WO2009067111A1 - Method of containing resin bleed - Google Patents

Method of containing resin bleed Download PDF

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Publication number
WO2009067111A1
WO2009067111A1 PCT/US2007/085258 US2007085258W WO2009067111A1 WO 2009067111 A1 WO2009067111 A1 WO 2009067111A1 US 2007085258 W US2007085258 W US 2007085258W WO 2009067111 A1 WO2009067111 A1 WO 2009067111A1
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WO
WIPO (PCT)
Prior art keywords
substrate
contact angle
bonding area
adhesive
containment material
Prior art date
Application number
PCT/US2007/085258
Other languages
French (fr)
Inventor
Pierino Italo Zappella
Original Assignee
Henkel Ag & Co. Kgaa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to PCT/US2007/085258 priority Critical patent/WO2009067111A1/en
Publication of WO2009067111A1 publication Critical patent/WO2009067111A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
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    • H01L2224/27011—Involving a permanent auxiliary member, i.e. a member which is left at least partly in the finished device, e.g. coating, dummy feature
    • H01L2224/27013—Involving a permanent auxiliary member, i.e. a member which is left at least partly in the finished device, e.g. coating, dummy feature for holding or confining the layer connector, e.g. solder flow barrier
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    • H01L2224/291—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29101—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
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    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
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    • H01L2224/838—Bonding techniques
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Definitions

  • This invention relates to an integrated circuit package or device, and a method of manufacturing such, in which the bleed of adhesive on the substrate is contained
  • the mounting of integrated circuits onto substrates for electrical interconnection to, for instance, a circuit board often requires the use of various types of adhesives and encapsulants
  • the adhesives may be used to bond a semiconductor die to a metal, ceramic, or organic substrate, or they may be used to bond a semiconductor die to another semiconductor die as in so-called "stacked die” configurations
  • Underfills, which are a type of encapsulant, are typically used to protect the solder bond between flip-chip semiconductor die and a substrate
  • the use of liquid or paste materials can prove problematic because of a phenomenon known in the art as "bleed" Bleed is the undesirable spread, or flow, of the encapsulant or adhesive on the substrate Bleed can occur either at room temperature or, more often, during the early stages of heating such as that experienced during a temperature-ramp up for a cure cycle This is due to the fact that most adhesives and encapsulants have a drop in viscosity upon heating, before polymerization and/or crosslinking occur in the curing operation.
  • Bleed presents a problem in semiconductor packaging because it typically is not easy to control Adhesive or encapsulant, or components thereof, can contaminate portions of the substrate outside of the intended bonding area If these portions include, for example, wire bond pads, subsequent manufacturing difficulties or device failures may result.
  • This invention is a method of containing the bleed of adhesive on a substrate
  • a narrow band of containment material is applied peripherally around a bonding area on the substrate, forming a border around the bonding area
  • An adhesive is then applied to the bonding area within the border formed by the containment material
  • the method is characterized by the fact that the contact angle of the containment material on the substrate is higher than the contact angle of the bonding area of the substrate
  • an adhesive is first applied to the bonding area of a substrate
  • a narrow band of containment material is then applied peripherally around the bonding area, forming a border around the bonding area and the adhesive.
  • the method is characterized by the fact that the contact angle of the containment material on the substrate is higher than the contact angle of the bonding area of the substrate
  • this invention is a substrate for the mounting of integrated circuits
  • the substrate has a bonding area.
  • An adhesive has been applied to the bonding area, and a narrow band of containment material has been applied peripherally around the bonding area, thereby forming a border around the bonding area and the adhesive
  • the substrate is characterized by the fact that the contact angle of the containment material on the substrate is higher than the contact angle of the bonding area of the substrate
  • this invention is an integrated circuit device
  • the device comprises a substrate for the mounting of integrated circuits, which has a bonding area thereon An adhesive has been applied to the bonding area, and a narrow band of containment material has been applied peripherally around the bonding area, thereby forming a border around the bonding area and the adhesive.
  • the device is characterized by the fact that the contact angle of the containment material on the substrate is higher than the contact angle of the bonding area of the substrate
  • FIGURE 1 illustrates a top perspective view of one embodiment of the containment material border on a substrate.
  • contact angle means the angle between the surface of a substrate and a tangent line drawn from a drop of deionized water resting on the surface of that substrate All contact angle measurements provided herein were measured on a Kruss goniometer at room temperature using a video capture system When the contact area of a material is cited, that contact angle was measured using deionized water on the surface as specified
  • adheresive refers to a material used to bond, encapsulate, or underfill an adherend to a substrate
  • Resin refers to any polymer, pre-polymer, oligomer, or monomer used in an adhesive formulation. Resins may be liquid at room temperature or may be solid at room temperature and dissolved within the adhesive formulation. Resins also may be solid at room temperature but liquid and/or flow-able at typical adhesive processing temperatures such as experienced during wirebonding, B-staging, and cure operations.
  • bleed refers to flow, wicking, or running of at least one adhesive component away from the adhesive application area on a substrate.
  • B-staging (and its variants) is used to refer to the processing of a material by heat or irradiation so that if the material is dissolved or dispersed in a solvent, the solvent is evaporated off with or without partial curing of the material, or if the material is neat with no solvent, the material is partially cured to a tacky or more hardened state, if the materia! is a flow-able adhesive, B-staging will provide extremely low flow without fully curing, such that additional curing may be performed after the adhesive is used to join one article to another.
  • the reduction in flow may be accomplished by evaporation of a solvent, partial advancement or curing of a resin or polymer, or both.
  • curing agent is used to refer to any material or combination of materials that initiate, propagate, or accelerate cure of the composition and includes but is not limited to accelerators, catalysts, initiators, and hardeners
  • FIGURE 1 illustrates a top perspective view of one embodiment of the containment material border on a substrate.
  • the containment material forms a border around the bonding area so that the substrate input/outputs (I/Os) are protected from the adhesive that is applied to the bonding area.
  • the specific substrate utilized for this invention is not especially important, and may be any that is suitable for a particular semiconductor package including ceramic, organic, or metallic substrates.
  • the substrate may also be a semiconductor itself
  • the substrate surface may be "bare” or may have been treated as required for the manufacture, functionality, and reliability of the device. Such treatments may include adhesion promoters, plasma treatments, organic surface protectants (OSP), or bleed reduction treatments (coatings) as may be performed by substrate manufacturers.
  • OSP organic surface protectants
  • the surface may have solder mask, electrical tracings, plating, or other surface enhancements.
  • the contact angle of the substrate is determined by measuring the angle between the surface of the substrate and a tangent line drawn from a drop of deionized water resting on the surface of that substrate, in the bonding area (where no containment material has been applied).
  • the bonding area of the substrate may include a bond pad, an underfill area, an encapsulant area, or any place where an adhesive composition is to be applied and within which the bleed of the adhesive must be controlled or contained.
  • the bonding area may be any size or shape as required for the particular application, and may include vacant or bare area in addition to area over which adhesive is to be applied and/or dies or components are to be placed
  • the bounds of the bonding area are defined by the portions of the substrate onto which it is undesirable for adhesive components to flow These portions may include, for instance, substrate input/output terminals (1/Os) such as wire bond pads and discrete components such as capacitors and resistors
  • the containment material is any material that (a) may be applied to the substrate in a narrow band peripherally around the bonding area, and (b) has a contact angle, when applied to the substrate, which is higher than the contact angle of the bonding area of the substrate
  • suitable containment materials include permanent ink markers, such as Sharpie ® , available from Sanford Brands, aliphatic hydrocarbons such as those found in Thompson's ® Water Seal ® , commercially available from The Thompson's Company, isoparaffinic hydrocarbons, fluoroaliphatic resins, and combinations thereof such as found in ScotchgardTM, which is commercially available from 3M
  • Suitable containment materials could also include natural or synthetic waxes such as paraffin, parowax, microcrystalline waxes, petroleum wax blends, amorphous waxes, polyester waxes, soy wax, beeswax, and blends of those Suitable containment materials could also include a polyfluo ⁇ nated compound
  • the specific containment material selected will depend on such factors as ease of application, availability, process compatibility, and cost
  • the effectiveness of a given containment material will depend, in part, on the specific resins to be contained, the substrate employed, and the downstream processing conditions In general, a larger difference between the contact angle of the substrate to which containment material has been applied and the contact angle of the bonding area of the substrate will yield more effective containment of the bleed
  • the containment material on the substrate has a contact angle that is at least 1 1 ° higher than the contact angle of the bonding area of the substrate In another embodiment the contact angle of the containment material on the substrate is at least 19° higher than the contact angle of the bonding area of the substrate In another embodiment the containment material on the substrate has a contact angle that is at least 55° higher than the contact angle of the bonding area of the substrate
  • the containment material is applied in a narrow band peripherally around the bonding area, such that a border is formed around the bonding area.
  • the interior of the border defines the bonding area and the exterior of the border defines the area of the substrate that is to be protected from the bleed, or flow, of the adhesive or adhesive components
  • the containment material is not applied in such a way as to form a physical dam or elevated barrier to the flow of the adhesive Rather, the containment material is applied in a thin layer, and is effective because it is not as easily wetted as the substrate Therefore, when adhesive or adhesive components flow to the containment material border, they are less likely to flow over the containment material because of the higher contact angle (lower surface energy) of the surface in that area. In this way the flow, or bleed, of the adhesive and its components is prevented from contaminating surfaces on the exterior of the border formed by the containment material.
  • the method of applying the containment material is not particularly important and may be any that is suited to yield a narrow band around a pre-defined area, such as dispensing, writing, painting, spreading, controlled spraying, stamping, transfer stamping, roller coating, jetting, and the like.
  • the containment material is applied such that it forms a thin film or coating on the substrate, rather than a thick bead or dam.
  • the containment material is specifically not applied universally to the whole substrate, and especially is not applied to the bonding area itself. That is, the containment material is not applied to the majority of the area of the substrate, but only in a narrow band around the bonding area.
  • the containment material will not interfere with the bonding of the adhesive to the substrate, as it might if it were applied to the bonding area itself. It also minimizes the chances that the containment material will interfere with circuitry or other structures on the surface of the substrate. Further, applying the containment material in this way minimizes material usage and cost compared to coating the majority of the substrate surface.
  • the fact that the containment material is applied peripherally around the bonding area, forming a completely closed border, means that the bleed is contained within that border and thus the rest of the substrate need not be coated with the containment material in order to prevent adhesive from contaminating it.
  • the adhesive utilized this invention may be any that is suitable for the particular device and industrial process. It contains at least one component that is prone to bleed on the substrate under the processing conditions to be employed in the manufacturing operation.
  • the adhesive may be used to bond an adherend to a substrate, such as in bonding a semiconductor chip to a metal leadframe or to an organic or ceramic substrate.
  • the adhesive also may be used to encapsulate or underfill a device, such as with flip chip semiconductor packages.
  • suitable adhesives include epoxies, acrylates or methacrylates, maleimides, vinyl ethers, polyesters, poly(butadienes), polyimides, benzocyclobutene, siliconized olefins, silicone resins, styrene resins, cyanate ester resins, polyolefins, or siloxanes and combinations thereof.
  • Adhesives may be filled or unfilled and may contain additives commonly used in the art including curing agents, solvents, adhesion promoters such as silanes, diluents, and surfactants.
  • the method of applying the adhesive is not particularly important and may be any that is suitable for the particular device and industrial process to be utilized.
  • the adhesive is applied within the interior portion of the border formed by the containment material. Examples of suitable methods of applying the adhesive include needle dispensing, coating, pen application, stamp transfer, roliers, controlled localized dipping, controlled localized spraying, and jetting.
  • the adhesive is applied to the bonding area of the substrate before the containment material is applied peripherally around the bonding area.
  • the containment material is then applied before any downstream operations that are prone to causing bleed.
  • the containment material must be applied in a timely fashion to contain the bleed within the desired area.
  • the containment material must be applied before the B-staging operation.
  • the containment material may be applied any time before curing, including after the B-staging operation and before the curing step.
  • the containment material is applied peripherally around the bonding area of the substrate before the adhesive is applied to the bonding area.
  • the substrate or device may be processed in any manner suitable for the particular industrial use.
  • the containment material blocks the bleed of the adhesive and its components during downstream operations such as room temperature staging or cure, B-staging, thermal and/or UV-cure, wirebonding, and reflow.
  • a black ceramic substrate was treated with argon plasma for 12 minutes (250 Watts, 400 mTorr), and then 4 dots of resin or formulated product were applied to the substrate.
  • a separate black ceramic substrate was also prepared without plasma treatment.
  • resin dots for each resin to be evaluated, were applied.
  • the black ceramic substrate was selected because it is known for its propensity for inducing bleed with a variety of adhesives.
  • the plasma treatment was employed to lower the substrate contact angle and thus enhance (make worse) bleed out or flow out.
  • pure resins were tested because fully formulated adhesives sometimes do not bleed as much as the pure resins.
  • the specific formulated products and resins selected were those that were known to be particularly prone to bleed, in this way the examples were designed to test "worst case" examples of adhesive and resin bleed on a substrate.
  • the following resins were tested: bismaleimide, epoxy, cyanate ester, and siliconized olefin.
  • the following formulated products were tested: ABLEBOND ® 3003 (siliconized olefin- based adhesive) and ABLEFILL ® UF8802 (cyanate ester-based underfill).
  • a Sharpie ® pen was used to draw on the substrate a narrow band, forming a border, around each of the dots.
  • the substrates were then subjected to a cure simulation of a 45 minute ramp from room temperature to 150 0 C, followed by 90 minutes at 150°C. This simulation was selected to represent a typical cure cycle, lowering the viscosity of the resins and inducing them to flow on the substrate.
  • the specimens were visually evaluated for bleed performance. If the material bled onto or beyond the band of containment material the dot was considered “not contained”. If the resin remained within the interior of the border formed by the containment material the dot was considered "contained”.
  • the Sharpie ® pen provided some control over the bleed of the bismaleimide resin, especially on the plasma-treated substrate.
  • the bleed with the other resins and adhesive formulations was very well-controlled. It is believed that the higher contact angle of the pen (see Example 4, below) prevented wetting of the substrate, containing the bleed of the resins and adhesives tested.
  • a black ceramic substrate was treated with argon plasma for 12 minutes (250 Watts, 400 mTorr), and then 4 dots of resin or formulated product were applied to the substrate.
  • a separate black ceramic substrate was also prepared without plasma treatment.
  • resin dots for each resin to be evaluated, were applied.
  • the black ceramic substrate was selected because it is known for its propensity for inducing bleed with a variety of adhesives.
  • the plasma treatment was employed to lower the substrate contact angle and thus enhance (make worse) bleed out or flow out.
  • pure resins were tested because fully formulated adhesives sometimes do not bleed as much as the pure resins.
  • the specific formulated products and resins selected were those that were known to be particularly prone to bleed. In this way the examples were designed to test "worst case" examples of adhesive and resin bleed on a substrate.
  • the Thompson's ® Water Seal ® provided some control over the bleed of the siliconized olefin resin, especially on the non-plasma-treated substrate.
  • the bleed with the other resins and adhesive formulations was very well-controlled. It is believed that the higher contact angle of the Thompson's ® Water Seal ® (see Example 4, below) prevented wetting of the substrate, containing the bleed of the resins and adhesives tested.
  • a biack ceramic substrate was treated with argon plasma for 12 minutes (250 Watts, 400 mTorr), and then 4 dots of resin or formulated product were applied to the substrate.
  • a separate black ceramic substrate was also prepared without plasma treatment. To this substrate 4 resin dots, for each resin to be evaluated, were applied.
  • the black ceramic substrate was selected because it is known for its propensity for inducing bleed with a variety of adhesives
  • the plasma treatment was employed to lower the substrate contact angle and thus enhance (make worse) bleed out or flow out
  • pure resins were tested because fully formulated adhesives sometimes do not bleed as much as the pure resins
  • the specific formulated products and resins selected were those that were known to be particularly prone to bleed In this way the examples were designed to test 'worst case" examples of adhesive and resin bleed on a substrate
  • ScotchgardTM was applied in a narrow band using a cotton swab to form a border around each dot
  • the substrates were then subjected to a cure simulation of a 45 minute ramp from room temperature to 15O 0 C, followed by 90 minutes at 15O 0 C This simulation was selected to represent a typical cure cycle, lowering the viscosity of the resins and inducing them to flow on the substrate.
  • the bare substrate had a lower average contact angle than each of the substrates that had containment material thereon
  • the higher contact angle (lower surface energy) of the surfaces with the containment material prevented wetting of the substrate, enabling a containment of the bleed

Abstract

This invention is a method of containing the bleed of adhesive on a substrate. A narrow band of containment material is applied peripherally around a bonding area on the substrate, forming a border around the bonding area. An adhesive is then applied to the bonding area within the border formed by the containment material. The method is characterized by the fact that the contact angle of the containment material on the substrate is higher than the contact angle of the bonding area of the substrate. This invention also includes a substrate and a semiconductor device produced according to the inventive method.

Description

METHOD OF CONTAINING RESIN BLEED
FIELD OF THE INVENTION
[0001] This invention relates to an integrated circuit package or device, and a method of manufacturing such, in which the bleed of adhesive on the substrate is contained
BACKGROUND OF THE INVENTION
[0002] The mounting of integrated circuits onto substrates for electrical interconnection to, for instance, a circuit board, often requires the use of various types of adhesives and encapsulants The adhesives may be used to bond a semiconductor die to a metal, ceramic, or organic substrate, or they may be used to bond a semiconductor die to another semiconductor die as in so-called "stacked die" configurations Underfills, which are a type of encapsulant, are typically used to protect the solder bond between flip-chip semiconductor die and a substrate In both cases, the use of liquid or paste materials can prove problematic because of a phenomenon known in the art as "bleed" Bleed is the undesirable spread, or flow, of the encapsulant or adhesive on the substrate Bleed can occur either at room temperature or, more often, during the early stages of heating such as that experienced during a temperature-ramp up for a cure cycle This is due to the fact that most adhesives and encapsulants have a drop in viscosity upon heating, before polymerization and/or crosslinking occur in the curing operation. The reduced viscosity makes the material more prone to flow, which can result in bleed
[0003] Bleed presents a problem in semiconductor packaging because it typically is not easy to control Adhesive or encapsulant, or components thereof, can contaminate portions of the substrate outside of the intended bonding area If these portions include, for example, wire bond pads, subsequent manufacturing difficulties or device failures may result.
[0004] For these reasons there is a need to develop a method for containing or controlling the bleed of adhesives and encapsulants on substrates for integrated circuit packaging
SUMMARY OF THE INVENTION
[0005] This invention is a method of containing the bleed of adhesive on a substrate A narrow band of containment material is applied peripherally around a bonding area on the substrate, forming a border around the bonding area An adhesive is then applied to the bonding area within the border formed by the containment material The method is characterized by the fact that the contact angle of the containment material on the substrate is higher than the contact angle of the bonding area of the substrate In another embodiment of this method an adhesive is first applied to the bonding area of a substrate A narrow band of containment material is then applied peripherally around the bonding area, forming a border around the bonding area and the adhesive. The method is characterized by the fact that the contact angle of the containment material on the substrate is higher than the contact angle of the bonding area of the substrate
[0006] In another embodiment this invention is a substrate for the mounting of integrated circuits The substrate has a bonding area. An adhesive has been applied to the bonding area, and a narrow band of containment material has been applied peripherally around the bonding area, thereby forming a border around the bonding area and the adhesive The substrate is characterized by the fact that the contact angle of the containment material on the substrate is higher than the contact angle of the bonding area of the substrate
[0007] In another embodiment this invention is an integrated circuit device The device comprises a substrate for the mounting of integrated circuits, which has a bonding area thereon An adhesive has been applied to the bonding area, and a narrow band of containment material has been applied peripherally around the bonding area, thereby forming a border around the bonding area and the adhesive. The device is characterized by the fact that the contact angle of the containment material on the substrate is higher than the contact angle of the bonding area of the substrate
BRIEF DESCRIPTION OF THE FIGURES
[0008] FIGURE 1 illustrates a top perspective view of one embodiment of the containment material border on a substrate.
DEFINITIONS
[0009] As used herein, the term "contact angle" means the angle between the surface of a substrate and a tangent line drawn from a drop of deionized water resting on the surface of that substrate All contact angle measurements provided herein were measured on a Kruss goniometer at room temperature using a video capture system When the contact area of a material is cited, that contact angle was measured using deionized water on the surface as specified
[0010] As used herein, the term "adhesive" refers to a material used to bond, encapsulate, or underfill an adherend to a substrate
[001 1] As used herein, the term "resin" refers to any polymer, pre-polymer, oligomer, or monomer used in an adhesive formulation. Resins may be liquid at room temperature or may be solid at room temperature and dissolved within the adhesive formulation. Resins also may be solid at room temperature but liquid and/or flow-able at typical adhesive processing temperatures such as experienced during wirebonding, B-staging, and cure operations.
[0012] As used herein the term "bleed" refers to flow, wicking, or running of at least one adhesive component away from the adhesive application area on a substrate. As used herein, the term "B-staging" (and its variants) is used to refer to the processing of a material by heat or irradiation so that if the material is dissolved or dispersed in a solvent, the solvent is evaporated off with or without partial curing of the material, or if the material is neat with no solvent, the material is partially cured to a tacky or more hardened state, if the materia! is a flow-able adhesive, B-staging will provide extremely low flow without fully curing, such that additional curing may be performed after the adhesive is used to join one article to another. The reduction in flow may be accomplished by evaporation of a solvent, partial advancement or curing of a resin or polymer, or both.
[0013] As used herein the term "curing agent" is used to refer to any material or combination of materials that initiate, propagate, or accelerate cure of the composition and includes but is not limited to accelerators, catalysts, initiators, and hardeners
DETAILED DESCRIPTION OF THE INVENTION
[0014] FIGURE 1 illustrates a top perspective view of one embodiment of the containment material border on a substrate. The containment material forms a border around the bonding area so that the substrate input/outputs (I/Os) are protected from the adhesive that is applied to the bonding area. The specific substrate utilized for this invention is not especially important, and may be any that is suitable for a particular semiconductor package including ceramic, organic, or metallic substrates. The substrate may also be a semiconductor itself The substrate surface may be "bare" or may have been treated as required for the manufacture, functionality, and reliability of the device. Such treatments may include adhesion promoters, plasma treatments, organic surface protectants (OSP), or bleed reduction treatments (coatings) as may be performed by substrate manufacturers. The surface may have solder mask, electrical tracings, plating, or other surface enhancements. The contact angle of the substrate is determined by measuring the angle between the surface of the substrate and a tangent line drawn from a drop of deionized water resting on the surface of that substrate, in the bonding area (where no containment material has been applied).
[0015] The bonding area of the substrate may include a bond pad, an underfill area, an encapsulant area, or any place where an adhesive composition is to be applied and within which the bleed of the adhesive must be controlled or contained. The bonding area may be any size or shape as required for the particular application, and may include vacant or bare area in addition to area over which adhesive is to be applied and/or dies or components are to be placed The bounds of the bonding area are defined by the portions of the substrate onto which it is undesirable for adhesive components to flow These portions may include, for instance, substrate input/output terminals (1/Os) such as wire bond pads and discrete components such as capacitors and resistors
[0016] The containment material is any material that (a) may be applied to the substrate in a narrow band peripherally around the bonding area, and (b) has a contact angle, when applied to the substrate, which is higher than the contact angle of the bonding area of the substrate Examples of suitable containment materials include permanent ink markers, such as Sharpie®, available from Sanford Brands, aliphatic hydrocarbons such as those found in Thompson's® Water Seal®, commercially available from The Thompson's Company, isoparaffinic hydrocarbons, fluoroaliphatic resins, and combinations thereof such as found in Scotchgard™, which is commercially available from 3M Suitable containment materials could also include natural or synthetic waxes such as paraffin, parowax, microcrystalline waxes, petroleum wax blends, amorphous waxes, polyester waxes, soy wax, beeswax, and blends of those Suitable containment materials could also include a polyfluoπnated compound
[0017] The specific containment material selected will depend on such factors as ease of application, availability, process compatibility, and cost The effectiveness of a given containment material will depend, in part, on the specific resins to be contained, the substrate employed, and the downstream processing conditions In general, a larger difference between the contact angle of the substrate to which containment material has been applied and the contact angle of the bonding area of the substrate will yield more effective containment of the bleed
[0018] In one embodiment the containment material on the substrate has a contact angle that is at least 1 1 ° higher than the contact angle of the bonding area of the substrate In another embodiment the contact angle of the containment material on the substrate is at least 19° higher than the contact angle of the bonding area of the substrate In another embodiment the containment material on the substrate has a contact angle that is at least 55° higher than the contact angle of the bonding area of the substrate
[0019] The containment material is applied in a narrow band peripherally around the bonding area, such that a border is formed around the bonding area. The interior of the border defines the bonding area and the exterior of the border defines the area of the substrate that is to be protected from the bleed, or flow, of the adhesive or adhesive components The containment material is not applied in such a way as to form a physical dam or elevated barrier to the flow of the adhesive Rather, the containment material is applied in a thin layer, and is effective because it is not as easily wetted as the substrate Therefore, when adhesive or adhesive components flow to the containment material border, they are less likely to flow over the containment material because of the higher contact angle (lower surface energy) of the surface in that area. In this way the flow, or bleed, of the adhesive and its components is prevented from contaminating surfaces on the exterior of the border formed by the containment material.
[0020] The method of applying the containment material is not particularly important and may be any that is suited to yield a narrow band around a pre-defined area, such as dispensing, writing, painting, spreading, controlled spraying, stamping, transfer stamping, roller coating, jetting, and the like. The containment material is applied such that it forms a thin film or coating on the substrate, rather than a thick bead or dam. The containment material is specifically not applied universally to the whole substrate, and especially is not applied to the bonding area itself. That is, the containment material is not applied to the majority of the area of the substrate, but only in a narrow band around the bonding area. In this way the containment material will not interfere with the bonding of the adhesive to the substrate, as it might if it were applied to the bonding area itself. It also minimizes the chances that the containment material will interfere with circuitry or other structures on the surface of the substrate. Further, applying the containment material in this way minimizes material usage and cost compared to coating the majority of the substrate surface. The fact that the containment material is applied peripherally around the bonding area, forming a completely closed border, means that the bleed is contained within that border and thus the rest of the substrate need not be coated with the containment material in order to prevent adhesive from contaminating it.
[0021] The adhesive utilized this invention may be any that is suitable for the particular device and industrial process. It contains at least one component that is prone to bleed on the substrate under the processing conditions to be employed in the manufacturing operation. The adhesive may be used to bond an adherend to a substrate, such as in bonding a semiconductor chip to a metal leadframe or to an organic or ceramic substrate. The adhesive also may be used to encapsulate or underfill a device, such as with flip chip semiconductor packages. Examples of suitable adhesives include epoxies, acrylates or methacrylates, maleimides, vinyl ethers, polyesters, poly(butadienes), polyimides, benzocyclobutene, siliconized olefins, silicone resins, styrene resins, cyanate ester resins, polyolefins, or siloxanes and combinations thereof. Adhesives may be filled or unfilled and may contain additives commonly used in the art including curing agents, solvents, adhesion promoters such as silanes, diluents, and surfactants.
[0022] The method of applying the adhesive is not particularly important and may be any that is suitable for the particular device and industrial process to be utilized. The adhesive is applied within the interior portion of the border formed by the containment material. Examples of suitable methods of applying the adhesive include needle dispensing, coating, pen application, stamp transfer, roliers, controlled localized dipping, controlled localized spraying, and jetting.
[0023] In one embodiment the adhesive is applied to the bonding area of the substrate before the containment material is applied peripherally around the bonding area. The containment material is then applied before any downstream operations that are prone to causing bleed. For instance, in the situation where room temperature staging causes bleed, the containment material must be applied in a timely fashion to contain the bleed within the desired area. In the situation where bleed is caused by B-staging, the containment material must be applied before the B-staging operation. As another example, in the situation where bleed is not caused by B-staging but is caused by curing, the containment material may be applied any time before curing, including after the B-staging operation and before the curing step.
[0024] In another embodiment the containment material is applied peripherally around the bonding area of the substrate before the adhesive is applied to the bonding area.
[0025] After the adhesive and containment material have been applied the substrate or device may be processed in any manner suitable for the particular industrial use. The containment material blocks the bleed of the adhesive and its components during downstream operations such as room temperature staging or cure, B-staging, thermal and/or UV-cure, wirebonding, and reflow.
EXAMPLES
[0026] EXAMPLE 1 - Sharpie® Pen as Containment Material
[0027] A black ceramic substrate was treated with argon plasma for 12 minutes (250 Watts, 400 mTorr), and then 4 dots of resin or formulated product were applied to the substrate. A separate black ceramic substrate was also prepared without plasma treatment. To this substrate 4 resin dots, for each resin to be evaluated, were applied. The black ceramic substrate was selected because it is known for its propensity for inducing bleed with a variety of adhesives. The plasma treatment was employed to lower the substrate contact angle and thus enhance (make worse) bleed out or flow out. In addition to fully formulated products, pure resins were tested because fully formulated adhesives sometimes do not bleed as much as the pure resins. The specific formulated products and resins selected were those that were known to be particularly prone to bleed, in this way the examples were designed to test "worst case" examples of adhesive and resin bleed on a substrate. [0028] The following resins were tested: bismaleimide, epoxy, cyanate ester, and siliconized olefin. The following formulated products were tested: ABLEBOND® 3003 (siliconized olefin- based adhesive) and ABLEFILL® UF8802 (cyanate ester-based underfill).
[0029] After applying the dots to the substrate, a Sharpie® pen was used to draw on the substrate a narrow band, forming a border, around each of the dots. The substrates were then subjected to a cure simulation of a 45 minute ramp from room temperature to 1500C, followed by 90 minutes at 150°C. This simulation was selected to represent a typical cure cycle, lowering the viscosity of the resins and inducing them to flow on the substrate. Upon cooling, the specimens were visually evaluated for bleed performance. If the material bled onto or beyond the band of containment material the dot was considered "not contained". If the resin remained within the interior of the border formed by the containment material the dot was considered "contained". The number of dots that were "contained" were counted for each resin/containment material combination and the following designations were assigned: 4 contained dots was rated "excellent", 2-3 contained dots was rated "good", and 0 -1 contained dot was rated "poor". The results are summarized in Table 1. 0030 TABLE 1 - Exam le 1 results Shar ie en as containment material.
Figure imgf000008_0001
[0031] The Sharpie® pen provided some control over the bleed of the bismaleimide resin, especially on the plasma-treated substrate. The bleed with the other resins and adhesive formulations was very well-controlled. It is believed that the higher contact angle of the pen (see Example 4, below) prevented wetting of the substrate, containing the bleed of the resins and adhesives tested.
[0032] EXAMPLE 2 - Thompson's® Water Seal® as Containment Material
[0033] A black ceramic substrate was treated with argon plasma for 12 minutes (250 Watts, 400 mTorr), and then 4 dots of resin or formulated product were applied to the substrate. A separate black ceramic substrate was also prepared without plasma treatment. To this substrate 4 resin dots, for each resin to be evaluated, were applied. The black ceramic substrate was selected because it is known for its propensity for inducing bleed with a variety of adhesives. The plasma treatment was employed to lower the substrate contact angle and thus enhance (make worse) bleed out or flow out. In addition to fully formulated products, pure resins were tested because fully formulated adhesives sometimes do not bleed as much as the pure resins. The specific formulated products and resins selected were those that were known to be particularly prone to bleed. In this way the examples were designed to test "worst case" examples of adhesive and resin bleed on a substrate.
[0034] The following resins were tested: bismaleimide, epoxy, cyanate ester, and siliconized olefin. The following formulated products were tested: ABLEBOND® 3003 (siliconized olefin- based adhesive) and ABLEFILL® UF8802 (cyanate ester-based underfill).
[0035] After applying the dots to the substrate, Thompson's® Water Seal® was applied in a narrow band using a cotton swab to form a border around each dot. The substrates were then subjected to a cure simulation of a 45 minute ramp from room temperature to 150°C, followed by 90 minutes at 1500C. This simulation was selected to represent a typical cure cycle, lowering the viscosity of the resins and inducing them to flow on the substrate. Upon cooling, the specimens were visually evaluated for bleed performance. If the material bled onto or beyond the band of containment material the dot was considered "not contained". If the resin remained within the interior of the border formed by the containment material the dot was considered "contained". The number of dots that were "contained" were counted for each resin/containment material combination and the following designations were assigned: 4 contained dots was rated "excellent", 2-3 contained dots was rated "good", and 0 -1 contained dot was rated "poor". The results are summarized in Table 2. 0036 TABLE 2 - Exam le 2 results, Thom son's Water Seal® as containment material.
Figure imgf000009_0001
[0037] The Thompson's® Water Seal® provided some control over the bleed of the siliconized olefin resin, especially on the non-plasma-treated substrate. The bleed with the other resins and adhesive formulations was very well-controlled. It is believed that the higher contact angle of the Thompson's® Water Seal® (see Example 4, below) prevented wetting of the substrate, containing the bleed of the resins and adhesives tested.
[0038] EXAMPLE 3 - Scotchgard™ as Containment Materia!
[0039] A biack ceramic substrate was treated with argon plasma for 12 minutes (250 Watts, 400 mTorr), and then 4 dots of resin or formulated product were applied to the substrate. A separate black ceramic substrate was also prepared without plasma treatment. To this substrate 4 resin dots, for each resin to be evaluated, were applied. The black ceramic substrate was selected because it is known for its propensity for inducing bleed with a variety of adhesives The plasma treatment was employed to lower the substrate contact angle and thus enhance (make worse) bleed out or flow out In addition to fuliy formulated products, pure resins were tested because fully formulated adhesives sometimes do not bleed as much as the pure resins The specific formulated products and resins selected were those that were known to be particularly prone to bleed In this way the examples were designed to test 'worst case" examples of adhesive and resin bleed on a substrate
[0040] The following resins were tested bismaleimide, epoxy, cyanate ester, and siliconized olefin The following formulated products were tested ABLEBOND® 3003 (siliconized olefin- based adhesive) and ABLEFILL® UF8802 (cyanate ester-based underfill)
[0041] After applying the dots to the substrate, Scotchgard™ was applied in a narrow band using a cotton swab to form a border around each dot The substrates were then subjected to a cure simulation of a 45 minute ramp from room temperature to 15O0C, followed by 90 minutes at 15O0C This simulation was selected to represent a typical cure cycle, lowering the viscosity of the resins and inducing them to flow on the substrate. Upon cooling, the specimens were visually evaluated for bleed performance If the material bled onto or beyond the band of containment material the dot was considered "not contained ' If the resin remained within the interior of the border formed by the containment material the dot was considered "contained" The number of dots that were "contained" were counted for each resin/containment material combination and the following designations were assigned 4 contained dots was rated "excellent", 2-3 contained dots was rated "good", and 0 -1 contained dot was rated "poor" The results are summarized in Table 2.
[0042] TABLE 3 - Example 3 results, Scotchgard™ as containment material
Figure imgf000010_0001
[0043] The Scotchgard™ provided good to excellent control of the bleed with all of the resins and adhesives tested It is believed that the much higher contact angle of the Scotchgard™ (see Example 4, below) prevented wetting of the substrate, resulting in very good bleed containment performance [0044] EXAMPLE 4 - Contact Angle Measurements
[0045] Contact angle measurements were performed using a Kruss goniometer and deinoized water at room temperature A black ceramic substrate was prepared for contact angle measurement testing by (1) plasma treating the substrate with argon plasma for 12 minutes (250 Watts, 400 mTorr), (2) applying containment material to portions of the substrate and allowing the containment material to dry, and (3) subjecting the substrate with the containment material applied to a cure profile simulation of a 45 minute ramp from room temperature to 150°C, followed by 90 minutes at 150αC The following day, measurements were performed on an area of the substrate to which no containment material had been applied, as well as on areas of the substrate to which containment material had been applied For each area tested five measurements were taken and an arithmetic average contact angle was calculated The individual measurements and average contact angle data are presented in Table 4 below 0046 TABLE 4 - Contact An le Measurements in De rees
Figure imgf000011_0001
[0047] The bare substrate had a lower average contact angle than each of the substrates that had containment material thereon The higher contact angle (lower surface energy) of the surfaces with the containment material prevented wetting of the substrate, enabling a containment of the bleed The containment material with the highest contact angle (Scotchgard™), and thus, the largest differential compared to the bare substrate, gave the best performance in terms of bleed containment This indicates that it is desirable to have a differential between the contact angles of the bare substrate and the substrate with containment material that is as large as possible
[0048] Many modifications and variations of this invention can be made without departing from its spirit and scope, as will be apparent to those skilled in the art The specific embodiments described herein are offered by way of example only, and the invention is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled

Claims

What is claimed
1 A method of containing the bleed of adhesive on a substrate comprising the steps of a providing a substrate having a bonding area thereon with a first contact angle, b providing a containment material having a second contact angle on the substrate, c applying to the substrate a narrow band of the containment material peripherally around the bonding area, thereby forming a border around the bonding area, and d applying an adhesive onto the bonding area and within the interior of the border, wherein the second contact angle is higher than the first contact angle
2 A method of containing the bleed of adhesive on a substrate comprising the steps of a providing a substrate having a bonding area thereon with a first contact angle, b applying an adhesive onto the bonding area, c providing a containment material having a second contact angle on the substrate, and d applying to the substrate a narrow band of the containment material peripherally around the bonding area, thereby forming a border around the bonding area and the adhesive, wherein the second contact angle is higher than the first contact angle
3 The method of either claim 1 or claim 2 wherein the second contact angle is at least 11 ° more than the first contact angle
The method of either Claim 1 or Claim 2 wherein the containment material is selected from the group consisting of permanent ink markers, aliphatic hydrocarbons, isoparaffinic hydrocarbons, fluoroaliphatic resins, and combinations of these
The method of either Claim 1 or Claim 2 wherein the adhesive comprises a resin selected from the group consisting of bismaleimide, epoxy, siloxane, , and cyanate ester
A substrate for the mounting of integrated circuits having a bonding area thereon with a first contact angle, wherein an adhesive has been applied to the bonding area, and a narrow band of containment material having a second contact angle on the substrate has been applied peripherally around the bonding area, thereby forming a border around the bonding area and the adhesive, wherein the second contact angle is higher than the first contact angle The substrate of Claim 6 wherein the second contact angle is at least 11 ° more than the first contact angle
The substrate of Claim 6 wherein the containment material is selected from the group consisting of permanent ink markers, aliphatic hydrocarbons, isoparaffinic hydrocarbons, fluoroaliphatic resins, and combinations of these
The substrate of Claim 6 wherein the adhesive comprises a resin selected from the group consisting of bismaleimide, epoxy, siloxane, and cyanate ester
An integrated circuit device comprising a substrate for the mounting of integrated circuits having a bonding area thereon with a first contact angle, wherein an adhesive has been applied to the bonding area, and a narrow band of containment material having a second contact angle on the substrate has been applied peripherally around the bonding area, thereby forming a border around the bonding area and the adhesive, wherein the second contact angle is higher than the first contact angle
The device of Claim 10 wherein the second contact angle is at least 11 ° more than the first contact angle
The device of Claim 10 wherein the containment material is selected from the group consisting of permanent ink markers, aliphatic hydrocarbons, isoparaffinic hydrocarbons, fluoroaliphatic resins, and combinations of these
The device of Claim 10 wherein the adhesive comprises a resin selected from the group consisting of bismaleimide, epoxy, siloxane, and cyanate ester
PCT/US2007/085258 2007-11-20 2007-11-20 Method of containing resin bleed WO2009067111A1 (en)

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