KR101341154B1 - Conductive die adhesive composition for semiconductor comprising silver or copper coated with silver - Google Patents
Conductive die adhesive composition for semiconductor comprising silver or copper coated with silver Download PDFInfo
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- KR101341154B1 KR101341154B1 KR20120029362A KR20120029362A KR101341154B1 KR 101341154 B1 KR101341154 B1 KR 101341154B1 KR 20120029362 A KR20120029362 A KR 20120029362A KR 20120029362 A KR20120029362 A KR 20120029362A KR 101341154 B1 KR101341154 B1 KR 101341154B1
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Abstract
The present invention relates to a conductive die adhesive composition for semiconductors, and more particularly, to an acrylic resin component and to copper coated with silver or silver, exhibiting excellent high temperature workability and low moisture absorption rate, and a semiconductor die or various leadframes. Conductive die adhesive, particularly suitable for imparting adhesion between (lead frame; bare copper plate, silver coated copper plate) and a plastic ball grid array (PBGA) coated with solder resist paint / ink. It relates to a composition.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive die adhesive composition for semiconductors, and more particularly, to an acrylic resin component and copper coated with silver or silver, exhibiting excellent high temperature workability and low moisture absorption rate, and a semiconductor die and various lead frames ( Conductive die adhesive composition particularly suitable for imparting adhesion between a lead frame; bare copper plate, silver coated copper plate, or plastic ball grid array (PBGA) coated with solder resist paint / ink It is about.
In the packaging of semiconductor devices in recent years, according to the trend of chip integration, various functionalization, light and small size. Faster, cheaper and higher density packaging systems are under development. Accordingly, the physical and chemical properties and the method of use required for the packaging material of the semiconductor device are also changing.
Various resins are used as binder resins for imparting adhesion to semiconductor die and PBGAs coated with various leadframes or solder resist paints / inks.
Among them, polyester resins, urethane resins, etc. are difficult to withstand up to 260 ° C., which is a die bonding operation condition, phenolic resins are inferior in flexibility, and alkyd resins must be reacted at high temperatures and solvents must be used.
In particular, in the case of an epoxy liquid paste adhesive containing a solvent or a diluent (for example, Korean Patent Laid-Open Publication No. 10-2008-0058822), an epoxy resin in equilibrium with the surrounding atmosphere absorbs moisture, and this moisture is absorbed by the PCB ( During the reflow process of the printed circuit board, it is converted into saturated steam, and the excessive pressure caused by the steam and the decrease in the bending strength of the mold compound and the die adhesive may cause a fatal imbalance in the package. Typical unbalanced modes of a package include cracking of encapsulant, cracking of the substrate, severe deformation of the package, and interlayer separation of one or more material joint surfaces.
In addition, the solvent type or diluent type liquid paste adhesive has a problem that the coating method is limited to the screen printing method, a B-stage process for solvent volatilization, there is a problem in the working environment according to the solvent volatilization process.
On the other hand, in integrated or high-density systems of the chip has the disadvantage that the heat generated to reduce the efficiency, it is necessary to discharge the generated heat quickly and efficiently. To this end, a metal material having electrical conductivity and thermal conductivity is used as a heat dissipating component in the adhesive, and the efficiency varies depending on the amount of the metal used. However, in order to obtain such an effect, the metal material should be used at a level of 55 to 90% by weight of the total amount of the composition, thus increasing the manufacturing cost, difficulty in processing, and deterioration or durability degradation due to oxidation or change of the metal powder. There is a problem.
In particular, the price of silver (Ag), which is mainly used as a metal material, is continuously increasing.As a low-cost conductive filler that replaces pure silver (Ag), inexpensive materials such as copper and glass may be converted into thin films of about 10-30 wt%. Coated substitutes have been tried, but there is still a need for the development of commercially available conductive die-bonding adhesives that can provide the desired heat release effect without degrading the performance or physical properties of the resin composition.
The present invention is to solve the problems of the prior art as described above, exhibits excellent high temperature workability and low hygroscopicity, impart adhesion between the semiconductor die and the PBGA coated with various leadframes or solder resist paint / ink It is a technical problem to provide a conductive die adhesive composition particularly suitable for the following.
To solve the above technical problem, the present invention provides a conductive die adhesive composition for a semiconductor comprising at least one acrylic monomer, butadiene compound, a thermosetting agent, a silane coupling agent and a copper powder coated with silver or silver as a conductive metal component. do.
According to another aspect of the invention, there is provided a semiconductor device comprising a cured layer of the conductive die adhesive composition for a semiconductor.
The adhesive composition according to the present invention exhibits excellent high temperature workability and low hygroscopicity, and also has excellent thermal conductivity and shock absorption, so that adhesion between the semiconductor die and various leadframes or PBGAs coated with solder resist paint / ink is low cost. It is particularly suitable to give.
Hereinafter, the present invention will be described in detail.
Acrylic monomers included in the adhesive composition of the present invention are used to improve the viscosity, thixotropic index and moisture absorption of the composition. As the acrylic monomers, various kinds of acrylic monomers such as mono-functional (acrylate), di-functional (diacrylate), tri-functional or more than tri-functional polyfunctional groups may be used, and preferably, di-functional acrylic monomers and tri- or more functional polyacryl One or more types selected from monomers can be used. According to one preferred embodiment of the invention, di- or poly-acrylates of aromatic diols or polyols (eg bisphenol A diacrylate), aliphatic diols or di- or poly-acrylates of polyols (eg hexanediol di) acrylate) and 3 multi-functional or more functional acrylate (e.g., pentaerythritol triacrylate, glycerol propoxylated triacrylate, trimethylolpropane triacrylate, trimethylolpropane (EO), such as 3-6 triacrylate 3 Trifunctional acrylate, or at least one acrylic monomer selected from the group consisting of pentaerythritol tetraacrylate, dimethylolpropane tetraacrylate, tetrafunctional acrylate) can be used.
In the adhesive composition of the present invention, the content of the acrylic monomer is preferably 60 to 80% by weight relative to the total 100% by weight of the acrylic monomer and the butadiene compound. If the content of the acrylic monomer is less than 60% by weight based on 100% by weight of the total amount of the acrylic monomer and the butadiene compound, there may be a problem in adhesion at high temperature due to the increase in moisture absorption and low modulus. Die cracks may occur.
The butadiene compound included in the adhesive composition of the present invention is used to absorb thermal shocks and mechanical shocks to eliminate cracking of semiconductor dies that may occur in the semiconductor package process. As this butadiene compound, 1 or more types chosen from carboxyl-terminal butadiene nitrile rubber (CTBN) and epoxy-substituted butadiene are used preferably. The butadiene compound is crosslinked with the acrylic resin by a thermosetting system to impart flexibility to the composition layer to increase impact absorption. Specific examples of the carboxyl-terminated butadiene nitrile rubber and the epoxy-substituted butadiene can be represented by the following formulas (1) and (2), respectively.
[Formula 1]
(2)
(Wherein x and y are each independently an integer of 1 to 100, and R is a C1-C4 alkyl group such as methyl group (CH 3 ))
In the adhesive composition of the present invention, the content of butadiene compound is preferably 20 to 40% by weight relative to the total 100% by weight of the acrylic monomer and the butadiene compound. If the content of the butadiene compound is less than 20% by weight based on 100% by weight of the total amount of the acrylic monomer and the butadiene compound, the modulus may be increased and die crack may occur. There may be a problem with adhesion at high temperatures.
In the adhesive composition of the present invention, the total content of the acrylic monomer and the butadiene compound is preferably 10 to 45% by weight, more preferably 20 to 35% by weight based on the total weight of the composition (100% by weight), and 25 to Even more preferred is 30% by weight. If the total content of the acrylic monomer and butadiene compound in the composition is less than 10% by weight, the viscosity, thixotropy index, and adhesion may be poor, which may result in the separation between the semiconductor die and the adhesive surface at 260 ° C, which is a semiconductor die bonding process, and 45% by weight. If exceeded, the content of the metal material may be relatively low, and the thermal conductivity effect may be insufficient. In 100% by weight of a preferred embodiment composition of the present invention, 10 to 25% by weight of the acrylic monomer and the butadiene compound include 5 to 15% by weight of carboxyl-terminated butadienenitrile rubber and epoxy-substituted butadiene in total.
The thermosetting agent included in the adhesive composition of the present invention serves to crosslink the butadiene compound with the acrylic resin formed from the acrylic monomer. As the thermosetting agent, a peroxide curing agent such as a peroxyester compound may be preferably used, but is not necessarily limited thereto. It is preferable that content of the thermosetting agent in the adhesive composition of this invention is 0.1-1 weight% with respect to composition total weight (100 weight%). If the content of the thermosetting agent in the composition is less than 0.1% by weight it may not be obtained the intended crosslinking rate, if it exceeds 1% by weight there may be a problem that crosslinking is excessive.
The silane coupling agent included in the adhesive composition of the present invention is used to increase the bonding force between the organic component (acrylic monomer, butadiene, etc.) and the inorganic component (conductive metal powder) in the composition. As such a silane coupling agent, for example, alkoxy silane (methyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, etc.), amino silane (3-aminopropyltriethoxysilane, N- (beta-aminoethyl)- Gamma-aminopropyltrimethoxysilane, etc.), epoxy silane (3-glycidoxypropyltrimethoxysilane, etc.), acrylic silane (3-methacryloxypropyltrimethoxysilane, etc.), mercapto silane (3-mer Captopropyltrimethoxysilane, etc.), fluorine silane, methacryloxy silane (gamma-methacryloxypropyl-trimethoxysilane, etc.), vinylsilane (vinyltrimethoxysilane, vinyltriethoxysilane, etc.) )
Etc. may be preferably used, but is not necessarily limited thereto. It is preferable that content of a silane coupling agent in the adhesive composition of this invention is 0.1-1 weight% with respect to composition total weight (100 weight%). If the content of the silane coupling agent in the composition is less than 0.1% by weight, there may be a problem in the adhesive force between the die and the substrate, and in excess of 1% by weight, there may be a problem in reliability due to the generation of impurities.
The adhesive composition of the present invention comprises silver or silver coated copper powder as a conductive metal for quickly and effectively releasing heat generated during semiconductor processing and operation. In the present invention, silver (Ag) having low oxidation rate and high thermal conductivity or copper powder coated with low cost silver is used in consideration of oxidation or change action and thermal conductivity among various conductive metal powders.
The copper powder coated with silver or silver can be classified into spherical or plate shape according to the shape thereof, and in the present invention, one of spherical or plate shape or a mixture of spherical and plate shape can be used. The average particle size (D50) of the conductive metal powder may be about 0.1 to 20㎛, but is not limited thereto.
In the adhesive composition of the present invention, the content of the copper powder coated with silver or silver is preferably 55 to 90% by weight, more preferably 65 to 80% by weight, based on the total weight of the composition (100% by weight), It is still more preferable that it is 70 to 75 weight%. If the content of the silver or silver-coated copper powder in the composition is less than 55% by weight, the thermal conductivity may be insufficient, and if it exceeds 90% by weight, the viscosity, thixotropy index and adhesion may be poor. In one embodiment of the present invention, when the plate-like pure silver (Ag) powder is used, the amount thereof is 65 to 75% by weight of the total weight of the composition. In another embodiment of the present invention, when using plate-like silver and plate-like copper powder coated with silver, both may be mixed in the same weight percent.
In addition to the components described above, the adhesive composition of the present invention may further include any optional additive components, such as a dispersant, a defoaming agent, and the like, as required.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.
Example One
8 g of bisphenol A diacrylate, 8 g of 1,6-hexanediol diacrylate and 4 g of tetrafunctional acrylate (dimethylolpropane tetraacrylate) as the acrylic monomer; As a butadiene compound, 4 g of carboxyl-terminated butadiene nitrile rubber (CTBN) of Formula 1 (where x is 9 and y is 27) and 5 g of epoxy-substituted butadiene of Formula 2 (where R is a methyl group); 0.4 g of peroxyester (t-amyl peroxyoctoate) as a thermosetting agent; And 0.6 g of a silane coupling agent (3-glycidoxypropyltrimethoxysilane) were thoroughly mixed at room temperature for about 1 hour using Dispomate. 70 g of pure silver (S-1) having a plate-like structure shown in Table 1 was added thereto, and the resultant was mixed at a speed of 750 rpm / 650 rpm for 5 minutes using a Paste mixer, followed by defoaming at a speed of 500 rpm / 150 rpm. A conductive die adhesive composition was prepared. The physical properties of the prepared adhesive composition were evaluated by the following method, and the results are shown in Table 2 below.
Example 2
An adhesive composition was prepared in the same manner as in Example 1, except that 70 g of plate-like copper powder (S-3) coated with silver shown in Table 1 was used as the conductive metal powder, and the physical properties thereof were evaluated by the same method. The results are shown in Table 2 below.
Example 3
An adhesive composition was prepared in the same manner as in Example 1 except that 70 g of plate-like copper powder (S-4) coated with silver shown in Table 1 was used as the conductive metal powder, and the physical properties thereof were evaluated by the same method. The results are shown in Table 2 below.
Example 4
25 g of the mixture of the composition prepared until the addition of the conductive metal powder in Example 1 was used, and as the conductive metal powder, 37.5 g of pure silver (S-2) having a spherical structure shown in Table 1 below and silver shown in Table 1 below Using 37.5 g of coated plated copper powder (S-6), an adhesive composition was prepared in the same manner as in Example 1, and physical properties were evaluated in the same manner, and the results are shown in Table 2 below.
Comparative Example One
10 g of liquid bisphenol F type epoxy resin (BPF resin), 4 g of carboxyl-terminated butadiene (CTBN) modified epoxy resin and 6 g of liquid phenol novolac epoxy resin as an epoxy resin component; 8 g of 1,4-butanediol diglycidyl ether as the reactive diluent; And 0.5 g of an imidazole compound (2MA-OK, manufactured by Shikoku Co., Ltd.) and 1.5 g of an amine compound (Seikacure S, manufactured by Wakayama Seika Co., Ltd.) as a curing accelerator were completely mixed at room temperature for about 1 hour using Dispomate. To 30 g of this mixture, 70 g of pure silver (S-1) having a plate-like structure shown in Table 1 was added, and the resultant was mixed at a speed of 750 rpm / 650 rpm for 5 minutes using a Paste mixer, and then defoaming was performed at a speed of 500 rpm / 150 rpm. Proceed to prepare a conductive die adhesive composition. The physical properties of the prepared adhesive composition were evaluated by the following method, and the results are shown in Table 2 below.
Property measurement and evaluation method
1) viscosity and thixotropic index
Approximately 0.5 ml of the composition sample was taken and the viscosity was measured at 25 ° C. at 0.5 rpm and 5 rpm rotation speed using a spindle CP-51 on a Brookfield cone / plate viscometer, respectively, and the measured viscosity at 0.5 rpm was divided by the viscosity at 5 rpm. Denaturation index was calculated.
2) shear strength
After dispensing the composition sample to a thickness of about 20 ~ 30㎛, after adhering the 120mil * 120mil size die was raised for 30 minutes from 25 ℃ to 175 ℃, and maintained at 175 ℃ for 15 minutes to cure the adhesive. The shear strength was measured at 25 degreeC and 250 degreeC using the DAGE-series 4000PXY about the sample which hardened and adhere | attached the die and the base material (PBGA).
3) moisture absorption rate
After coating the composition sample with a certain thickness and length on the slide glass, the conductive adhesive was cured under the same conditions as the shear strength measurement, and exposed for 24 hours at 85 ° C./85%RH, and then the weight deviation was measured to determine the moisture absorption rate. It was.
4) Glass transition temperature and modulus
The composition samples were placed in a 250mm * 120mm * 1.4mm mold and cured at 175 ° C for about 3 hours, and then measured using a PerkinELmer DMA 8000.
5) thermal conductivity
The composition sample was placed in a Teflon mold and cured at 175 ° C. for 3 hours, and smoothly ground to a size of 10 mm * 10 mm * 2 mm, and measured by Laser Flash Apparatus (LFA) 457 of NETZCH.
6) Storage stability
0.5 ml of the composition sample was taken and left at room temperature (25 ° C.) for one day (24 hrs), then the viscosity was measured at 25 rpm at 5 rpm using a spindle CP-51 on a Brookfield cone / plate viscometer. It was evaluated that the measured viscosity did not rise more than 20%.
[Table 1]
[Table 2]
As can be seen in Table 2, the example compositions according to the present invention showed improved low and high temperature shear strength, reduced moisture absorption and improved high temperature modulus compared to the comparative composition, and also excellent storage stability.
Claims (8)
1 type selected from pentaerythritol triacrylate, glycerin propoxylated triacrylate, trimethylolpropane triacrylate, trimethylolpropane (EO) 3-6 triacrylate, pentaerythritol tetraacrylate and dimethylolpropane tetraacrylate Tri- or tetra-functional acrylic monomers described above;
At least one butadiene compound selected from carboxyl-terminated butadienenitrile rubber and epoxy-substituted butadiene;
Thermal curing agent;
Silane coupling agents; And
Comprising; or a copper powder coated with silver as the conductive metal component,
Conductive die adhesive composition for semiconductors.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20120029362A KR101341154B1 (en) | 2012-03-22 | 2012-03-22 | Conductive die adhesive composition for semiconductor comprising silver or copper coated with silver |
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| Application Number | Priority Date | Filing Date | Title |
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| KR20120029362A KR101341154B1 (en) | 2012-03-22 | 2012-03-22 | Conductive die adhesive composition for semiconductor comprising silver or copper coated with silver |
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| KR20130107513A KR20130107513A (en) | 2013-10-02 |
| KR101341154B1 true KR101341154B1 (en) | 2013-12-13 |
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| KR101677924B1 (en) * | 2014-05-08 | 2016-11-22 | 주식회사 케이씨씨 | Non-conductive acrylic adhesive composition having excellent adhesion at high temperature |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100050561A (en) * | 2007-10-03 | 2010-05-13 | 히다치 가세고교 가부시끼가이샤 | Adhesive composition, electronic component-mounted substrate using the adhesive composition, and semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20100050561A (en) * | 2007-10-03 | 2010-05-13 | 히다치 가세고교 가부시끼가이샤 | Adhesive composition, electronic component-mounted substrate using the adhesive composition, and semiconductor device |
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