EP0953008A4 - HARDENABLE RESIN COMPOSITIONS - Google Patents

HARDENABLE RESIN COMPOSITIONS

Info

Publication number
EP0953008A4
EP0953008A4 EP98904585A EP98904585A EP0953008A4 EP 0953008 A4 EP0953008 A4 EP 0953008A4 EP 98904585 A EP98904585 A EP 98904585A EP 98904585 A EP98904585 A EP 98904585A EP 0953008 A4 EP0953008 A4 EP 0953008A4
Authority
EP
European Patent Office
Prior art keywords
composition
meth
epoxy resin
weight
semiconductor device
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP98904585A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0953008A1 (en
Inventor
Kazutoshi Iida
Jon Wigham
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Loctite Corp
Original Assignee
Henkel Loctite Corp
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 Loctite Corp filed Critical Henkel Loctite Corp
Publication of EP0953008A1 publication Critical patent/EP0953008A1/en
Publication of EP0953008A4 publication Critical patent/EP0953008A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
    • C08K5/3155—Dicyandiamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/284—Applying non-metallic protective coatings for encapsulating mounted components
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
    • H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA

Definitions

  • This invention relates to underfilling sealing resin compositions useful for mounting onto circuit board semiconductor devices, such as chip size or chip scale packages (“CSPs”), ball grid arrays (“BGAs”), and the like, each of which having a semiconductor chip, such as large scale integration (“LSI”), on a carrier substrate.
  • circuit board semiconductor devices such as chip size or chip scale packages (“CSPs), ball grid arrays (“BGAs”), and the like, each of which having a semiconductor chip, such as large scale integration (“LSI”), on a carrier substrate.
  • CSPs chip size or chip scale packages
  • BGAs ball grid arrays
  • LSI large scale integration
  • CSPs and BGAs are being used to reduce the size of packages substantially to that of bare chips.
  • Such CSPs and BGAs improve the characteristics of the electronic device while retaining many of their operating features, thus serving to protect semiconductor bare chips, such as LSIs, and facilitate testing thereof.
  • the CSP/BGA assembly is connected to electrical conductors on a circuit board by use of a solder connection or the like.
  • a solder connection or the like.
  • the reliability of the solder connection between the circuit board and the CSP/BGA often becomes suspect .
  • the space between the CSP/BGA assembly and the circuit board is often now filled with a sealing resin (often referred to as underfill sealing) in order to relieve stresses caused by thermal cycling, thereby improving heat shock properties and enhancing the reliability of the structure .
  • thermosetting resins are typically used as the underfill sealing material
  • thermosetting resins are typically used as the underfill sealing material
  • techniques for mounting a bare chip on a circuit board are accepted as substantially similar to the mounting of a CSP/BGA assembly onto a circuit board.
  • One such technique disclosed in Japanese Laid-Open Patent Publication No. 102343/93, involves a mounting process where a bare chip is fixed and connected to a circuit board by use of a photocurable adhesive, where, in the event of failure, this bare chip is removed therefrom.
  • Japanese Laid-Open Patent Publication No. 69280/94 discloses a process where a bare chip is fixed and connected to a substrate by use of a resin capable of hardening at a predetermined temperature. In the event of failure, this bare chip is removed from the substrate by softening the resin at a temperature higher than the predetermined temperature.
  • a resin capable of hardening at a predetermined temperature In the event of failure, this bare chip is removed from the substrate by softening the resin at a temperature higher than the predetermined temperature.
  • no specific resin is disclosed, and there is no disclosure about treating the resin which
  • 25 251516/93 also discloses a mounting process using bisphenol A type epoxy resin (CV5183 or CV5183S; manufactured by Matsushita Electric Industrial Co-., Ltd.). However, the removal process so disclosed does not consistently permit
  • the present invention provides a thermosetting resin composition useful as an underfilling sealing resin.
  • the composition enables a semiconductor device, such as a CSP/BGA assembly which includes a semiconductor chip mounted on a carrier substrate, to be securely connected to a circuit board by short-time heat curing and with good productivity, which demonstrates excellent heat shock properties (or thermal cycle properties) , and permits the CSP/BGA assembly to be easily removed from the circuit board in the event of semiconductor device or connection failure.
  • thermosetting resin composition which is used as a sealer underfilling between such a semiconductor device and a circuit board to which the semiconductor device is electrically connected, includes about 100 parts by weight of an epoxy resin, about 3 to about 60 parts by weight of a curing agent, and about 1 to about 90 parts by weight of a plasticizer .
  • the thermosetting resin composition of the present invention is curable at a relatively low temperature in a short period of time, cured reaction products thereof have excellent heat shock properties and, moreover, can be easily split by the application of force under heated conditions.
  • semiconductor devices attached to circuit boards and the like by cured reaction products of the thrmosetting resin compositions of this invention can be easily removed by heating the reaction product, allowing it to swell with a solvent, or allowing it to swell with a solvent under heated conditions.
  • thermosetting resin compositions of this invention By using the thermosetting resin compositions of this invention, semiconductor devices, such as CSP/BGA assemblies, can be securely connected to a circuit board by short-time heat curing and with good productivity, with the resulting mounting structure demonstrating excellent heat shock properties (or thermal cycle properties) . Moreover, in the event of failure, the semiconductor device can be easily removed. This makes it possible to reuse the semiconductor device or circuit board and thereby achieve an improvement in the yield of the production process and a " reduction in production cos .
  • FIG. 1 depicts a cross-sectional view showing an example of the mounting structure in which the thermosetting resin composition of the present invention is used.
  • FIG. 2 depicts a cross-sectional view of a semiconductor device which has been removed from the circuit board for repairing purposes after the thermosetting resin composition of the present invention has been cured.
  • thermosetting resin composition which is used as a sealer underfilling between a semiconductor device and a circuit board to which the semiconductor device is electrically connected, includes about 100 parts by weight of an epoxy resin, about 3 to about 60 parts by weight of a curing agent, and about 1 to about 90 parts by weight of a plasticizer .
  • the epoxy resin used in the present invention can be any common epoxy resin.
  • This epoxy resin may comprise at least one multifunctional epoxy resin and 0 to 30%, such as 20%, by weight based on the total epoxy resin of at least one monofunctional epoxy resin used as a reactive diluent, or crosslink density modifier.
  • the multifunctional epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol-novolac type epoxy resin cresol-novolac type epoxy resin and appropriate combinations thereof. Consideration should be given to the viscosity and other properties of the epoxy resin, and ordinarily the multifunctional epoxy resin should include an amount within about the range of 10 to 100%, of bisphenol A type epoxy resin. Desirably, the amount of bisphenol A type resin should be in the range of from about 50 to 100%.
  • the monofunctional epoxy resin has one epoxy group.
  • the epoxy group should have an alkyl group of about 6 to about 28 carbon atoms, examples of which include C 6 -C 28 alkyl glycidyl ethers, C 6 -C 28 fatty acid glycidyl esters and C 6 -C 28 alkylphenol glycidyl ethers.
  • the plasticizer used in the present invention is one which has relatively low volatility as characterized by a boiling point of at least about 130°C and which lowers the Tg of cured reaction products of the resin. It is desirable to use a plasticizer material which causes microscopic phase separation when the resin is cured. While these materials are referred to herein as plasticizers , they need not perform the function (s) conventionally associated with plasticizers .
  • plasticizers examples include (meth) acrylic esters, and aromatic or aliphatic esters.
  • (Meth) acrylic esters useful as plasticizers in this invention include monofunctional (meth) acrylic esters, such as (meth) acrylic esters of straight-chain or branched aliphatic alcohols, (meth) acrylic esters of aliphatic alcohols having an aromatic hydrocarbon substituent group, (meth) acrylic esters of alicyclic alcohols, hydroxyl-containing alkyl (meth) acrylic esters, and (meth) acrylic esters of hydroxy aliphatic amines; and multifunctional (meth) acrylic esters, such as (meth) acrylic esters of polyethers and (meth) acrylic esters of polyhydric epoxy compounds .
  • monofunctional (meth) acrylic esters such as (meth) acrylic esters of straight-chain or branched aliphatic alcohols, (meth) acrylic esters of aliphatic alcohols having an aromatic hydrocarbon substituent group, (meth) acrylic esters of alicyclic alcohols, hydroxyl-containing alkyl (meth) acrylic esters, and (
  • (Meth) acrylic esters of straight-chain or branched aliphatic alcohols useful as plasticizers in this invention include those with about 4 to about 16 carbon atoms, such as ⁇ -butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl
  • (meth) acrylate 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate and cetyl (meth) acrylate .
  • (Meth) acrylic esters of aliphatic alcohols having an aromatic hydrocarbon substituent group include (meth) acrylic esters of aliphatic alcohols having from 1 to about 8 carbon atoms having an aromatic " hydrocarbon substituent group, such as benzyl (meth) acrylate .
  • (Meth) acrylic esters of alicyclic alcohols useful as plasticizers in this invention include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate .
  • Hydroxyl-containing alkyl (meth) acrylic esters useful as plasticizers in this invention include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and 3 -phenoxy-2 -hydroxypropyl (meth) acrylate .
  • (Meth) acrylic esters of hydroxy aliphatic amines useful in this invention include (meth) acrylic esters of amines represented by NR 1 R 2 R 3 where R 1 , R 2 and R 3 independently represent hydrogen, alkyl groups, hydroxyalkyl groups or hydro-poly (oxyalkylene) groups, and at least one of R 1 , R 2 and R 3 is a hydroxyalkyl group or a hydro-poly (oxyalkylene) group .
  • Examples of (meth) acrylic esters of polyethers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate .
  • Examples of the (meth) acrylic esters of polyhydric epoxy compounds include di (meth) acrylic esters of bisphenol A epichiorohydrin reaction products .
  • Aromatic or aliphatic esters useful as plasticizers in the present invention include dialkyl esters of aromatic carboxylic acids, e.g., di (C 1 -C 12 alkyl)phthalates, such as dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate and octyl decyl phthalate; aliphatic monobasic acid esters, such as butyl oleate and glycerol mono-oleate; and aliphatic dibasic acid esters, such as dibutyl adipate, di-2-ethylhexyl adipate, dibutyl sebacate and di-2-ethylhexyl sebacate.
  • di (C 1 -C 12 alkyl)phthalates such as dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, di-2-eth
  • (meth) acrylic esters of alkanolamines or hydro-poly (oxyalkylene) amines as represented by the formula above, di (C ⁇ C ⁇ alkyl) phthalates, hydroxyl-containing alkyl esters of (meth) acrylic acid, and (meth) acrylic esters of alicyclic alcohols are especially desirable.
  • the plasticizer component is usually used in an amount of 1 to about 90 parts by weight, per 100 parts by weight of the epoxy resin. Desirably, that range is within 5 to 50 parts by weight of the resin.
  • thermosetting resin composition of the present invention may be formulated as a one-part composition, in which all the ingredients are mixed together, or as a two-part composition, in which the epoxy resin and the curing agent are stored separately and mixed thereafter prior to use.
  • the curing agent used in the present invention can generally be any of the curing agents which are used in one-part and two-part epoxy resin formulations.
  • desirable curing agents for use with the present invention include amine compounds, imidazole compounds, modified amine compounds and modified imidazole compounds .
  • amine compounds include dicyandiamide; aliphatic polyamines, such As diethylenetriamine, triethylenetetramine and diethylaminopropylamine ; aromatic polyamines, such as m-xylenediamine and diaminodiphenylamine; alicyclic polyamines, such as isophoronediamine and menthenediamine; and polyamides .
  • Examples of the imidazole compounds include 2-methyl imidazole, 2-ethyl-4-methylimidazole and 2 -phenylimidazole .
  • Examples of the modified amine compounds include epoxy-added polyamines formed by the addition of an amine compound to an epoxy compound, and examples of the modified imidazole compounds include imidazole adducts formed by the addition of an imidazole compound to an epoxy compound.
  • latent curing agents used in one-pack epoxy resins are particularly desirable. From the viewpoint of repairability, it is especially desirable to use 5 to 95% by weight of a modified amine in combination with 95 to 5% by weight of dicyandiamide, based on the total weight of the curing agent.
  • the curing agent itself is ordinarily used in an amount of from about 3 to about 60 parts by weight, per 100 parts by weight of the epoxy resin. Desirably, that range is within 5 to 40 parts by weight of the resin. It is desirable for the thermosetting resin compositions of the present invention to contain the aforesaid plasticizer and monofunctional epoxy resin in a combined amount of about 5 to about 40% by weight.
  • the thermosetting resin compositions according to the present invention are capable of penetrating into the space between the circuit board and the semiconductor device. These inventive compositions also demonstrate a reduced viscosity, at least under elevated temperature conditions, and thus are capable of penetrating into that space.
  • thermosetting resin composition by selecting the types and proportions of various ingredients to reach a viscosity at 25°C of 50,000 mPa-s or less, such as 30,000 mPa-s or less, so as to improve its ability to penetrate into the space (e.g. , of 100 to 200 ⁇ m) between the circuit board and the semiconductor device.
  • thermosetting resin composition of the present invention may further contain other additives, such as defoaming agents, leveling agents, dyes, pigments and fillers.
  • photopolymerization initiators may also be incorporated therein, provided that such initiators do not adversely affect the properties of the composition or reaction products formed therefrom.
  • thermosetting resin composition of the present invention is used is shown in FIG. 1.
  • the semiconductor device 4 is one formed by connecting a semiconductor chip (so-called bare chip) 2, such as LSI, to a carrier substrate 1 and sealing the space therebetween suitably with resin 3.
  • This semiconductor device is mounted at a predetermined position of the circuit board 5, and electrodes 8 and 9 are electrically connected by a suitable connection means such as solder.
  • the space between carrier substrate 1 and circuit board 5 is sealed with the cured product 10 of a thermosetting resin composition.
  • the cured product 10 of the thermosetting resin composition need not completely fill the space between carrier substrate 1 and circuit board 5, but may fill it to such an extent as to relieve stresses caused by thermal cycles.
  • Carrier substrates may be constructed from ceramic substrates made of A1 2 0 3 , SiN 3 and mullite (Al 2 0 3 -Si0 2 ) ; substrates or tapes made of heat-resistant resins such as polyimides; glass-reinforced epoxy, ABS and phenolic substrates which are also used commonly as circuit boards; and the like.
  • the means for electrically connecting the semiconductor chip to the carrier substrate there may be employed connection by a high-melting solder or electrically (or anisotropically) conductive adhesive, wire bonding, and the like.
  • the electrodes may be formed as bumps.
  • the space between the semiconductor chip and the carrier substrate may be sealed with a suitable resin.
  • the semiconductor devices which can be used in the present invention include CSPs and BGAs.
  • circuit board used in the present invention No particular limitation is placed on the type of circuit board used in the present invention, and there may be used any of various common circuit boards such as glass-reinforced epoxy, ABS and phenolic boards.
  • cream solder is printed at the necessary positions of a circuit board and suitably dried to expel the solvent.
  • a semiconductor device is mounted in conformity with the pattern on the circuit board.
  • This circuit board is passed through a reflowing furnace to melt the solder and thereby solder the semiconductor device.
  • the electrical connection between the semiconductor device and the circuit board is not limited to the use of cream solder, but may be made by use of solder balls. Alternatively, this connection may also be made through an electrically conductive adhesive or an anisotropically conductive adhesive.
  • cream solder or the like may be applied or formed on either the circuit board or the semiconductor device.
  • the solder, electrically or anisotropically conductive adhesive used should be chosen bearing in mind its melting point, bond strength and the like.
  • the resulting structure should ordinarily be subjected to a continuity test or the like. After passing such test, the semiconductor device may be fixed thereto with a resin composition. In this way, in the event of a failure, it is easier to remove the semiconductor device before fixing it with the resin composition.
  • thermosetting resin composition is applied to the periphery of the semiconductor device.
  • a thermosetting resin composition is applied to the semiconductor device, it penetrates into the space between the circuit board and the carrier substrate of the semiconductor device by capillary action.
  • thermosetting resin composition is cured by the application of heat.
  • the thermosetting resin composition shows a significant reduction in viscosity and hence an increase in fluidity, so that it more easily penetrates into the space between the circuit board and the semiconductor device.
  • the thermosetting resin composition is allowed to penetrate fully into the entire space between the circuit board and the semiconductor device.
  • thermosetting resin composition applied should be suitably adjusted so as to fill the space between the circuit board and the semiconductor device almost completely.
  • thermosetting resin composition When the above-described thermosetting resin composition is used, it is usually cured by heating at 120 to 150°C for a period of time of about 5 to 20 minutes.
  • the present invention can employ relatively low-temperature and short-time curing conditions and hence achieve very good productivity.
  • the mounting structure illustrated in FIG. 1 is completed in this manner. Where a (meth) acrylic ester is used as a plasticizer in the thermosetting resin composition and a photopolymerization initiator is added thereto, the thermosetting resin composition can be tentatively cured by exposure to light prior to heat curing.
  • thermosetting resin composition of the present invention In the mounting process by using the thermosetting resin composition of the present invention, after the semiconductor device is mounted on the circuit board as described above, the resulting structure is tested with respect to characteristics of the semiconductor device, connection between the semiconductor device and the circuit board, other electrical characteristics, and the state of sealing. In case that a failure is found, repair can be made in the following manner.
  • the area around the semiconductor device which has failed is heated at a temperature of about 190 to about 260°C for a period of time ranging from about 10 seconds to about 1 minute.
  • the heating means local heating is preferred.
  • a residue 12 of the cured reaction product of the thermosetting resin composition and a residue 14 of the solder are left on the circuit board 5.
  • the residue of the cured product of the thermosetting resin composition can be removed, for example, by scraping it off after the residue has been softened by heating it to a predetermined temperature, allowing it to swell with solvent, or allowing it to swell with solvent while heating it to a predetermined temperature .
  • the residue can be most easily removed by using both heating and solvent.
  • the residue can be scraped off after it has been softened by allowing the residual resin to swell with solvent while keeping the entire circuit board at a temperature of the order of 100°C
  • the solvent used for this purpose is one which causes cured reaction products of the thermosetting resin composition to swell, thereby reducing bond strength to such an extent that the cured material can be scraped off from the circuit board.
  • Useful solvents include organic ones, for example, alkyl chlorides, such as methylene chloride; glycol ethers, such as ethyl cellulose and butyl cellulose; diesters of dibasic acids, such as diethyl succinate; and N-methylpyrrolidone . Of course, appropriate combinations may also be employed.
  • the chosen solvents should cause no damage to the resist.
  • Desirable solvents with this in mind include glycol ethers and N-methylpyrrolidone.
  • the residue of the solder can be removed, for example, by use of a solder-absorbing braided wire.
  • the semiconductor device can be reused by removing the residue 13 of the cured reaction product of the thermosetting resin composition and the residue 15 of the solder left on the bottom of the semiconductor device in the same manner as described above.
  • thermosetting resin composition was prepared by mixing together an epoxy resin prepared from 85 parts by weight of bisphenol A type epoxy resin, 4 parts by weight of novolac epoxy resin, and 11 parts by weight of a mixture of alkyl glycidyl ethers of 12 to 14 carbon atoms; a curing agent prepared from 3 parts by weight of dicyandiamide, and 19 parts by weight of an epoxy adduct of an amine and 12 parts by weight of an acrylated amine oligomer as a plasticizer. In addition, 0.1 part by weight of a defoaming agent was also mixed therewith. The viscosity of the so-formed composition was determined to be 5,200 mPa • s .
  • thermosetting resin composition was applied to the periphery of the CSP by means of a dispenser, and then cured by heating in an environment where the temperature was held at about at 150°C for a period of time of about 5 minutes.
  • the thermosetting resin composition penetrated into the space between the semiconductor device and the circuit board before curing completely.
  • the area around the CSP fixed to the circuit board with the thermosetting resin composition as described above was heated by applying hot air at 250°C for 1 minute. Then, the CSP could be easily removed by inserting a metal piece between the CSP and the glass-reinforced epoxy board, and lifting the CSP.
  • the glass-reinforced epoxy board was kept at about 100°C by placing it on a hot plate (or by heating it with a far-infrared heater or the like) , the resin left on the glass-reinforced epoxy board was allowed to swell with a solvent such as PS-1 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) or 7360 (manufactured by Loctite Corporation), and then scraped off with a spatula. The solder left on the glass-reinforced epoxy board was removed by use of a solder-absorbing braided wire. The time required for this repairing operation was within 3 minutes, which was sufficiently short from a practical point of view.
  • a solvent such as PS-1 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) or 7360 (manufactured by Loctite Corporation)
  • Cream solder was applied again to the glass-reinforced epoxy board from which the CSP had been removed in the above-described manner, and a new CSP was mounted thereon. In this operation, cream solder may be printed on the new CSP.
  • thermosetting resin composition was applied to the periphery of the CSP and then cured by heating at 150°C for 5 minutes.
  • Example 1 The procedure of Example 1 was repeated except that the amount of the acrylated amine oligo er used as a plasticizer in Example 1 was altered as shown below. The resulting mounting structures passed a heat shock test, and their repair time was within 3 minutes.
  • Example 2 1.2 parts by weight.
  • Example 3 6.0 parts by weight .
  • Example 4 21.0 parts by weight.
  • Example 5 50.0 parts by weight.
  • Example 1 The procedure of Example 1 was repeated except that no plasticizer was used.
  • the resulting mounting structure exhibited acceptable repairability, but did not pass a heat shock test because continuity was lost at less than 1,000 cycles.
  • Example 1 The procedure of Example 1 was repeated except that the amount of the acrylated amine oligomer used as a plasticizer in Example 1 was altered to 120 parts by weight The resulting mounting structure exhibited acceptable repairability, but did not pass a heat shock test because continuity was lost at less than 1,000 cycles.
  • Example 1 The procedure of Example 1 was repeated except that the amount of the mixture of alkyl glycidyl ethers of 12 to 14 carbon atoms used in Example 1 was altered as shown below. The resulting mounting structures passed a heat shock test, and their repair time was within 3 minutes.
  • Example 6 0 parts by weight .
  • Example 7 2.7 parts by weight.
  • Example 8 5.3 parts by weight
  • Example 9 20.0 parts by weight Comparative Example 3
  • Example 1 The procedure of Example 1 was repeated except that the amount of the mixture of alkyl glycidyl ethers of 12 to 14 carbon atoms used in Example 1 was altered to 40 parts by weight.
  • the resulting mounting structure exhibited acceptable repairability, but did not pass a heat shock test because continuity was lost at less than 1,000 cycles.
  • Example 1 The procedure of Example 1 was repeated except that the acrylated amine oligomer used as a plasticizer in Example 1 was replaced by each of the compounds shown below.
  • the resulting mounting structures passed a heat shock test, and their repair time was within 3 minutes.
  • Example 11 Isobornyl acrylate.
  • Example 12 2 -Hydroxyethy1 methacry1ate
  • Example 1 The procedure of Example 1 was repeated except that the epoxy adduct of amine used as a curing agent in Example 1 was replaced by the epoxy adduct of imidazole.
  • the resulting mounting structure passed a heat shock test, and its repair time was within 3 . minutes.
  • Example 1 The procedure of Example 1 was repeated except that, in place of the thermosetting resin composition used in Example 1, an adhesive (TB3006B; manufactured by Three Pond Co., Ltd.) comprising acrylate oligomers, acrylate monomers and a photopolymerization initiator was used and cured by exposure to light through the gap between the semiconductor device and the circuit board and by the application of heat.
  • an adhesive (TB3006B; manufactured by Three Pond Co., Ltd.) comprising acrylate oligomers, acrylate monomers and a photopolymerization initiator was used and cured by exposure to light through the gap between the semiconductor device and the circuit board and by the application of heat.
  • this adhesive was used, the semiconductor device could be easily removed in its semicured state. After the adhesive was completely cured, the resulting mounting structure was subjected to a heat shock test. Its heat shock properties were unacceptable because continuity was lost at less than 1,000 cycles.
  • Example 1 The procedure of Example 1 was repeated except that in place of the thermosetting resin composition used in Example 1, an epoxy resin sealant (SA-51-2; manufactured by Asahi Kaken Co., Ltd.) was applied in the same manner as in Example 1 and cured by heating at 100° for 90 seconds. In a heat shock test, the resulting mounting structure exhibited the same degree of reliability as in Example 1. However, an attempt was made to separate the semiconductor device by the application of heat for repairing purposes, but in vain. The full scope of the invention is measured by the claims .
  • SA-51-2 epoxy resin sealant manufactured by Asahi Kaken Co., Ltd.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Wire Bonding (AREA)
EP98904585A 1997-01-17 1998-01-16 HARDENABLE RESIN COMPOSITIONS Withdrawn EP0953008A4 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP657197 1997-01-17
JP00657197A JP3613367B2 (ja) 1997-01-17 1997-01-17 熱硬化性樹脂組成物
PCT/US1998/000858 WO1998031738A1 (en) 1997-01-17 1998-01-16 Thermosetting resin compositions

Publications (2)

Publication Number Publication Date
EP0953008A1 EP0953008A1 (en) 1999-11-03
EP0953008A4 true EP0953008A4 (en) 2000-05-03

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EP98904585A Withdrawn EP0953008A4 (en) 1997-01-17 1998-01-16 HARDENABLE RESIN COMPOSITIONS

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JP (1) JP3613367B2 (ja)
KR (1) KR100554323B1 (ja)
CN (1) CN1243526A (ja)
BR (1) BR9806743A (ja)
ID (1) ID22238A (ja)
MY (1) MY118700A (ja)
TW (1) TW561178B (ja)
WO (1) WO1998031738A1 (ja)

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BR0012273A (pt) * 1999-07-08 2002-04-02 Sunstar Engineering Inc Material de subenchimento para embalagem de semicondutor
US6255500B1 (en) 2000-01-21 2001-07-03 Loctite Corporation Process for the epoxidation of diene esters
US20050288458A1 (en) 2002-07-29 2005-12-29 Klemarczyk Philip T Reworkable thermosetting resin composition
US7012120B2 (en) 2000-03-31 2006-03-14 Henkel Corporation Reworkable compositions of oxirane(s) or thirane(s)-containing resin and curing agent
JP4609617B2 (ja) * 2000-08-01 2011-01-12 日本電気株式会社 半導体装置の実装方法及び実装構造体
US6627683B1 (en) 2000-09-05 2003-09-30 Henkel Loctite Corporation Reworkable thermosetting resin compositions and compounds useful therein
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US6936664B2 (en) 2000-10-04 2005-08-30 Henkel Corporation Reworkable epoxidized 1-(cyclo) alkenyl ether/polycarboxylic acid product
WO2002058108A2 (en) 2000-11-14 2002-07-25 Henkel Loctite Corporation Wafer applied fluxing and underfill material, and layered electronic assemblies manufactured therewith
TW574739B (en) * 2001-02-14 2004-02-01 Nitto Denko Corp Thermosetting resin composition and semiconductor device using the same
JP5280597B2 (ja) 2001-03-30 2013-09-04 サンスター技研株式会社 一液加熱硬化型エポキシ樹脂組成物および半導体実装用アンダーフィル材
JP3566680B2 (ja) 2001-09-11 2004-09-15 富士通株式会社 半導体装置の製造方法
US6916890B1 (en) 2001-10-09 2005-07-12 Henkel Corporation Thermally reworkable epoxy resins and compositions based thereon
US6887737B1 (en) 2001-12-13 2005-05-03 Henkel Corporation Epoxidized acetals and thioacetals, episulfidized acetals and thioacetals, and reworkable thermosetting resin compositions formulated therefrom
US7242082B2 (en) 2002-02-07 2007-07-10 Irvine Sensors Corp. Stackable layer containing ball grid array package
JP2007521631A (ja) * 2003-08-08 2007-08-02 アービン センサーズ コーポレーション 積層可能な層及びその製造方法
JP5175431B2 (ja) * 2005-09-16 2013-04-03 日本電気株式会社 半導体装置のリペア方法
JP2007258207A (ja) * 2006-03-20 2007-10-04 Three M Innovative Properties Co バンプ付きチップもしくはパッケージの実装方法
EP2026973B1 (en) 2006-04-28 2011-04-06 Telecom Italia S.p.A. Ink-jet printhead die and manufacturing method thereof
WO2007142654A1 (en) * 2006-06-09 2007-12-13 Advanced Applied Adhesives Reworkable compositions and methods for use thereof
US7714426B1 (en) 2007-07-07 2010-05-11 Keith Gann Ball grid array package format layers and structure
WO2009147828A1 (ja) 2008-06-05 2009-12-10 住友ベークライト株式会社 半導体装置の製造方法および半導体装置
WO2010050185A1 (ja) 2008-10-27 2010-05-06 パナソニック株式会社 半導体の実装構造体およびその製造方法
CN103172306A (zh) * 2013-04-08 2013-06-26 天津大学 一种水弹性模型材料及其制备方法
KR102340799B1 (ko) * 2018-09-20 2021-12-16 주식회사 엘지화학 금속 박막 코팅용 열경화성 수지 조성물, 이를 이용한 수지 코팅 금속 박막 및 금속박 적층판
KR102092649B1 (ko) * 2018-11-07 2020-03-24 (주)티에이치엔 방열 및 방사 기능이 구비된 전자 기기 패키징 장치 제조방법
DE102020127468A1 (de) 2020-10-19 2022-04-21 Werner H. Salewski Multifunktionale Epoxyd-Systeme
DE102022120396A1 (de) 2022-08-12 2024-02-15 Delo Industrie Klebstoffe Gmbh & Co. Kgaa Verwendung einer härtbaren und wiederlösbaren Masse zur Herstellung eines Bauteils, und Masse dafür

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WO1998031738A1 (en) 1998-07-23
CN1243526A (zh) 2000-02-02
TW561178B (en) 2003-11-11
EP0953008A1 (en) 1999-11-03
ID22238A (id) 1999-09-23
BR9806743A (pt) 2000-02-29
JPH10204259A (ja) 1998-08-04
MY118700A (en) 2005-01-31
JP3613367B2 (ja) 2005-01-26
KR20000070203A (ko) 2000-11-25
KR100554323B1 (ko) 2006-02-24

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