoxy resin composition.
(C component), it is preferable to set within the range of 1 to 10%. That is, if the amount of the brominated epoxy resin is less than 1%, the effect of improving the flame retardancy becomes insufficient, and if it exceeds 10%, the generation of hydrogen halide gas tends to increase, which tends to adversely affect the semiconductor element. Because it can be done.

The D component used together with the above A to C components includes a special hydrotalcite compound (d1) represented by the general formula (3) and a content of chloride ion, bromide ion and nitrate ion. One or both of Bi and Al hydroxides and oxides (d2) each having a specific value or less are used, and these convert halogen ions and organic acid ions in the epoxy resin composition into their own CO _3.
^{It is} considered that the above-described impurity ions are trapped by substituting with or coordinating with ^2-, and an effect of preventing generation of hydrogen bromide due to thermal decomposition of the brominated epoxy resin is exerted.

The types of the hydrotalcite compounds are classified into many types depending on the ratio of the numbers x, y and z in the general formula (3). Such hydrotalcite compounds are used alone or in combination of two or more. Such a compound preferably has an average particle size of 5 μm or less and a maximum particle size of 30 μm or less from the viewpoint of dispersibility in the epoxy resin composition. The content of such a hydrotalcite compound is determined by the resin component (A) of the epoxy resin composition.
+ B + C) is preferably set to 0.1 to 5%. That is, if the compounding amount is less than 0.1%, the effect of improving the high-temperature storage characteristics is not sufficiently exhibited, and if it exceeds 5%, a phenomenon of a decrease in moisture resistance is observed.

The D component other than the above hydrotalcite compounds is a hydroxide of Bi, an oxide of Bi, a hydroxide of Al, and an oxide of Bi, which are chlorine ion, bromide ion, and nitric acid, respectively. Those having an ion content of 5 ppm or less are used alone or in combination. Representative examples of such compounds include bismuth hydroxide, aluminum hydroxide, bismuth trioxide, and dialuminum trioxide. And, in such a compound, it is necessary that the content of each ion is 5 ppm or less.
That is, when each ion content exceeds 5 ppm, the moisture resistance of the semiconductor device is reduced. The above compounds may be used alone or in combination. The content of the Bi and Al hydroxides and oxides is preferably set so that the content of the compound is 1 to 10% with respect to the resin component (A + B + C component) of the epoxy resin composition. That is, if the content is less than 1%, the effect of improving the high-temperature storage characteristics is not sufficiently exhibited,
Conversely, if it exceeds 10%, a phenomenon of a decrease in moisture resistance is observed. The Bi and Al hydroxides and oxides have an average particle size of 0.5 to 30 μm and a maximum particle size of 7 μm.
Fine particles having a size of 4 μm or less are preferred. If the particle size is larger than this, the dispersibility is remarkably reduced, and the effect of improving the high-temperature storage characteristics tends to be hardly obtained.

Further, when both the above-mentioned hydrotalcite compounds and the hydroxides and oxides of Bi and Al are used as the D component, their content is based on the resin component (A + B + C component) of the epoxy resin composition. It is preferable that the total amount of the above compounds is set so as to be 1 to 10%.

The epoxy resin composition used in the present invention contains, if necessary, other additives conventionally used in addition to the above-mentioned components A to D.

Examples of the other additives include a curing accelerator, a release agent, a coloring agent, a silane coupling agent and the like.

Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, imidazoles, organic phosphorus compounds and boron compounds, and can be used alone or in combination.

Examples of the releasing agent include conventionally known long-chain carboxylic acids such as stearic acid and palmitic acid, metal salts of long-chain carboxylic acids such as zinc stearate and calcium snareate, and waxes such as carnauba wax and montan wax. Can be used.

The epoxy resin composition used in the present invention can be produced, for example, as follows. That is, first, the above A to D components and the above other additives are appropriately blended, the mixture is melted and mixed in a kneading machine such as a mixing roll machine in a heated state, and the mixture is cooled to room temperature and then cooled by a known means. It can be manufactured by a series of steps of crushing and, if necessary, tableting. In the epoxy resin composition thus obtained, it is preferable to set the total amount of ions (the total amount of chloride ion, bromide ion, and nitrate ion) contained in the composition to 100 ppm or less.

The sealing of the semiconductor element using such an epoxy resin composition is not particularly limited, and can be performed by a known molding method such as ordinary transfer molding.

The semiconductor device obtained in this manner is a special epoxy resin (component A) represented by the general formula (1) contained in the epoxy resin composition, and the general formula (2)
By the action with the phenol aralkyl resin represented by
Low moisture absorption of the sealing resin itself is realized, and there is no occurrence of a package crack or the like during solder mounting. Further, by the action of one or both of the hydrotalcite compound represented by the general formula (3) and the specific Bi or Al hydroxide or oxide, the generation of hydrogen bromide generated at high temperatures is prevented. Excellent storage reliability under high temperature atmosphere.

[0030]

As described above , according to the production method of the present invention,
If, with the specific epoxy resin (A component), and a specific phenol resin (B component), and brominated epoxy resin (C component), hydrotalcite compound (d1), Oyo <br/> Beauty, Simplified by using a special epoxy resin composition containing one or both (D component) of specific Bi and Al hydroxides and oxides (d2), and sealing the semiconductor element with resin
First, a semiconductor device is manufactured. And the obtained semiconductor device
In the above, due to the action of the specific epoxy resin (A component) and the specific phenol resin (B component), moisture absorption of the sealing resin is suppressed, and a package crack may occur even under severe conditions such as solder mounting. And has excellent moisture resistance reliability. In addition, the action of the hydrotalcite compound and / or one or both of the above-mentioned specific Bi and Al hydroxides and oxides (D component) makes it possible for the halogenated compound generated by leaving the compound to stand in a high-temperature atmosphere for a long time. It is highly reliable even when used in a high-temperature atmosphere such as an outdoor device because it is trapped.

Next, examples will be described together with comparative examples.

First, prior to the examples, the compounds shown in Table 1 below were prepared.

[0033]

[Table 1]

[0034]

Examples 1 to 20 and Comparative Examples 1 to 9 Next, the compounds shown in the above Table 1 and the components shown in the following Tables 2 to 5 were added to Table 2
After mixing at a ratio shown in Table 5 below, kneading with a mixing roll machine, cooling, and then pulverizing, a desired powdery epoxy resin composition was obtained. Further, the total ion content (total content of each of chloride ion, bromide ion and nitrate ion) contained in the epoxy resin composition thus obtained is shown in Tables 2 to 5 below. Shown.

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

[Table 5]

Next, Examples 1 to 20 and Comparative Examples 1 to
A semiconductor device was obtained by molding a semiconductor element by transfer molding using the powdery epoxy resin composition obtained in 9 above. This semiconductor device is an 80-pin four-way flat package (QFP) (20 mm × 14 mm ×
It has a die bond plate of 7 mm × 7 mm and a chip size of 6.5 mm × 6.5 mm. The semiconductor device thus obtained was immersed in solder at 260 ° C., and the critical moisture absorption time at 85 ° C./85% RH until a package crack occurred was measured. Using the epoxy resin composition, a disk-shaped cured product having a thickness of 3 mm x a diameter of 50 mm was prepared (curing conditions: 180 ° C for 5 hours). Moisture was absorbed under RH for 500 hours, and the saturated moisture absorption was measured. In addition, the bending strength of the cured
It measured at 260 degreeC according to -K-6911, 5.17. The measurement of element failure in a high temperature state was performed by assembling a semiconductor device by sealing a semiconductor element with a resin, exposing a total of 20 semiconductor devices to a predetermined high temperature, and evaluating the number of defective devices. In addition, as a reliability test, a semiconductor device was assembled by sealing the model semiconductor element with a resin using the epoxy resin composition, and was left in a pressure cooker state (121 ° C. × 2 atm × 100% RH) to prevent aluminum corrosion. A pressure cooker test (PCT test) for measurement was performed, and the number of generated defects was counted. The results of these measurement evaluations are shown in Tables 6 to 9 below.

[0040]

[Table 6]

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

[Table 9]

From the results of Tables 6 to 9, the products of Comparative Example 3 and Comparative Example 6 have low saturated moisture absorption and a long limit moisture absorption time.
Poor conduction has occurred in a high-temperature atmosphere. As in Comparative Example 5, the product of Comparative Example 5 has a low saturated moisture absorption rate, a long critical moisture absorption time, and excellent reliability in a high-temperature atmosphere, but has a defective number in the PCT test. The products of Comparative Examples 1, 2 and 8 did not show any failure in a high-temperature atmosphere, but had a high saturated moisture absorption and a short critical moisture absorption time. The product of Comparative Example 4 has a high saturated water absorption and a short critical moisture absorption time. Further, a defect occurs in a high-temperature atmosphere. The product of Comparative Example 9 has a high saturated water absorption and a short critical moisture absorption time. Further, conduction failure occurs in a high-temperature atmosphere. On the other hand, the products of Examples have a low saturated water absorption and a long limit moisture absorption time. Further, no defect occurred in a high-temperature atmosphere. Therefore, it can be seen that the product of the example is superior to the product of the comparative example in terms of moisture resistance reliability, does not cause a package crack or the like at the time of solder mounting, and is superior in reliability when left at high temperature.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view illustrating a state of occurrence of a package crack in a conventional semiconductor device.

FIG. 2 is a longitudinal sectional view illustrating a state of occurrence of a package crack in a conventional semiconductor device.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI H01L 23/29 H01L 23/30 R 23/31 (72) Inventor Kazumasa Igarashi 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Toku Nagasawa 1-2-1, Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation (72) Inventor Kazuhiro Ikemura 1-1-1, Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation (72) Inventor Fujio Kitamura 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Minoru Nakao 1-1-2 Shimohozumi, Ibaraki-shi, Osaka In Nitto Denko Corporation (56) References JP-A-1-206655 (JP, A) JP-A-1-206656 (JP, A) JP-A-2-86148 (JP, A) JP-A-2-94654 (JP, A) Patent 3088435 (JP, A 2) (58) investigated the field (Int.Cl. ^7, DB name) C08G 59/24 C08G 59/62 C08L 63/00 - 63/10 C08K 3/22 C08K 3/26 H01L 23/29

Claims (4)

(57) [Claims] 1. A step of preparing an epoxy resin composition containing the following components (A) to (D):
Including a step of sealing a semiconductor element using a resin composition
Manufacturing method of a semiconductor device are. (A) An epoxy resin represented by the following general formula (1). Embedded image (B) A phenol aralkyl resin represented by the following general formula (2). Embedded image (C) Brominated epoxy resin. (D) At least one of the following components (d1) and (d2). (D1) A hydrotalcite compound represented by the following general formula (3). Embedded image (D2) at least one compound selected from the group consisting of a bismuth hydroxide, a bismuth oxide, an aluminum hydroxide and an aluminum oxide, wherein the content of chlorine ion, bromide ion and nitrate ion is each Compounds of 5 ppm or less. 2. The brominated epoxy resin as component (C)
The content is the resin component (A + B + C) of the epoxy resin composition.
Component), the content is set in the range of 1 to 10% by weight.
Item 2. A method for manufacturing a semiconductor device according to Item 1 . 3. Hydrotalcite as the component (d1)
The average particle size of the class compound is 5 μm or less and its maximum particle size
3. The semiconductor device according to claim 1, wherein
Method of installation . 4. Hydroxidation of bismuth as the component (d2)
Material, bismuth oxide, aluminum hydroxide and
At least one selected from the group consisting of aluminum oxides
The average particle size of one compound is in the range of 0.5 to 30 μm
And the maximum particle size is 74 μm or less.
4. The method for manufacturing a semiconductor device according to any one of claims 3 to 3.