WO1993012190A1 - Conductive adhesive compositions based on thermally depolymerisable polymers - Google Patents

Conductive adhesive compositions based on thermally depolymerisable polymers Download PDF

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Publication number
WO1993012190A1
WO1993012190A1 PCT/GB1992/002290 GB9202290W WO9312190A1 WO 1993012190 A1 WO1993012190 A1 WO 1993012190A1 GB 9202290 W GB9202290 W GB 9202290W WO 9312190 A1 WO9312190 A1 WO 9312190A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
adhesive
thermally
polymer
depolymerisable
Prior art date
Application number
PCT/GB1992/002290
Other languages
French (fr)
Inventor
Alison Mary Wagland
Andrew David Price
Geoffrey Andrew Paterson
Charles Edmund King
Andrew M'intosh Soutar
Original Assignee
Cookson Group Plc
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
Priority claimed from GB919126923A external-priority patent/GB9126923D0/en
Priority claimed from GB919126928A external-priority patent/GB9126928D0/en
Application filed by Cookson Group Plc filed Critical Cookson Group Plc
Publication of WO1993012190A1 publication Critical patent/WO1993012190A1/en

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    • H—ELECTRICITY
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
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    • C09J201/00—Adhesives based on unspecified macromolecular compounds
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Definitions

  • the present invention relates to conductive filled adhesive compositions which can be reworked on heating.
  • Conductive adhesive compositions are known which generally comprise an adhesive, such as an epoxy adhesive, loaded with conducting metal particles such as silver. Such adhesives are used to attach components, such as silicon chips, or leads to circuits which may not be suitable for soldering.
  • a particular disadvantage of conducting adhesives is that they are difficult, if not impossible, to remove without destroying the substrate and/or the components attached to the substrate. Thus, reworking of the circuit, for example by replacement of an outdated component, or repair of the circuit, for example by replacement of a damaged component, is very difficult.
  • the present invention provides an electrically or thermally conductive adhesive composition which comprises at least one thermally depolymerisable polymer which decomposes to volatile or gaseous products at a temperature in the range of from 100°C to 350°C and silver, gold, aluminium nitride, alumina, aluminium, copper, nickel, silicon, diamond or silver coated particles, or a mixture thereof.
  • Conductivity is imparted to the composition by the incorporation of the silver, gold, aluminium, nitride, alumina, aluminium, copper, silicon, diamond or silver coated particles therein, which may be included in an amount of up to 85% by volume of the adhesive, more preferably 25 to 45% by volume of the adhesive.
  • the thermally depolymerisable polymers are preferably incoporated into the adhesive compositions of the present invention in an amount of from 1 to 20% by weight, more preferably from 1 to 10% by weight when the polymers are solid and more preferably from 5 to 20% by weight when the polymers are liquid.
  • thermally depolymerisable polymers which are used in the adhesive compositions of the present invention may be the thermally depolymerisable polycarbonates which are described in our European Patent Application No. 91305298.1, i.e. the thermally depolymerisable polymer may be a thermally depolymerisable polycarbonate containing the repeating units
  • R and R are the same or different and each independently represents a hydrocarbon group containing from 4 to 30 carbon atoms, the said group having a tertiary carbon atom, an allylie, propargylic or benzylic group attached directly to at least one oxygen atom.
  • the thermally depolymerisable polycarbonates used in the present invention may be produced by the condensation reaction between a diol, or a mixture of diols, and phosgene or a phosgene analogue such as 1,l ⁇ -carbonyldiimidazole.
  • the polycarbonates owe their thermal lability to the structure of the diols which are used in their production.
  • the diols generally possess tertiary benzylic, allylic or propargylic groups bonded to the hydroxyl functional groups in the diols.
  • thermally depolymerisable polymers which may be used in the present invention are the polyoxalates and polymalonates which are disclosed in our PCT Patent Application PCT/GB92/01573.
  • the poly ⁇ oxalates and polymalonates as described therein are polymers or copolymers containing repeating groups of the formula
  • R 1 and R2 are each independently a hydrocarbon group containing from 4 to 30 carbon atoms which has a tertiary carbon atom attached to at least one of the bridging oxygen atoms,
  • R 3 , R 3 ' , R 4 and R 4 ' are each independently a hydrogen atom, an alkyl group containing from 1 to 12 carbon atoms, an aryl group, a heterocyclic group or an acyl group containing from 1 to 12 carbon atoms, and n and n are 0 to 1.
  • R , R ' and R , R ' are all hydrogen atoms, or one of R 3, R3 and R4, R4 i.s a hydrogen atom and the other is an acyl group containing from 1 to 12 carbon atoms.
  • Copolymers which comprise groups of the formula
  • R and R each independently represents a hydrocarbon group containing from 4 to 30 carbon atoms, the said group having a tertiary carbon atom, an allylic, propargylic or benzylic group attached directly to at least one oxygen atom, i.e. copolymers of oxalate/carbonate or malonate/carbonate, may also be used.
  • the oxalate and malonate polymers used in the present invention may be produced by the condensation reaction between a diol, or a mixture of diols and an oxalyl and/or malonyl moiety, such as an acid chloride, acid or ester.
  • the diols which may be used in the preparation of the polymers have the general formula:
  • R 1 and R2 are as defined above.
  • the polyoxalates and polymalonates used in the present invention owe their thermal lability to the structure of the diols which are used in their preparation, as a result of the diols possessing a tertiary carbon atom bonded to at least one of the hydroxyl functional groups in the diol.
  • diols which may be used are 2,5- dimethylhexane-2,5-diol, 2-5-dimethylhex-3-yne-2,5- diol and ⁇ , ⁇ , ⁇ ' , ⁇ '-tetramethyl-l,4-benzene dimethanol, or a mixture of two or more thereof.
  • thermally depolymerisable polymers which may be used in the present invention are: i) poly(methylmethacrylate) , the decomposition of which is essentially a reverse of its polymerisation leading to a monomer in 100% yield, ii) poly( ⁇ -methylstyrene) , the decomposition of which begins at 250 C and proceeds rapidly at 300°C to essentially 100% monomer. iii) poly(oxymethylene) , which depolymerises between 100° and 180°C to form formaldehyde.
  • the uncapped polymer is unstable in most solvents but end-capped poly(oxymethylene) is stable, the end-capped polymers containing thermally removable groups such as tertiary butyl being thermally depolymerisable.
  • thermally removable groups such as tertiary butyl being thermally depolymerisable.
  • acid depolymerisable polymers such as polyacetals, polyketals, polyorthoesters, polyamidoacetals, polyenolethers and poly-N- acylaminocarboxylic acids, which undergo cleavage under the influence of acid catalysis. Materials of this type have been described for lithographic use in US Patents Nos. 4101323, 4427611, 4248957 and 4250247.
  • poly(phthaldehydes) as described in Polymer Engineering and Science, 1983, 2_3, 1012 as materials for dry film resists.
  • the polymers have ceiling temperatures well • below room temperature and must therefore be prepared at cryogenic temperatures. If the polymers are end-capped by acylation or alkylation prior to warming, they are stable to about 180 C and will decompose totally by 230°C.
  • polyesters which incorporate a tertiary, benzylic, allylic or propargylic group adjacent to the ester oxygen in the main chain will depolymerise on heating to a temperature in the range of from 100 C to 350°C.
  • polyesters are derived from dicarboxylic acids, such as isophthalic or terephthalic acids, with appropriately substituted diols containing the tertiary, benzylic, allylic or propargylic groups.
  • dicarboxylic acids such as isophthalic or terephthalic acids
  • diols containing the tertiary, benzylic, allylic or propargylic groups are described in Poly. Mater. Sci. Eng. , 1989, ' 60, 170 and J. Photopolym. Sci. Techno1. , 1990, 3 . , 235. It should be noted that the temperatures of decomposition of this family of polymers can be reduced if a catalytic amount of a strong acid is present.
  • Such an acid can be released thermally from suitable materials, vii) polyethers which incorporate a tertiary, benzylic, allylic or propargylic group adjacent to the ether oxygen will decompose in the temperature range 150 C to 300°C, if a catalytic amount of strong acid is present.
  • This acid can be released thermally from suitable materials.
  • the synthesis and use of these polymers as self-developing imaging systems are described in Poly. Mater. Sci. Eng. , 1989, 60, 170.
  • the thermally depolymerisable polymer may be used to form the base of the adhesive composition.
  • the thermally depolymerisable polymer may be combined with an adhesive composition based upon another material, for example an epoxy adhesive a silicone adhesive, a cyano-acrylate adhesive, a phenolic adhesive, a polyurethane adhesive or an isocyanate adhesive.
  • an adhesive composition based upon another material
  • an epoxy adhesive a silicone adhesive, a cyano-acrylate adhesive, a phenolic adhesive, a polyurethane adhesive or an isocyanate adhesive.
  • Conventional curing agents, hardeners and other well known additives may be incorporated in the adhesive compositions of the invention, as desired.
  • the thermally depolymerisable polymer may thus be blended with the other material or materials to form either a homogeneous or non-homogeneous blend.
  • the thermally depolymerisable polymer may, for example, be incorporated into an anisotropic conducting adhesive.
  • the conductive adhesive composition of the present invention is in the form of a paste
  • other types of adhesive composition are included within the scope of the present invention, for example, adhesives which are very dilute and where there is a lot of solvent loss before an adhesive bond is formed, and adhesives which are in the form of a tape.
  • the thermally depolymerisable polymers used in the adhesive compositions of the present invention depolymerise when heated to a temperature of below 350°C to form small volatile molecules.
  • the decomposition on heating of the thermally depolymerisable polymer enables the adhesive to be reworked and any components attached by means of the adhesive to be demounted and replaced or upgraded, as necessary.
  • On decomposition of the thermally depolymerisable polymer residue levels of less than 5% by weight are formed, based on the thermally depolymerisable polymer, and the low residue levels are clearly advantageous when the adhesive requires to be reworked.
  • the electrically conductive adhesives of the present invention may be used for the attachment of leads or components to a circuit. Such adhesives would therefore find use in surface mount technology, so called SMT, where lead/tin solders are commonly used to provide mechanical and electrical interconnection between components and, for instance, a printed circuit board.
  • the compositions of the present invention may be used as die attach compositions for the attachment of silicon chips or thin layer integrated circuits to a suitable substrate.
  • the die attach compositions which contain silver, silver coated or aluminium nitride particles possess a high thermal conductivity which is required to remove heat from an active silicon chip.
  • the die attach compositions can be thermally decomposed if rework or repair is required.
  • the present invention also includes within its scope an adhesive joint or bond which is formed from an adhesive composition as hereinbefore defined.
  • Aluminium stubs (base diameter 7mm and base height 2mm) coated with an epoxy resin, for use with a Sebastian pull tester - Model III were clamped firmly to squares of "Hyperpure" polished silicon (thickness 381 ⁇ m, resistivity 2-15 ⁇ cm and type/dopant p/B) of side 9mm. The stubs were then cured for one hour at 150 C to cure the epoxy resin coatings.
  • the conducting adhesive had a bond strength of
  • the dispersion of a depolymerisable polycarbonate in the adhesive and subsequent heating to cause depolymerisation significantly reduced the bond strength of the silicon to the substrate.
  • Samples were prepared as for Example 1 above but using a 50 ⁇ m wire to control the bond thickness.
  • the adhesives tested in this case were: a) Cured conducting silver adhesive only. b) Cured conducting silver adhesive only with subsequent heating at 220 C for ten minutes. c) Cured conducting silver adhesive containing 3% by weight of a polycarbonate as described in Example 1, milled and sieved to sub 16 ⁇ m particle size and dispersed as before. d) Cured conducting silver adhesive containing 3% by weight of a polycarbonate as described in Example 1, milled and sieved to sub 16 ⁇ m particle size and dispersed as before with subsequent heating at 220 C for ten minutes.
  • the conducting adhesive had a bond strength of
  • the mode of failure prior to depolymerisation invariably includes intra silicon fracture, whereas after depolymerisation the failure mode shifts to interbond line failure.

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Abstract

An electrically or thermally conductive adhesive composition which comprises at least one thermally depolymerisable polymer which decomposes to volatile or gaseous products at a temperature in the range of from 100 °C to 350 °C and silver, gold, aluminium nitride, alumina, aluminium, copper, nickel, silicon, diamond or silver coated-particles, or a mixture thereof.

Description

CONDUCTIVE ADHESIVE COMPOSITIONS BASED ON THERMALLY DEPOLYMERISABLE POLYMERS.
The present invention relates to conductive filled adhesive compositions which can be reworked on heating.
Conductive adhesive compositions are known which generally comprise an adhesive, such as an epoxy adhesive, loaded with conducting metal particles such as silver. Such adhesives are used to attach components, such as silicon chips, or leads to circuits which may not be suitable for soldering. A particular disadvantage of conducting adhesives is that they are difficult, if not impossible, to remove without destroying the substrate and/or the components attached to the substrate. Thus, reworking of the circuit, for example by replacement of an outdated component, or repair of the circuit, for example by replacement of a damaged component, is very difficult.
We have now developed a conductive adhesive composition which overcomes the above described problems and enables the adhesive composition to be reworked on heating.
Accordingly, the present invention provides an electrically or thermally conductive adhesive composition which comprises at least one thermally depolymerisable polymer which decomposes to volatile or gaseous products at a temperature in the range of from 100°C to 350°C and silver, gold, aluminium nitride, alumina, aluminium, copper, nickel, silicon, diamond or silver coated particles, or a mixture thereof.
Conductivity is imparted to the composition by the incorporation of the silver, gold, aluminium, nitride, alumina, aluminium, copper, silicon, diamond or silver coated particles therein, which may be included in an amount of up to 85% by volume of the adhesive, more preferably 25 to 45% by volume of the adhesive.
The thermally depolymerisable polymers are preferably incoporated into the adhesive compositions of the present invention in an amount of from 1 to 20% by weight, more preferably from 1 to 10% by weight when the polymers are solid and more preferably from 5 to 20% by weight when the polymers are liquid.
The thermally depolymerisable polymers which are used in the adhesive compositions of the present invention may be the thermally depolymerisable polycarbonates which are described in our European Patent Application No. 91305298.1, i.e. the thermally depolymerisable polymer may be a thermally depolymerisable polycarbonate containing the repeating units
(R -0-C-0-R -O-C-0)
where R and R are the same or different and each independently represents a hydrocarbon group containing from 4 to 30 carbon atoms, the said group having a tertiary carbon atom, an allylie, propargylic or benzylic group attached directly to at least one oxygen atom.
The thermally depolymerisable polycarbonates used in the present invention may be produced by the condensation reaction between a diol, or a mixture of diols, and phosgene or a phosgene analogue such as 1,lΛ-carbonyldiimidazole.
The polycarbonates owe their thermal lability to the structure of the diols which are used in their production. The diols generally possess tertiary benzylic, allylic or propargylic groups bonded to the hydroxyl functional groups in the diols. Examples of diols which may be used in the preparation of the polycarbonates used in the present invention include m-benzenedimethanol, 2,5-dimethyl-2,5-hexanediol, 2-cyclohexen-l,4-diol, 2-butyne-l,4-diol, p-bis(l- hydroxyethyl)benzene and α, α, α' , α'-tetramethyl- 1,4-benzenedimethanol, or a mixture of two or more thereof.
Other thermally depolymerisable polymers which may be used in the present invention are the polyoxalates and polymalonates which are disclosed in our PCT Patent Application PCT/GB92/01573. The poly¬ oxalates and polymalonates as described therein are polymers or copolymers containing repeating groups of the formula
Figure imgf000005_0001
wherein R 1 and R2 are each independently a hydrocarbon group containing from 4 to 30 carbon atoms which has a tertiary carbon atom attached to at least one of the bridging oxygen atoms,
R3 , R3' , R4 and R4' are each independently a hydrogen atom, an alkyl group containing from 1 to 12 carbon atoms, an aryl group, a heterocyclic group or an acyl group containing from 1 to 12 carbon atoms, and n and n are 0 to 1.
When n and n' are 0 the polymers are oxalates and when n and n' are 1 the polymers are malonates. When
3 3 4 4 n and n' are 1 preferably R , R ' and R , R ' are all hydrogen atoms, or one of R 3, R3 and R4, R4 i.s a hydrogen atom and the other is an acyl group containing from 1 to 12 carbon atoms.
Copolymers which comprise groups of the formula
Figure imgf000006_0001
are each as defined above and groups of the formula
0 0 (R 5-0-1C1-O-R6-0-ICI-O)
where. R and R each independently represents a hydrocarbon group containing from 4 to 30 carbon atoms, the said group having a tertiary carbon atom, an allylic, propargylic or benzylic group attached directly to at least one oxygen atom, i.e. copolymers of oxalate/carbonate or malonate/carbonate, may also be used.
The oxalate and malonate polymers used in the present invention may be produced by the condensation reaction between a diol, or a mixture of diols and an oxalyl and/or malonyl moiety, such as an acid chloride, acid or ester.
The diols which may be used in the preparation of the polymers have the general formula:
HO-R^OH and/or H0-R2-0H
where R 1 and R2 are as defined above.
The polyoxalates and polymalonates used in the present invention owe their thermal lability to the structure of the diols which are used in their preparation, as a result of the diols possessing a tertiary carbon atom bonded to at least one of the hydroxyl functional groups in the diol.
Examples of diols which may be used are 2,5- dimethylhexane-2,5-diol, 2-5-dimethylhex-3-yne-2,5- diol and α,α,α' ,α'-tetramethyl-l,4-benzene dimethanol, or a mixture of two or more thereof.
Further examples of thermally depolymerisable polymers which may be used in the present invention are: i) poly(methylmethacrylate) , the decomposition of which is essentially a reverse of its polymerisation leading to a monomer in 100% yield, ii) poly(α-methylstyrene) , the decomposition of which begins at 250 C and proceeds rapidly at 300°C to essentially 100% monomer. iii) poly(oxymethylene) , which depolymerises between 100° and 180°C to form formaldehyde. The uncapped polymer is unstable in most solvents but end-capped poly(oxymethylene) is stable, the end-capped polymers containing thermally removable groups such as tertiary butyl being thermally depolymerisable. iv) acid depolymerisable polymers, such as polyacetals, polyketals, polyorthoesters, polyamidoacetals, polyenolethers and poly-N- acylaminocarboxylic acids, which undergo cleavage under the influence of acid catalysis. Materials of this type have been described for lithographic use in US Patents Nos. 4101323, 4427611, 4248957 and 4250247. v) poly(phthaldehydes) as described in Polymer Engineering and Science, 1983, 2_3, 1012 as materials for dry film resists. The polymers have ceiling temperatures well • below room temperature and must therefore be prepared at cryogenic temperatures. If the polymers are end-capped by acylation or alkylation prior to warming, they are stable to about 180 C and will decompose totally by 230°C. vi) polyesters which incorporate a tertiary, benzylic, allylic or propargylic group adjacent to the ester oxygen in the main chain will depolymerise on heating to a temperature in the range of from 100 C to 350°C. These polyesters are derived from dicarboxylic acids, such as isophthalic or terephthalic acids, with appropriately substituted diols containing the tertiary, benzylic, allylic or propargylic groups. The synthesis and use of these materials as self-developing imaging systems, are described in Poly. Mater. Sci. Eng. , 1989, ' 60, 170 and J. Photopolym. Sci. Techno1. , 1990, 3., 235. It should be noted that the temperatures of decomposition of this family of polymers can be reduced if a catalytic amount of a strong acid is present. Such an acid can be released thermally from suitable materials, vii) polyethers which incorporate a tertiary, benzylic, allylic or propargylic group adjacent to the ether oxygen will decompose in the temperature range 150 C to 300°C, if a catalytic amount of strong acid is present. This acid can be released thermally from suitable materials. The synthesis and use of these polymers as self-developing imaging systems are described in Poly. Mater. Sci. Eng. , 1989, 60, 170. The thermally depolymerisable polymer may be used to form the base of the adhesive composition. Alternatively, the thermally depolymerisable polymer may be combined with an adhesive composition based upon another material, for example an epoxy adhesive a silicone adhesive, a cyano-acrylate adhesive, a phenolic adhesive, a polyurethane adhesive or an isocyanate adhesive. Conventional curing agents, hardeners and other well known additives may be incorporated in the adhesive compositions of the invention, as desired. The thermally depolymerisable polymer may thus be blended with the other material or materials to form either a homogeneous or non-homogeneous blend. The thermally depolymerisable polymer may, for example, be incorporated into an anisotropic conducting adhesive.
Whilst it is preferred that the conductive adhesive composition of the present invention is in the form of a paste, other types of adhesive composition are included within the scope of the present invention, for example, adhesives which are very dilute and where there is a lot of solvent loss before an adhesive bond is formed, and adhesives which are in the form of a tape.
The thermally depolymerisable polymers used in the adhesive compositions of the present invention depolymerise when heated to a temperature of below 350°C to form small volatile molecules. The decomposition on heating of the thermally depolymerisable polymer enables the adhesive to be reworked and any components attached by means of the adhesive to be demounted and replaced or upgraded, as necessary. On decomposition of the thermally depolymerisable polymer residue levels of less than 5% by weight are formed, based on the thermally depolymerisable polymer, and the low residue levels are clearly advantageous when the adhesive requires to be reworked.
The electrically conductive adhesives of the present invention may be used for the attachment of leads or components to a circuit. Such adhesives would therefore find use in surface mount technology, so called SMT, where lead/tin solders are commonly used to provide mechanical and electrical interconnection between components and, for instance, a printed circuit board.
Alternatively, the compositions of the present invention, particularly when containing silver, silver coated or aluminium nitride particles, may be used as die attach compositions for the attachment of silicon chips or thin layer integrated circuits to a suitable substrate. The die attach compositions which contain silver, silver coated or aluminium nitride particles possess a high thermal conductivity which is required to remove heat from an active silicon chip. In accordance with the present invention, the die attach compositions can be thermally decomposed if rework or repair is required.
The present invention also includes within its scope an adhesive joint or bond which is formed from an adhesive composition as hereinbefore defined.
The present invention will be further described with reference to the following non-limiting Examples.
Exam le l
Aluminium stubs (base diameter 7mm and base height 2mm) coated with an epoxy resin, for use with a Sebastian pull tester - Model III were clamped firmly to squares of "Hyperpure" polished silicon (thickness 381μm, resistivity 2-15 Ωcm and type/dopant p/B) of side 9mm. The stubs were then cured for one hour at 150 C to cure the epoxy resin coatings.
The silicon squares, with the aluminium bonded studs, were then bonded to alumina substrates with particular test adhesives and cured for one hour at 120°C, followed by one hour at 170°C. The bond thickness was 150μm which was controlled by placing a ring of 150μm wire beneath the silicon squares.
Four adhesive variants were tested, as follows: a) Cured conducting silver adhesive only. b) Cured conducting silver adhesive with subsequent heating at 220 C for ten minutes. c) Cured conducting adhesive containing 2% by weight of a polycarbonate sieved to sub 75μm particle size and dispersed using a mixer. The polycarbonate was prepared from 2,5-dimethyl-0,0 -bis-(1-imidazolylcarbony1) 2,5-hexandiol and 1,4-benzenedimethanol. d) Cured conducting adhesive containing 2% by weight of the polycarbonate described in (c) above sieved to sub 75/.m particle size and dispersed as above, with subsequent heating at 220° for ten minutes.
Heating at 220 C for ten minutes was sufficient for all of the polycarbonate to depolymerise.
The samples then underwent Sebastian tensile pull tests and the following results were obtained.
1) The conducting adhesive had a bond strength of
2 ~70kg/cm and this bond strength was reduced by
14% by the process of heating at 220 C for ten minutes .
2) The addition of 2% of the polycarbonate to the adhesive reduced the bond strength by 43%.
3) However on depolymerising the polycarbonate in the conducting adhesive by heating at 220°C for ten minutes the bond strength was further reduced by 30%.
The dispersion of a depolymerisable polycarbonate in the adhesive and subsequent heating to cause depolymerisation significantly reduced the bond strength of the silicon to the substrate.
Example 2
Samples were prepared as for Example 1 above but using a 50μm wire to control the bond thickness. The adhesives tested in this case were: a) Cured conducting silver adhesive only. b) Cured conducting silver adhesive only with subsequent heating at 220 C for ten minutes. c) Cured conducting silver adhesive containing 3% by weight of a polycarbonate as described in Example 1, milled and sieved to sub 16μm particle size and dispersed as before. d) Cured conducting silver adhesive containing 3% by weight of a polycarbonate as described in Example 1, milled and sieved to sub 16μm particle size and dispersed as before with subsequent heating at 220 C for ten minutes.
The samples were cured and tested as before using a Sebastian pull tester - Model III and the following results were obtained:
1) The conducting adhesive had a bond strength of
2
-76kg/cm and this was reduced by only 8% by the process of heating for ten minutes at 220 C.
2) The addition of 3% of the polycarbonate to the adhesive reduced the bond strength to ~35kg/cm 2.
3) On depolymerising the polycarbonate in the conducting adhesive by heating at 220°C for ten minutes the bond strength was further reduced by 34%.
To conclude, the dispersion of a depolymerisable polycarbonate in the adhesive and subsequent heating to cause depolymerisation significantly reduced the bond strength of the silicon to the substrate.
In both Examples the mode of failure prior to depolymerisation invariably includes intra silicon fracture, whereas after depolymerisation the failure mode shifts to interbond line failure.

Claims

CLAIMS :
1. An electrically or thermally conductive adhesive composition which comprises at least one thermally depolymerisable polymer which decomposes to volatile or gaseous products at a temperature in the range of from 100°C to 350°C and silver, gold, aluminium nitride, alumina, aluminium, copper, nickel, silicon, diamond or silver coated-particles, or a mixture thereof.
2. An adhesive composition as claimed in claim 1 which is rendered conductive by the incorporation of silver or silver coated particles therein.
3. An adhesive composition as claimed in claim 1 which is rendered conductive by the incorporation of aluminium nitride particles therein.
4. An adhesive composition as claimed in any one of claims 1 to 3 wherein the particles comprise up to 85% by volume of the adhesive composition.
5. An adhesive composition as claimed in claim 4 wherein the said particles comprise from 25 to 45% by volume of the adhesive composition.
6. An adhesive composition as claimed in any one of the preceding claims wherein the thermally depolymerisable polymer is a thermally depolymerisable polycarbonate containing the repeating units
0 0 II " II (R -0-C-O-R -0-C-O) I It where R and R are the same or different and each independently represents a hydrocarbon group containing from 4 to 30 carbon atoms, the said group having a tertiary carbon atom, an allylic, propargylic or benzylic group attached directly to at least one oxygen atom.
7. An adhesive composition as claimed in claim 6
I II wherein the groups R and R in the thermally depolymerisable polycarbonate each independently represent a hydrocarbon group containing from 4 to 12 carbon atoms.
8. An adhesive composition as claimed in claim 6 or claim 7 wherein the thermally depolymerisable polycarbonate is prepared by the condensation reaction between a diol, or mixture of diols, and phosgene or a phosgene analogue.
9. An adhesive composition as claimed in any one of claims 1 to 5 wherein the thermally depolymerisable polymer is a polymer or copolymer containing repeating groups of the formula:
- R1-O- -o- »-O4 C*1- L -
Figure imgf000015_0001
wherein R 1 and R2 are each independently a hydrocarbon group containing from 6 to 30 carbon atoms which has a tertiary carbon atom attached to at least one of the bridging oxygen atoms,
Figure imgf000015_0002
independently a hydrocarbon atom, an alkyl group containing from 1 to 12 carbon atoms, an aryl group, a heterocylic group or an acyl group containing from 1 to 12 carbon atoms, and n and n' are 0 to 1.
10. An adhesive composition as claimed in claim 9 wherein n and n' are 1 and R 3, R3' and R4,
R 4' are all hydrogen atoms, or one of R3 and R 4, or R3' and R4 , s a hydrogen atom and the other is an acyl group containing from 1 to 12 carbon atoms.
11. An adhesive composition as claimed in claim 9 or claim 10 wherein one of n and nr is 0 and the other of n and n' is 1.
12. A adhesive composition as claimed in any one of claims 9 to 11 wherein the polymer or copolymer is prepared by the condensation of a diol of the general formula:
H0-R1-0H and/or H0-R2-0H
wherein R 1 and R2 are as defi.ned i.n clai.m 5 wi.th an oxalyl and/or malonyl moiety.
13. A conducting adhesive composition as claimed in any one of claims 1 to 6 wherein the thermally depolymerisable polymer is poly(methylmethacrylate) , poly(α-methylstyrene) , poly(oxymethylene) , poly(phthaldehyde) , a polyester with a tertiary group adjacent to an ester oxygen in the main chain, a polyether with a tertiary group adjacent to an ether oxygen in the main chain, or an acid depolymerisable polymer.
14. An adhesive composition as claimed in any one of the preceding claims wherein the thermally depolymerisable polymer is combined with an adhesive composition based upon another material.
15. An adhesive compostion as claimed in claim 14 wherein the other material is an epoxy adhesive, a silicone adhesive, a cyano-acrylate adhesive, a phenolic adhesive, a polyurethane adhesive, or an isocyanate adhesive.
16. An adhesive composition as claimed in claim 14 or claim 15 wherein the thermally depolymerisable polymer is blended with the other material.
17. An adhesive composition as claimed in any one of the preceding claims which comprises from 1 to . 20% by weight of the thermally depolymerisable polymer.
18. An adhesive composition as claimed in any one of claims 1 to 17 which is used for the attachment of components or leads to a circuit.
19. An adhesive composition as claimed in any one of claims 1 to 17 containing silver, silver coated or aluminium nitride particles which is a die attach composition for use in the attachment of a silicon chip to a substrate.
20. A silicon chip or any thin layer integrated circuit whenever mounted on a substrate using a die attach composition as claimed in claim 19.
21. An adhesive joint or bond between two surfaces which is formed from an adhesive composition as claimed in any one of claims 1 to 17.
PCT/GB1992/002290 1991-12-19 1992-12-10 Conductive adhesive compositions based on thermally depolymerisable polymers WO1993012190A1 (en)

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GB919126923A GB9126923D0 (en) 1991-12-19 1991-12-19 Conductive silver filled adhesive compositions
GB9126923.3 1991-12-19
GB919126928A GB9126928D0 (en) 1991-12-19 1991-12-19 Die attach compositions

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DE19527476A1 (en) * 1995-07-27 1997-01-30 Leybold Ag Sputtering target with highly adherent sputtering material - bonded to base plate by inexpensive metal powder-contg. epoxide adhesive
EP1041380A2 (en) * 1999-04-01 2000-10-04 Matsushita Electric Industrial Co., Ltd. Hydrocarbon sensor and method of producing the same
DE102006007528B4 (en) * 2005-03-02 2007-08-02 Mitac Technology Corp. Process for the preparation of a bonding agent
DE102008034952A1 (en) * 2008-07-26 2010-01-28 Semikron Elektronik Gmbh & Co. Kg Noble metal compounding agents and methods of use for this purpose
CN110549040A (en) * 2019-09-11 2019-12-10 桂林电子科技大学 Aluminum nitride/nano-silver solder paste heat conduction material and preparation method thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19527476A1 (en) * 1995-07-27 1997-01-30 Leybold Ag Sputtering target with highly adherent sputtering material - bonded to base plate by inexpensive metal powder-contg. epoxide adhesive
EP1041380A2 (en) * 1999-04-01 2000-10-04 Matsushita Electric Industrial Co., Ltd. Hydrocarbon sensor and method of producing the same
EP1041380B1 (en) * 1999-04-01 2010-12-29 Panasonic Corporation Hydrocarbon sensor and method of producing the same
DE102006007528B4 (en) * 2005-03-02 2007-08-02 Mitac Technology Corp. Process for the preparation of a bonding agent
DE102008034952A1 (en) * 2008-07-26 2010-01-28 Semikron Elektronik Gmbh & Co. Kg Noble metal compounding agents and methods of use for this purpose
DE102008034952B4 (en) * 2008-07-26 2016-05-19 Semikron Elektronik Gmbh & Co. Kg Noble metal compounding agents and methods of use for this purpose
CN110549040A (en) * 2019-09-11 2019-12-10 桂林电子科技大学 Aluminum nitride/nano-silver solder paste heat conduction material and preparation method thereof
CN110549040B (en) * 2019-09-11 2021-09-14 桂林电子科技大学 Aluminum nitride/nano-silver solder paste heat conduction material and preparation method thereof

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