WO1993024564A1

WO1993024564A1 - Low temperature flexible die attach adhesive and articles using same

Info

Publication number: WO1993024564A1
Application number: PCT/US1993/004904
Authority: WO
Inventors: My Nhu Nguyen; Yuan Yung Chien
Original assignee: Johnson Matthey Inc.
Priority date: 1992-05-28
Filing date: 1993-05-25
Publication date: 1993-12-09
Also published as: AU4388493A; US5612403A; US5489637A; MX9303106A; US5399907A; US5250600A

Abstract

Described is a flexible adhesive formulation for bonding a semiconductor device to a flexible substrate and a flexible card containing a semiconductor device which can be processed in a computer.

Description

LOW TEMPERATURE FLEXIBLE DIE ATTACH ADHESIVE

AND ARTICLES USING SAME

Field of the Invention

The present invention relates to a flexible die attach adhesive. The flexible die adhesive can be modified to be capable of developing very good adhesive strength at low curing temperatures. One embodiment of the invention relates to a flexible card for processing in a computer that includes a semiconductor device enveloped therein adhered to a substrate by the aforementioned adhesive.

Background of the Invention

As uses for semiconductor devices continue to increase there is a growing demand for adhesive compositions and formulations capable of securing semiconductor devices to substrates under a variety of conditions. The wide variety of applications using semiconductor devices sometimes require that such adhesive formulations be flexible where the device must be flexible and sometimes that the adhesive formulation be capable of developing very good adhesive strength at low curing temperatures so that significant stress is not imparted to the die and the curing conditions do not adversely affect other components. To improve workability, a modified adhesive formulation as described above but of low viscosity is also desirable. One application employing semiconductor devices which is gaining increasing importance is in the field of cards to be processed in computers where such cards incorporate one or more semiconductor devices and are therefore able to store more information than magnetic cards. Such cards may be useful over a broad spectrum of applications including, for example, credit and telephone cards. These cards, which are referred to as "smart cards," must be thin and must be able to bend without breaking, i.e., the card and card components must be flexible. Typically, "smart cards" are constructed of a material such as polyester reinforced with glass fibers and have enveloped within the card one or more semiconductor devices. Desirably, such devices should be secured within the card by a die attach adhesive which is flexible but which provides very good adhesive strength and does not impart stress to the die during curing. It is also important that the adhesive be capable of being cured at relatively low temperatures to facilitate fabrication of the cards without damage to the card or the semiconductor devices.

Cards including semiconductor devices enveloped therein are disclosed in an article by Hans Steinegger, Microelectronics Manufacturing Technology, pp.13-15, December 1991 , the disclosure of which is expressly incorporated herein by reference.

As disclosed in the aforementioned article, the semiconductor devices have heretofore been bonded directly to a metal conductor or other substrate using an epoxy adhesive followed by encapsulation with epoxy resin. The obstacles to the production of such "smart cards" include problems arising in wire bonding because the basic material of the film is not as heat resistant as might be desired. It is pointed out in the article that for smart cards wire bonding must be performed at temperatures that do not exceed 180°C. It is apparent therefore that there is a need for a flexible die attach adhesive which is capable of being cured at relatively low temperatures but has very good adhesive strength.

Summary of the Invention

Adhesive formulations have been proposed which cure rapidly, i.e., are capable of being cured in under 5 minutes at 200°C. However, these formulations contain cyanate esters and are not flexible. The present invention provides a method of rendering cyanate esters flexible by reacting therewith at least one elastomeric and thermo plastic modifier from the group of hydroxyl (-OH), amine (NH) or epoxide reactive groups, or mixtures thereof, by, for example, grafting such groups to cyanate molecular structures. Where flexible adhesive formulations with low viscosity are desired for better workability, etc., the cyanate esters are reacted with a polyhydroxyl polymer compound having the formula:

HO - (CH _m - CO - O - (CH^ - OH and/or

HO - (CH₂) _m - O - C - O - R - C - O - (CH₂) _n - OH. Advantageously, the polyhydroxyl polymer compound used has a molecular weight of between about 200 and about 5,000 and contains at least two hydroxyl groups.

In addition to the foregoing, the invention includes adhesive formulation for bonding a semiconductor device to a substrate, which comprises a reaction product of cyanate ester and the elastomeric modifier, as discussed above, having a low glass transition temperature of less than about 25°C. To impart rapid curability at low temperature, the adhesive may include an alkylphenol, a metal-containing curing catalyst, and/or silver in the form of flake or powder. Advantageously, the alkylphenol is nonylphenol, the metal-containing curing catalyst is from the group consisting of cobalt acetylacetonate and copper naphthenate and the silver is present in amounts up to 90 wt. % . In one preferred embodiment the adhesive comprises the reaction product of 6 to 24 wt.% modifier and 4 to 16 wt.% cyanate ester, 0.01 to 0.06 wt.% metal- containing curing catalyst, 0.5 to 2 wt.% alkylphenol and up to 90 wt.% silver flake and/or powder. Where alkylphenol and/or metal-containing catalyst are present as little as 4 to 20% silver may be sufficient. Where these curing catalysts are absent 60 to 90 wt. % silver may be needed to impart rapid curability to the adhesive formulation.

A novel card in accordance with the invention, for processing in a computer, comprises a semiconductor device enveloped widiin the card and adhered with a flexible adhesive to a substrate. The substrate is advantageously a flexible organic polymeric substrate and/or a lead frame or metal conductor. The adhesive comprises the reaction product of cyanate ester and modifier, as described above, having a glass transition temperature of less than about 25°C, and which may include an alkylphenol, a metal-containing curing catalyst and/or silver in the form of flake and/or powder.

Brief Description of the Drawings

Figure 1 is a graph showing the relationship between the percentage of modifier, i.e., flexibilizer and radius of curvature, ("ROC");

Figure 2 is a graph of die stress against ROC;

Figure 3 is a schematic view partly in section of a card within which one or more semiconductor devices are enveloped and showing such devices bonded to a substrate; and

Figure 4 is a graph illustrating % conversion of the polyhydroxyl polymer flexibilizer as a function of time and temperature.

Detailed Description of the Invention

As has been previously explained, a flexible adhesive is needed for a number of applications where semiconductor devices with large surface areas are attached to flexible substrates, particularly where there is a significant difference between the thermal expansion coefficients of the silicon of the semiconductor device and the substrates. In such cases, a low-stress die attach adhesive is required for maximum performance. This is especially important where the semiconductor device is to be attached to lead frames, such as copper lead frames, and polymeric substrates such as polyester, polyamide films, etc. if a conventional rigid adhesive such as epoxy referred to in the aforementioned

Steinegger article is used in the above described applications, the thermally induced tensile stress imparted to the surface of the semiconductor die is so high that it usually results in a silicon fracture.

To assess the phenomenon involved it is necessary to measure the die stress. One such method is by determining the radius of curvature ("ROC"). A stress free die would be flat and would have a very large radius of curvature. The relationship between tensile stress imparted on the die surface and the radius of curvature is illustrated in Figure 1. Since the tensile stress of silicon is about 100 MPa, an ROC value of about 1 meter or above is advantageous to eliminate silicon fracture with dies of customary size.

Die attach adhesive compositions including cyanate ester and silver do not give the flexible properties needed for the above applications. However, flexible properties can be achieved by reacting cyanate esters with at least one elastomeric and thermo plastic modifier from the group of hydroxyl (-OH), amine (NH) or epoxide reactive functional groups, or mixtures thereof by, for example, grafting such group to cyanate ester molecular structures.

To illustrate the foregoing, blends of low Tg, (Tg <25°C), flexible epoxy and cyanate ester resin undergo the following reactions:

1) 3 R-O-C≡N →

OR Cyan rate N

// \

2 ) R-O-C≡N + R' -CH-CH₂ R-O-C CH₂

\ / \ /

O-CH

R'

Oxazoline

R

R"OH I

3 ) N R' -CH-CH₂ > H - (-0-CH-CH₂-) -OR"

\ / N

O

Polyetherification

The effect of flexible epoxy on ROC is shown in Figure 2. As can be seen, a mixture of at least 50% epoxy gives acceptable performance and the cyanate ester in this mixture also acts as curing agent for the epoxy. However, at least about 15% cyanate ester is needed in the adhesive formulation to provide satisfactory curing in this system. Other elastomeric modifiers containing hydroxyl reactive groups, including hydroxyl terminated butadiene and butadiene-acrylonitrile copolymers, such as "HYCAR" sold by B.F. Goodrich and "VITEL-3600" which is a saturated copolyester resin with a Tg of -11 ^CC, and polyhydroxyl polymer compounds are useful as well as amine functional groups such as polyurethane, elastomer, urethane acrylate, silicone imides, etc.

All of the foregoing modifiers have proven to be miscible with cyanate ester in the uncured state. During curing, the system is phase-separated, forming a co- continuous structure of hard and soft domains composed of cyanate ester-rich and elastomer-rich agglomerates. This system exhibits many advantageous properties, such as increased flexibility due to the soft modifier, while maximizing adhesive strength at high temperature.

The following are examples of some flexible adhesive formulations; with amounts in wt. % : EXAMPLES 1-4

EXAMPLE 5

A so-called "smart card" is shown in the schematic illustration depicted in Figure 3. As can be seen, a card 10, usually made of plastic, includes a metal conductor 12 to which is bonded a semiconductor device 14. Glass fiber reinforced polyester pads 16 may be included and the entire device is encapsulated, such as within an epoxy resin 18. The epoxy resin may be ground flat to produce a thin plastic card.

The adhesive formulation of the present invention is especially suitable for bonding the semiconductor device to a substrate because it is capable of being cured at comparatively low temperatures of 100 to 150°C and has very good adhesive strength while imparting low stress on the die. It is highly desirable for smart card application to employ a die attach adhesive capable of being cured at temperatures not substantially greater than about 150°C, preferably not greater than about 130°C. The die may be attached to a lead frame, such as a copper lead frame in which case the low temperature curing adhesive minimizes oxidation of the copper and thereby eliminates the need of nitrogen or other inert atmosphere such as is often used in curing ovens.

The following examples are of flexible adhesive compositions used to bond semiconductor devices suitable for smart card manufacture.

EXAMPLE 6

The cyanate ester Arocy L10 is available from Rhone-Poulenc of Louisville, Kentucky. The modified bisphenol epoxy resin such as XB 4122 or XUGY 376 is a flexible epoxy supplied by Ciba Geigy. The catalyst system is a solution of copper naphthenate or copper acetylacetonate in nonylphenol. The silver flake has the same physical properties described in the previous examples. Adhesive strength results appear in Table I. TABLE I

The following is another example of a low curing adhesive formulation:

EXAMPLE 7

The catalysts in the foregoing systems and in the systems hereinafter described may be copper naphthenate or copper acetylacetonate, nonylphenol and silver. The formulation in Example 3 was cured at 100°C for 15 minutes and exhibited an adhesive strength of over 30 Kg for a semiconductor die 150 mil² attached on a copper lead frame.

Where flexible adhesive formulations with low viscosity are desired, die cyanate esters are reacted with a polyhydroxyl polymer compound having the formula: HO - (CH^ - CO - o - ( y,, - OH and/or

HO - (CHa)., - 0 - C - O - R - C - O - (CHj). - OH. Preferred polyhydroxyl polymer compounds include polyhydroxyl polyester and polyhydroxyl polyether. Advantageously, the polyhydroxyl polymer compound used has a molecular weight of between about 200 and about 5,000 and contains at least two hydroxyl groups. Such preferred low molecular weight polyhydroxyl polymer compounds result in low viscosity adhesive formulations of about 5 to 50 poise, the molecular weight being empirically related to viscosity. A molecular weight range of about 200 to about 5,000 is preferred because below about 200 the material tends to be too volatile and above about 5,000 the viscosity may be too high for processing conditions. Low viscosity adhesives which have improved workability enabling the formulation to be applied to a wide range of die sizes with varying substrate types, from flexible to rigid, and with reliable performance. Formulations employing polyhydroxyl polymers reacted with cyanate ester can be cured at temperatures between

30°C to 200°C, as shown in Figure 4, in the absence of a catalyst to form partially cross length (partially polymerized) B-stage, non-tacking films which can be subsequently hardened by heat to complete the polymerization in the actually applied process, such as during attaching of electronic devices to substrates. These formulations can be more rapidly cured, and at temperatures up to 200°C, in the presence of catalysts by either heat or UV to form adhesive formulations comprising soft rubber-like layers mass or layer and when combined with a rigid, hard, or elastic layer, both layers would be inseparable from one another. Of course, the compositions may be cured at higher temperatures with shorter curing time. It has been found that adhesive formulations made from the reaction of polyhydroxyl polymers of compounds having the formula described above with cyanate ester possess a high adhesion strength over a wide range of curing temperatures and on different substrates. They also possess high temperature heat resistance of up to 350 °C and considerable flexibility, thereby providing low stress and low modulus characteristics which are useful with a wide range micro-electronic packages and devices. Suitable substrates for die attach adhesives include copper lead frames, printed circuit boards, laminates with "glob"-top coating for substrates varying from rigid to flexible.

The presently preferred low viscosity formulation comprises, in wt.%, 2-22% cyanate ester, 8-32% polyhydroxyl polymer compound, 0.01-0.06 wt.% metal- containing curing catalyst, up to 4.0% of an additive such as amorphous fiime silica or clay, e.g., bentonite, for thixotropic behavior control, 0.5-2%, preferably 0.1-0.5%, alkylphenol and up to 90% silver flake and/or powder. The silver flake and/or powder preferably has a particle size within the range of 0.1-50 μm, a surface area of 0.1-2 m/g and a tap density of 2-6 g/cc.

Low viscosity flexible adhesive formulations of the present invention can be applied to a wide range of semiconductor die size and shape. For example, die sizes from 10 mil. to 700 mil. (0.4 mm to .28 mm) either square or rectangular may be employed. A substrate, which may be rigid or flexible, from material such as alumina, gold coatings or silver coatings, plain copper lead frames and of varying thicknesses from 4 mil. and above, may be used. The curing temperature can be from 30 °C to 300°C, but can be reduced with curing catalysts to 200°C and the processing temperature may vary from 30 °C to 350 °C, if required.

Other advantages ofthe low viscosity flexible adhesive formulation as described is that it is able to resist change even during high temperature thermal aging at 150°C-

185°C and during thermal cycling from -60°C - 150°C for at least 200 cycles. The formulations may be rapidly cured within 5 minutes at 200°C or for longer times at lower temperatures.

The following Table II summarizes a number of examples of low viscosity flexible adhesive formulations employing polyhydroxyl polymer compounds described by their trade names, "Multron R-18", "Desmophen 1700, 1915 U, and 1652", respectively. The material identified as "SD-2" is a bentonite clay additive which may be added to assist in improving thixotropic behavior, i.e., thixotropic characteristics. The physical properties of the examples in Table II are summarized in Table III.

TABLE Π

TABLE III

To illustrate that the shear strength of the formulations described in Table II is maintained and does not degrade over time the composition of Example 8 was subjected to adhesion stability testing to compare die share against aging time. The average results of ten samples are reported in Table IV. For this test, the substrate used was a copper lead frame of 6 mil. thickness, a curing temperature of 150°C, an aging temperature of 150°C, and a die size of 5.08 x 5.08 mm - 200 x 200 mil. TABLE IV

In order to determine whether the die stress remains at acceptable levels for the polyhydroxyl polymer containing adhesive formulations, test of flexibility tests were run to determine the radius of curvature change, if any, over time. The average results of ten samples of the Example 8 composition are reported in Table V which summarizes the tests conducted on die same substrate at the same curing and aging temperature described in connection with the tests reported in Table IV but with different die size. The die size for these tests were 15.24 x 15.24 mm - 600 x 600 mil.

TABLE V

It is apparent from the foregoing that various changes and modifications may be made without departing from the spirit of the invention. Accordingly, the scope of the invention should be limited only by the appended claims wherein what is claimed is:

Claims

1. A method of making a cyanate ester containing material flexible which comprises reacting the cyanate ester with at least one flexibilizer from the group of polyhydroxyl polymer compounds within at least one of the following formula:

HO - (CI . - CO - O - (CH^ - OH and

HO - (CHj)_n - 0 - C - O - R - C - O - (CHj). - OH.

2. A method according to claim 12 wherein said polyhydroxyl polymer has a molecular weight in the range of about 200 to about 5,000 and contains at least two hydroxyl groups.

3. A method according to claim 13 wherein said polyhydroxyl polymer compound is one from the group consisting of polyhydroxyl polyesters and polyhydroxyl polyethers.

4. A flexible adhesive formulation comprising the reaction product of a cyanate ester-containing material and at least one flexibilizer from the group of polyhydroxyl polymer compounds within at least one of the following formula:

and

HO - (CH^ - 0 - C - O - R - C - O - (CH- , - OH.

5. A flexible adhesive formulation according to claim 15 wherein said polyhydroxyl polymer has a molecular weight in the range of about 200 to about 5,000 and contains at least two hydroxyl groups.

6. A flexible adhesive formulation according to claim 16 wherein said polyhydroxyl polymer compound is one from the group consisting of polyhydroxyl polyesters and polyhydroxyl polyethers.

7. A flexible adhesive formulation according to claim 15 having a viscosity of about 5 to about 50 poise.

8. A flexible adhesive formulation according to claim 15 further comprising silver flake and/or powder in an amount sufficient to function as a curing catalyst and to enable said adhesive to be cured in not greater than 5 minutes at 200 °C.

9. A flexible adhesive formulation according to claim 15 further comprising an alkylphenol, a metal-containing curing catalyst and an electrically and/or thermally conductive filler.

10. A flexible adhesive formulation according to claim 20 wherein said filler comprises 60 to 90 wt. % silver.

11. A semiconductor device adhered with an adhesive to a substrate from the group of flexible organic polymeric substrates and lead frames, said adhesive comprising a cyanate ester vehicle rendered flexible by reaction with at least one polyhydroxyl polymer compounds within at least one of the following formula:

HO - (CH^ - CO - O - (CH_JX, - OH and

HO - (CH_a - 0 - C - O - R - C - O - (CHJ,. - OH and silver in an amount sufficient to function as a curing catalyst and to enable said adhesive to be cured in not greater than 5 minutes at 200°C.

12. A semiconductor device according to claim 22 wherein said polyhydroxyl polymer has a molecular weight in the range of about 200 to about 5,000 and contains at least two hydroxyl groups.

13. A semiconductor device according to claim 22 wherein said adhesive contains at least one material from the group consisting of thermally and/or electrically conductive fillers.

14. A semiconductor device according to claim 22 wherein said adhesive further includes an alkylphenol.

15. A semiconductor device according to claim 22 wherein said adhesive further includes a metal-containing co-curing catalyst.

16. A method of rendering a cyanate ester containing composition flexible which comprises adding to the cyanate ester at least one polyhydroxyl polymer compound within at least one of the following formula:

and

HO - (CH₂)_m -0-C-O-R-C-O- (CR_\ - OH or mixtures thereof by grafting such group to the cyanate ester molecular structure.

17. A method according to claim 27 wherein said polyhydroxyl polymer has a molecular weight in the range of about 200 to about 5,000 and contains at least two hydroxyl groups.

18. A card for processing in a computer, said card having a semiconductor device enveloped therein and adhered with an adhesive to a substrate from the group of flexible organic polymeric substrates and leadframes, said adhesive comprising a flexible resin with a glass transition temperature of less than about 25 °C, a cyanate ester vehicle containing at least one polyhydroxyl polymer compound within at least one of the following formula:

HO - (CΑJ_n - CO - O - (CH-λ - OH and

HO - (CH₂)_m -0-C-O-R-C-O- (CHjλ, - OH, an alkylphenol, a metal-containing curing catalyst and a thermally and/or electrically conductive filler.

19. A card according to claim 29 wherein said polyhydroxyl polymer has a molecular weight in the range of about 200 to about 5,000 and contains at least two hydroxyl groups.

20. A flexible adhesive formulation comprising the reaction product of 6 to 24 wt.% modifier and 4 to 16 wt.% cyanate ester, 0.01 to 0.06 wt.% metal- containing curing catalyst, 0.5 to 2 wt.% alkylphenol and up to 90 wt.% silver flake and/or powder, said modifier comprising a polyhydroxyl polymer compound within at least one of the following formulae:

HO - (CH-^ - CO - O - (CH^ - OH and

HO - (CH^ -0-C-O-R-C-O- (CH^ - OH.

21. A low viscosity flexible adhesive formulation comprising, in wt. % , 2-

22% cyanate ester, 8-32% polyhydroxyl polymer compound, 0.01-0.06% metal-curing catalyst, up to 4% of an additive for thixotropic behavior control, 0.5 to 2% alkylphenol and up to 90% silver flake and/or powder.

22. A flexible adhesive formulation according to claim 19 comprising up to 90 wt. % silver.

23. A flexible adhesive formulation according to claim 31 wherein said modifier comprises a polyhydroxyl polymer wi in at least one of the following formulae:

HO - (CH^ - CO - O - (CHa). - OH and

HO - (CH^ - O - C - O - R - C - O - (CH_a),, - OH.

24. A flexible adhesive formulation according to claim 34 wherein said polyhydroxyl polymer compound is one from the group consisting of polyhydroxyl polyesters and polyhydroxyl polyethers.

25. A flexible adhesive formulation according to claim 32 wherein said polyhydroxyl polymer compound is wimin at least one of the following formulae:

HO - (CH_a)_m - CO - O - (CH_a)_n - OH and

HO - (CH-).. - O - C - O - R - C - O - (CHa)_n - OH.

26. A flexible adhesive formulation according to claim 36 wherein said polyhydroxyl polymer compound is one from the group consisting of polyhydroxyl polyesters and polyhydroxyl polyethers.

27. A flexible adhesive formulation according to claim 32 wherein said additive comprises amorphous fume silica or clay.