WO2010046996A1 - 半導体用接着剤組成物およびそれを用いて製造した半導体装置 - Google Patents
半導体用接着剤組成物およびそれを用いて製造した半導体装置 Download PDFInfo
- Publication number
- WO2010046996A1 WO2010046996A1 PCT/JP2008/069358 JP2008069358W WO2010046996A1 WO 2010046996 A1 WO2010046996 A1 WO 2010046996A1 JP 2008069358 W JP2008069358 W JP 2008069358W WO 2010046996 A1 WO2010046996 A1 WO 2010046996A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- adhesive composition
- meth
- acrylate
- adhesive
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/16—Fillings or auxiliary members in containers or encapsulations, e.g. centering rings
- H01L23/18—Fillings characterised by the material, its physical or chemical properties, or its arrangement within the complete device
- H01L23/24—Fillings characterised by the material, its physical or chemical properties, or its arrangement within the complete device solid or gel at the normal operating temperature of the device
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/02—Polysilicates
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- 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
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- 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
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
-
- 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
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- 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
-
- 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
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
-
- 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
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—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
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/00011—Not relevant to the scope of the group, the symbol of which is combined with the symbol of this group
-
- 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
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/00013—Fully indexed content
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01005—Boron [B]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01006—Carbon [C]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01012—Magnesium [Mg]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01013—Aluminum [Al]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01019—Potassium [K]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01029—Copper [Cu]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/0103—Zinc [Zn]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01033—Arsenic [As]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01043—Technetium [Tc]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01045—Rhodium [Rh]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01047—Silver [Ag]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01049—Indium [In]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/0105—Tin [Sn]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01067—Holmium [Ho]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01077—Iridium [Ir]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01079—Gold [Au]
-
- 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
- H01L2924/01—Chemical elements
- H01L2924/01082—Lead [Pb]
-
- 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
- H01L2924/013—Alloys
- H01L2924/014—Solder alloys
-
- 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
- H01L2924/0665—Epoxy resin
-
- 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
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/102—Material of the semiconductor or solid state bodies
- H01L2924/1025—Semiconducting materials
- H01L2924/10251—Elemental semiconductors, i.e. Group IV
- H01L2924/10253—Silicon [Si]
-
- 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
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12044—OLED
-
- 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
- H01L2924/156—Material
- H01L2924/157—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
- H01L2924/15738—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 greater than or equal to 950 C and less than 1550 C
- H01L2924/15747—Copper [Cu] as principal constituent
Definitions
- the present invention relates to an adhesive composition for a semiconductor and a semiconductor device manufactured using the same.
- Japanese Patent Application Laid-Open No. 2002-305212 proposes a semiconductor adhesive that can be cured at a low temperature.
- thermosetting resin composition when the curability at low temperature of the thermosetting resin composition is improved, the reactivity at room temperature is improved and the viscosity of the resin composition is increased.
- adhesive strength in addition to the deterioration of workability due to increased viscosity, there is a tendency for adhesive strength to decrease in high-temperature processes such as wire bonding and solder reflow, and an adhesive composition for semiconductors with excellent storage stability at room temperature, That is, the thing with little characteristic change by storage at room temperature is desired.
- the present inventors have disclosed a compound having a radical polymerizable functional group in Japanese Patent Application Laid-Open No. 2007-262243 (Document 2) as an adhesive composition for a semiconductor having excellent adhesive properties and storage stability at room temperature.
- a resin composition containing a polymerization initiator, silver powder, and a compound having a sulfide bond (preferably a compound having a sulfide bond and an alkoxysilyl group) is proposed.
- the present invention has been made in view of the above-mentioned problems of the prior art, and has an adhesive property and a semiconductor adhesive composition that is superior in storage stability at room temperature, and in particular, a small increase in viscosity even when stored for a long time at room temperature. And it aims at providing the adhesive composition for semiconductors with which the outstanding adhesive characteristic is maintained.
- the reason why the adhesive properties of the resin composition are lower than those immediately after preparation is the following formula (2) contained in the compound having a sulfide bond and an alkoxysilyl group: X— (CH 2 ) m —SiR 1 R 2 R 3 (2) (In the formula (2), R 1 to R 3 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of R 1 to R 3 represents the number of carbon atoms. 1 to 10 alkoxy groups, X represents a halogen atom, and m is an integer of 1 to 10.) As a result, the present invention has been completed.
- the semiconductor adhesive composition of the present invention includes a thermosetting resin (A) and the following formula (1): -(S) n- (1) (In formula (1), n is an integer of 1 or more.) And a compound (B) having a sulfide bond and an alkoxysilyl group.
- the compound (B) the following formula (2): X— (CH 2 ) m —SiR 1 R 2 R 3 (2) (In the formula (2), R 1 to R 3 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of R 1 to R 3 represents the number of carbon atoms. 1 to 10 alkoxy groups, X represents a halogen atom, and m is an integer of 1 to 10.)
- the content rate of the component represented by is 0.6 mass% or less.
- the semiconductor adhesive composition of the present invention preferably further contains filler particles (C).
- the compound (B) is preferably a compound having an average value of n in the formula (1) of 3.5 to 4.5. Furthermore, in the adhesive composition for semiconductors of this invention, it is preferable that the hot water extraction halogen ion density
- the semiconductor device of the present invention is a semiconductor device that is bonded with the semiconductor adhesive composition of the present invention and has excellent reflow resistance and high reliability.
- the present inventors infer as follows. That is, a compound having a sulfide bond and an alkoxysilyl group is added in order to improve adhesive properties, but the component represented by the formula (2) contained in this compound is a hydrolyzate of the alkoxysilyl group in the compound. Decomposition is promoted, and bonds between alkoxysilyl groups occur. The compound in which the alkoxysilyl groups are bonded to each other reduces the effect of improving the adhesive properties of the adhesive composition.
- the halogenated alkyl group in the component represented by the formula (2) is highly reactive and has functional groups such as a cyanate ester group, an epoxy group, a (meth) acryl group, and a maleimide group in the thermosetting resin. React at room temperature. For this reason, it is presumed that the viscosity of the adhesive composition is increased by storing at room temperature for a long time, or the adhesive properties are remarkably lowered as compared with those immediately after preparation.
- the content of the component represented by the formula (2) is small, and the compound having the sulfide bond and the alkoxysilyl group is bonded to each other at room temperature. Difficult to change into compounds. For this reason, the amount of the compound having a sulfide bond and an alkoxysilyl group is hardly reduced even when stored for a long time at room temperature, and the adhesive properties of the adhesive composition are sufficiently maintained even after long storage at room temperature. Inferred.
- the content of the component represented by the formula (2) is small, the functional group in the thermosetting resin exists in an unreacted state even after long storage at room temperature, and the viscosity of the adhesive composition It is presumed that the adhesion property is sufficiently maintained.
- the adhesive composition for semiconductors which was excellent by the adhesive characteristic and the preservability at room temperature, especially the adhesive for semiconductors with which a viscosity increase is small and the outstanding adhesive characteristic is maintained even if it preserve
- the adhesive composition for semiconductors of the present invention (hereinafter simply referred to as “adhesive composition”) includes a thermosetting resin (A) and the following formula (1): -(S) n- (1) (In formula (1), n is an integer of 1 or more.) And a compound (B) having a sulfide bond and an alkoxysilyl group.
- the compound (B) includes the following formula (2): X— (CH 2 ) m —SiR 1 R 2 R 3 (2) (In the formula (2), R 1 to R 3 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of R 1 to R 3 represents the number of carbon atoms. 1 to 10 alkoxy groups, X represents a halogen atom, and m is an integer of 1 to 10.) The content rate is contained and the content rate is 0.6 mass% or less.
- Such an adhesive composition is excellent in adhesive properties and storage stability at room temperature. Particularly, even when stored for a long time at room temperature, the viscosity increase is small and excellent adhesive properties are maintained.
- thermosetting resin (A) used in the present invention is a resin that forms a three-dimensional network structure by heating and is cured.
- a thermosetting resin (A) is not particularly limited, but is preferably liquid at room temperature in order to obtain a paste-like adhesive resin composition.
- thermosetting resin (A) for example, cyanate resin, epoxy resin, acrylic resin, maleimide resin and the like are preferable from the viewpoints of curability, adhesiveness, and reliability. Moreover, these thermosetting resins may be used individually by 1 type, or may use 2 or more types together.
- the adhesive composition of the present invention may contain a curing agent, a curing accelerator, a polymerization initiator, a catalyst, and the like of the thermosetting resin (A).
- the cyanate resin used in the present invention is a compound having an —NCO group in the molecule, and forms a three-dimensional network structure by the reaction of the —NCO group by heating, and is cured.
- cyanate resins include 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanato.
- a prepolymer having a triazine ring formed by trimerization of cyanate groups of cyanates can also be used.
- This prepolymer can be obtained by polymerizing the cyanates using, for example, acids such as mineral acids and Lewis acids, bases such as sodium alcoholates and tertiary amines, and salts such as sodium carbonate as catalysts.
- the said cyanates may be used individually by 1 type, or may use 2 or more types together.
- a cyanate resin curing accelerator generally known ones can be used.
- organometallic complexes such as zinc octylate, tin octylate, cobalt naphthenate, zinc naphthenate and acetylacetone iron, metal salts such as aluminum chloride, tin chloride and zinc chloride, and amines such as triethylamine and dimethylbenzylamine.
- metal salts such as aluminum chloride, tin chloride and zinc chloride
- amines such as triethylamine and dimethylbenzylamine.
- these hardening accelerators may be used individually by 1 type, or may use 2 or more types together.
- the cyanate resin may be used alone, but may be used in combination with at least one resin selected from epoxy resin, oxetane resin, acrylic resin and maleimide resin.
- the epoxy resin used in the present invention is a compound having one or more glycidyl groups in one molecule, and is a resin that forms a three-dimensional network structure and cures when the glycidyl group reacts by heating. Even if the glycidyl group is reacted with only one compound per molecule, sufficient cured product characteristics tend not to be exhibited. Therefore, it is preferable that two or more glycidyl groups are contained in one molecule.
- Compounds containing two or more glycidyl groups per molecule include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol, or derivatives thereof, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, and cyclohexanedimethanol.
- Diols having an alicyclic structure such as shidilohexanediethanol or derivatives thereof, bifunctional ones obtained by epoxidizing aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, decanediol, or derivatives thereof , Trihydroxyphenylmethane skeleton, trifunctional one having aminophenol skeleton, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, biff Alkenyl aralkyl resins, and the naphthol aralkyl resin as polyfunctional epoxidized include, but are not limited to.
- the compound which has the said glycidyl group may be used individually by 1 type, or may use 2 or more types together.
- the adhesive composition of the present invention is preferably liquid at room temperature, it is preferable to use an epoxy resin that is liquid at room temperature.
- a reactive diluent as is usually done.
- the reactive diluent include monofunctional aromatic glycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether, and aliphatic glycidyl ethers.
- epoxy resin curing agent examples include aliphatic amines, aromatic amines, dicyandiamide, dihydrazide compounds, acid anhydrides, and phenol resins. These curing agents may be used alone or in combination of two or more.
- dihydrazide compound examples include carboxylic acid dihydrazides such as adipic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, and p-oxybenzoic acid dihydrazide.
- Acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydroanhydride, and the like. Examples thereof include phthalic acid, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, a reaction product of maleic anhydride and polybutadiene, and a copolymer of maleic anhydride and styrene.
- the phenol resin used as a curing agent for the epoxy resin is a compound having two or more phenolic hydroxyl groups in one molecule, and preferably has 2 to 5 phenolic hydroxyl groups in one molecule. Those having the number are more preferable.
- the number of phenolic hydroxyl groups is less than the lower limit, a crosslinked structure cannot be formed, the cured product characteristics deteriorate, and the phenol resin cannot be used as a curing agent for the epoxy resin.
- the upper limit is exceeded, the molecular weight becomes too large and the viscosity of the adhesive composition tends to be too high.
- Such phenol resins include bisphenol F, bisphenol A, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, dihydroxy diphenyl ether, dihydroxy benzophenone, tetramethyl biphenol, ethylidene bisphenol, methyl ethylidene bis (methyl Phenol), cyclohexylidene bisphenol, bisphenols such as biphenol and derivatives thereof, trifunctional phenols such as tri (hydroxyphenyl) methane, tri (hydroxyphenyl) ethane and derivatives thereof, phenols such as phenol novolac and cresol novolac A compound obtained by reacting aldehydes with formaldehyde, dinuclear or Nuclear bodies like those and their derivatives of the main component.
- epoxy resin curing accelerator examples include imidazoles, triphenylphosphine or tetraphenylphosphine salts, amine compounds such as diazabicycloundecene, and salts thereof, among which 2-methylimidazole, 2 -Ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-C 11 H 23
- An imidazole compound such as an imidazole or an adduct of 2-methylimidazole and 2,4-diamino-6-vinyltriazine is preferable from the viewpoint of curability, and from the viewpoint of storage stability at room temperature, an imidazole having a melting point of 180 ° C. or higher. Especially preferred for compounds That's right.
- these hardening accelerators may be used individually by 1 type, or may use 2 or more types
- the epoxy resin may be used alone, but it can also be used in combination with at least one of a cyanate resin, an oxetane resin, an acrylic resin and a maleimide resin.
- the acrylic resin used in the present invention is a compound having a (meth) acryloyl group in the molecule, and is a resin that forms a three-dimensional network structure by the reaction of the (meth) acryloyl group and cures.
- One or more (meth) acryloyl groups may be contained in one molecule, but in order to obtain sufficient cured product properties, it is preferable that two or more (meth) acryloyl groups are contained.
- acrylic resins polyether, polyester, polycarbonate, poly (meth) acrylate, polybutadiene, butadiene acrylonitrile copolymer having a molecular weight of 500 to 10,000 and having a (meth) acryl group are workable and hardened. Is particularly preferred from the viewpoints of adhesiveness and adhesiveness. Moreover, such an acrylic resin may be used individually by 1 type, or may use 2 or more types together.
- polyether those in which a divalent organic group having 3 to 6 carbon atoms is repeated via an ether bond are more preferable, and those that do not contain an aromatic ring from the viewpoint of lowering the elastic modulus of the cured product.
- the polyether having a (meth) acryl group can be obtained by a reaction between a polyether polyol and (meth) acrylic acid or a derivative thereof.
- polyester those in which a divalent organic group having 3 to 6 carbon atoms is repeated through an ester bond are more preferable, and those having no aromatic ring are more preferable from the viewpoint of lowering the elastic modulus of the cured product.
- the polyester having a (meth) acryl group can be obtained by a reaction between a polyester polyol and (meth) acrylic acid or a derivative thereof.
- a polycarbonate having a (meth) acryl group can be obtained by a reaction between a polycarbonate polyol and (meth) acrylic acid or a derivative thereof.
- Examples of the poly (meth) acrylate include a copolymer of (meth) acrylic acid and (meth) acrylate, or a copolymer of (meth) acrylate having a hydroxyl group and (meth) acrylate having no polar group. Is preferred. When these copolymers have a carboxy group, an acrylate having a hydroxyl group, and when these copolymers have a hydroxyl group, (meth) acrylic acid or a derivative thereof is reacted with the copolymer to form a (meth) acrylic group. The poly (meth) acrylate possessed can be obtained.
- the polybutadiene having a (meth) acryl group can be obtained by a reaction between a polybutadiene having a carboxy group and a (meth) acrylate having a hydroxyl group, a reaction between a polybutadiene having a hydroxyl group and (meth) acrylic acid or a derivative thereof, It can also be obtained by reaction of polybutadiene added with maleic anhydride and (meth) acrylate having a hydroxyl group.
- the butadiene acrylonitrile copolymer having a (meth) acryl group can be obtained by a reaction between a butadiene acrylonitrile copolymer having a carboxy group and a (meth) acrylate having a hydroxyl group.
- dicarboxylic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and tetrahydrophthalic acid. Acid, hexahydrophthalic acid and derivatives thereof. These compounds may be used individually by 1 type, or may use 2 or more types together.
- the thermal radical polymerization initiator is not particularly limited as long as it is a compound that is usually used as a thermal radical polymerization initiator, but a rapid heating test (when 1 g of a sample is placed on an electric heating plate and heated at 4 ° C./min.
- the decomposition temperature at the decomposition start temperature is preferably 40 to 140 ° C. When the decomposition temperature is less than 40 ° C., the preservability of the adhesive composition at normal temperature tends to be lowered, and when it exceeds 140 ° C., the curing time tends to be extremely long.
- thermal radical polymerization initiators examples include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane.
- the acrylic resin may be used alone, but it can also be used in combination with at least one of a cyanate resin, an epoxy resin, an oxetane resin and a maleimide resin.
- the maleimide resin used in the present invention is a compound that contains one or more maleimide groups in one molecule, and forms a three-dimensional network structure when the maleimide group reacts by heating, and is cured.
- maleimide resins include N, N ′-(4,4′-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and 2,2-bis [4 -(4-maleimidophenoxy) phenyl] propane and the like.
- compounds obtained by reaction of dimer acid diamine and maleic anhydride and compounds obtained by reaction of maleimidated amino acids such as maleimidoacetic acid and maleimidocaproic acid and polyols are more preferred.
- Maleimidated amino acids are obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid.
- polyether polyol, polyester polyol, polycarbonate polyol, and poly (meth) acrylate polyol are preferable from the viewpoint of workability, and those not containing an aromatic ring are particularly preferable.
- Such a maleimide resin may be used alone, but it can also be used in combination with at least one of a cyanate resin, an epoxy resin, an oxetane resin and an acrylic resin. Further, since the maleimide group can react with an allyl group, it is possible to use a maleimide resin and an allyl ester resin in combination.
- the allyl ester resin an aliphatic resin is preferable from the viewpoint of lowering the elastic modulus of the cured product, and among them, a compound obtained by transesterification of cyclohexane diallyl ester and aliphatic polyol is particularly preferable.
- (B) Compound having sulfide bond and alkoxysilyl group
- the compound (B) used in the present invention has the following formula (1): -(S) n- (1) (In formula (1), n is an integer of 1 or more.) It has a sulfide bond represented by and an alkoxysilyl group.
- the adhesive composition of the present invention exhibits excellent adhesive properties and can produce a highly reliable semiconductor device with excellent reflow resistance. It becomes possible.
- the number of sulfide bonds in one molecule is not particularly limited as long as it is 1 or more.
- the number of alkoxysilyl groups in one molecule is not particularly limited as long as it is one or more, but two is preferable.
- the alkoxysilyl group is a group in which 1 to 3 alkoxy groups are bonded to one Si atom, and from the viewpoint of reactivity, a group in which 2 to 3 alkoxy groups are bonded to one Si atom is preferable. More preferred are those in which three alkoxy groups are bonded. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group, and among them, a methoxy group and an ethoxy group are preferable from the viewpoint of reactivity.
- the alkoxy groups bonded to one Si atom may be the same or different.
- Examples of such a compound (B) include bis (trimethoxysilylpropyl) monosulfide, bis (triethoxysilylpropyl) monosulfide, bis (tributoxysilylpropyl) monosulfide, bis (dimethoxymethylsilylpropyl) monosulfide, Bis (diethoxymethylsilylpropyl) monosulfide, bis (dibutoxymethylsilylpropyl) monosulfide, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bis (tributoxysilylpropyl) disulfide, bis (Dimethoxymethylsilylpropyl) disulfide, bis (diethoxymethylsilylpropyl) disulfide, bis (dibutoxymethylsilylpropyl) disulfide, bis (trimethoxysilane) Rupropyl) trisulfide
- bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bis (trimethoxysilylpropyl) trisulfide, and bis (triethoxy) are particularly preferred because of their excellent adhesive properties.
- Silylpropyl) trisulfide, bis (trimethoxysilylpropyl) tetrasulfide, and bis (triethoxysilylpropyl) tetrasulfide are preferred.
- the compound (B) is preferably such that the average value of n in the formula (1) is 2.0 to 4.5, and the average value of n is 3 Particularly preferred is a value of .5 to 4.5.
- the average value of n in the formula (1) is less than the lower limit, the adhesive properties tend not to be sufficiently improved.
- silver powder is used as filler particles (C) described later.
- the reaction with silver powder is likely to occur even at room temperature, and the storage stability tends to decrease.
- a compound having a sulfide bond and an alkoxysilyl group includes the following formula (2): X— (CH 2 ) m —SiR 1 R 2 R 3 (2)
- R 1 to R 3 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of R 1 to R 3 represents the number of carbon atoms. 1 to 10 alkoxy groups, X represents a halogen atom, and m is an integer of 1 to 10.
- the component represented by may be contained.
- the component represented by the formula (2) is one of the causes of an increase in viscosity when the adhesive composition is stored for a long time at room temperature, and the adhesion characteristics due to long storage at room temperature. It is also the cause of the manifestation of the decline. Therefore, in the adhesive composition of the present invention, the compound (B) having a content of the component represented by the formula (2) of 0.6% by mass or less (preferably 0.3% by mass or less) is used. It is done.
- the adhesive composition of the present invention has a good viscosity, high adhesive properties, and excellent reflow resistance even after long storage at room temperature.
- a highly reliable semiconductor device can be manufactured.
- the content rate of the component represented by the formula (2) exceeds the above upper limit, the viscosity increases due to long storage at room temperature, and the adhesive properties of the adhesive composition are remarkably deteriorated.
- the halogenated alkyl group in the component represented by the above formula (2) generates halogen ions in a high-temperature and high-humidity atmosphere as it is or after reacting with the functional group in the thermosetting resin (A).
- This halogen ion corrodes the wiring of the semiconductor element and the bonding pad for metal wire bonding, which causes a decrease in the reliability of the semiconductor product.
- the content of the component represented by the formula (2) needs to be within the above range, and is preferably as small as possible.
- an adhesive layer (cured product) having a hot water extraction halogen ion concentration of preferably 30 ppm or less, more preferably 20 ppm or less can be formed.
- a highly reliable semiconductor device can be manufactured.
- the content of the component represented by the formula (2) is determined by gas chromatography (for example, apparatus: “GC-14B” manufactured by Shimadzu Corporation, column: TC-5 (diameter 0.25 mm ⁇ 30 m)).
- Detector: FID carrier gas: He
- temperature program 50 ° C. ⁇ 2 minutes ⁇ 6.5 ° C./minute ⁇ 260° C. ⁇ 15 minutes
- internal standard substance 20% by mass of undecane
- measurement sample 0.5 ⁇ l
- the hot water extraction halogen ion concentration is 2 g of cured product and 40 g of distilled water in an extraction kettle, subjected to extraction treatment at 125 ° C. for 20 hours, and the halogen ion concentration in the supernatant after cooling (unit: ppm) Is a value measured by ion chromatography.
- a commercially available compound having a sulfide bond and an alkoxysilyl group can be used as long as the content of the component represented by the formula (2) is within the above range. Moreover, if the content rate of the component represented by the formula (2) exceeds the upper limit, if the content rate of the component represented by the formula (2) is reduced within the range by performing a purification treatment, It can be used as the compound (B) according to the present invention.
- the filler particle (C) may be contained as needed.
- Such filler particles (C) are not particularly limited, and various particles can be used according to various purposes, for example, silver powder, gold powder, copper powder, aluminum powder, nickel powder, palladium powder.
- metal powder silica powder, alumina powder, titania powder, aluminum nitride powder, boron nitride powder, etc., polyethylene powder, polyacrylate powder, polytetrafluoroethylene powder, polyamide powder, polyurethane powder, poly Examples thereof include polymer powders such as siloxane powders.
- filler particles (C) may be used alone or in combination of two or more depending on the application. Further, examples of the shape of the filler particles (C) include flakes, spheres, resins, needles, fibers, and the like, and are not particularly limited. Since the adhesive composition of the present invention may be discharged using a nozzle, the average particle diameter of the filler particles (C) is preferably 30 ⁇ m or less in order to prevent nozzle clogging. In order to maintain the reliability of the semiconductor device, it is preferable that the filler particles (C) have few ionic impurities such as sodium and chlorine.
- the content of the filler particles (C) in the adhesive composition of the present invention can be appropriately set according to the use form, application, type of filler particles, etc. 10 mass% or more and 95 mass% or less.
- silver powder is particularly preferable from the viewpoint of being hardly oxidized and excellent in workability. Moreover, it becomes possible by using silver powder as filler particle
- the silver powder is pure silver or a silver alloy powder.
- silver alloy a silver-copper alloy, silver-palladium alloy, silver-tin alloy containing 50% by mass or more, preferably 70% by mass or more of silver, Examples thereof include a silver-zinc alloy, a silver-magnesium alloy, and a silver-nickel alloy.
- the silver powder used in the present invention reduced powder, atomized powder or the like can be used as long as it is commercially available for electronic materials. It should be noted that some silver powders other than those for electronic materials have a large amount of ionic impurities. In particular, in order to maintain the reliability of the semiconductor device, it is preferable that the filler particles (C) have few ionic impurities such as sodium and chlorine.
- the average particle diameter of the silver powder is preferably 0.5 ⁇ m or more and 30 ⁇ m or less, and more preferably 1 ⁇ m or more and 10 ⁇ m or less. If the average particle size of the silver powder is less than the lower limit, the viscosity of the adhesive composition tends to be too high. On the other hand, exceeding the upper limit may cause nozzle clogging during dispensing as described above.
- the shape of the silver powder is not particularly limited, such as a flake shape or a spherical shape, but a flake shape is preferable.
- the content of silver powder is preferably 70% by mass or more and 95% by mass or less with respect to the entire adhesive composition.
- the silver powder content is less than the lower limit, the thermal conductivity and conductivity of the cured product tend to decrease.
- the upper limit is exceeded, the viscosity of the adhesive composition becomes too high and the coating workability decreases. There is a tendency.
- a metal powder having a particle size of 1 ⁇ m or less, preferably 10 nm or more and 100 nm or less can be used in combination with silver powder as required, and the viewpoint that the thermal conductivity is improved. Therefore, it is preferable to use a low melting point metal containing indium, tin or the like as a component.
- the adhesive composition for a semiconductor of the present invention may further contain various additives such as an antifoaming agent, a surfactant, a polymerization inhibitor, and an antioxidant, if necessary. Moreover, you may mix
- the adhesive composition for semiconductors of the present invention can be produced, for example, by premixing the above components, kneading using three rolls, and then performing a defoaming treatment under vacuum. Manufacturing conditions can be set as appropriate according to the type and amount of components used.
- the semiconductor device of the present invention is manufactured using the semiconductor adhesive composition of the present invention and can be manufactured by the following method, but the present invention is not limited thereto.
- the adhesive composition of the present invention is dispense-applied to a predetermined part of the support, and then a semiconductor element such as a chip is mounted, and the adhesive composition is heated and cured. A layer is formed.
- the semiconductor device of this invention can be manufactured by performing wire bonding and transfer molding using an epoxy resin.
- the adhesive composition of the present invention is dispensed on the back surface of a chip such as flip chip BGA (Ball Grid Array) sealed with an underfill material, and heat dissipating parts such as heat spreaders and lids are mounted. It can also be produced by heat curing.
- a chip such as flip chip BGA (Ball Grid Array) sealed with an underfill material, and heat dissipating parts such as heat spreaders and lids are mounted. It can also be produced by heat curing.
- the support examples include a lead frame and an organic substrate when bonding a semiconductor element, and a semiconductor element, a lead frame, an organic substrate, and a semiconductor product when bonding a heat dissipation member.
- the present invention is not limited to these.
- the thickness of the adhesive layer formed by the adhesive composition of the present invention is not particularly limited, but is preferably 5 ⁇ m or more and 100 ⁇ m or less, more preferably 10 ⁇ m or more and 50 ⁇ m or less, and particularly preferably 10 ⁇ m or more and 30 ⁇ m or less.
- the thickness of the adhesive layer is less than the lower limit, the adhesive properties tend to be lowered.
- the thickness exceeds the upper limit the thickness of the adhesive layer tends to be difficult to control.
- the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.
- the measuring method of the content rate of the component represented by the said Formula (2) in a compound (B), and the raw material used in the Example and the comparative example are shown below.
- (Compound A10) A diallyl ester compound obtained by reacting a diallyl ester of cyclohexanedicarboxylic acid with polypropylene glycol (molecular weight 1000, but containing about 15% of the diallyl ester of cyclohexanedicarboxylic acid used as a raw material).
- (Compound A13) 1,4-cyclohexanedimethanol monoacrylate (“CHDMMA” manufactured by Nippon Kasei Co., Ltd.).
- Compound (B) having sulfide bond and alkoxysilyl group (Compound B1) Cabras 4 (trade name, manufactured by Daiso Corporation, average value of n in the formula (1): about 3.8, 3-chloropropyltriethoxysilane (R 1 in the formula (2) To R 3 are all ethoxy groups, X is chlorine, and m is 3)): 0.11% by mass) (Compound B2)
- the above-mentioned Cabras 4 was treated at 50 ° C. for 168 hours.
- Solvent ⁇ -butyrolactone (boiling point 204 ° C.).
- Example 1 Compound A1 to Compound A3 and the solvent were charged in a separable flask in the proportions (unit: parts by mass) shown in Table 1, and stirred at 150 ° C. for 1 hour to obtain a pale yellow transparent liquid. After cooling this to room temperature, Compound B1, Compound Z3 and phosphorus catalyst were added in the proportions (unit: parts by mass) shown in Table 1 and stirred at room temperature for 30 minutes. This liquid was filtered through a 1 ⁇ m mesh to obtain a liquid adhesive composition.
- the spin coating conditions are set appropriately so as to be 50 ⁇ 5 ⁇ m, spin-coated using a spin coater (“1H-DX” manufactured by Mikasa Co., Ltd.), and heat-treated for 10 minutes in a dryer adjusted to 120 ° C. Thus, a wafer with an adhesive layer was obtained.
- the film thickness after spin coating was measured with a non-contact thickness meter.
- a dicing sheet (“FSL-N4003” manufactured by Sumitomo Bakelite Co., Ltd.) was attached to the surface of the adhesive layer of the obtained wafer with the adhesive layer, and then separated into 6 mm ⁇ 6 mm pieces using a dicing saw.
- the lead frame after curing is sealed with an epoxy-based sealing resin (“EME-G700” manufactured by Sumitomo Bakelite Co., Ltd.) using biphenyl aralkyl epoxy resin, and the sealing resin is post-mold cured at 175 ° C. for 4 hours.
- EME-G700 epoxy-based sealing resin manufactured by Sumitomo Bakelite Co., Ltd.
- biphenyl aralkyl epoxy resin biphenyl aralkyl epoxy resin
- test semiconductor devices were dried at 125 ° C. for 20 hours, and then moisture-absorbed at 60 ° C. and 60% RH for 120 hours. Thereafter, these test semiconductor devices were passed three times through an IR reflow apparatus set so that the time of 260 ° C. or higher was 10 seconds or longer. When the semiconductor device for test after the moisture absorption / reflow treatment was observed with a transmission ultrasonic flaw detector, no cracks or peeling of the adhesive layer was observed.
- solder reflow test (2)> A semiconductor device for solder reflow test was produced in the same manner as the solder reflow test (1) except that the adhesive composition immediately after preparation was used for 72 hours at 25 ° C. Observation with an apparatus confirmed that no voids or peeling occurred in the adhesive layer. Thereafter, these test semiconductor devices were subjected to moisture absorption / reflow treatment in the same manner as in the solder reflow test (1) and observed with a transmission ultrasonic flaw detector, and as a result, cracking and peeling of the adhesive layer were observed. There wasn't.
- a dicing sheet (“FSL-N4003” manufactured by Sumitomo Bakelite Co., Ltd.) was attached to the surface of the adhesive layer of the obtained wafer with the adhesive layer, and then separated into 3 mm ⁇ 3.5 mm pieces using a dicing saw. .
- the separated wafer is attached to a die bonder, picked up under the conditions that the ejector pin height is 350 ⁇ m (the bottom surface of the dicing film is 0) and the pickup time is 500 ms, the bond weight is 1.0 N, the heating temperature is 130 ° C., and the heating time is 8 seconds ( So that the surface temperature overlaps with a chip (3 mm ⁇ 3.5 mm, wire bond is reverse-bonded) that has been previously wire-bonded with a gold wire under the condition of the temperature of the surface to 130 ° C. (including the time for 7 seconds)
- the adhesive layer was cured by heating at 175 ° C. for 30 minutes.
- the lead frame after curing is sealed with an epoxy-based sealing resin (“EME-G700” manufactured by Sumitomo Bakelite Co., Ltd.) using biphenyl aralkyl epoxy resin, and the sealing resin is post-mold cured at 175 ° C. for 4 hours.
- EME-G700 epoxy-based sealing resin manufactured by Sumitomo Bakelite Co., Ltd.
- biphenyl aralkyl epoxy resin biphenyl aralkyl epoxy resin
- the sealing resin is post-mold cured at 175 ° C. for 4 hours.
- the outer leads were solder plated to obtain a semiconductor device for a high temperature and high humidity test. The resistance of the obtained test semiconductor device was measured, and it was confirmed that there was no electrical connection failure such as disconnection.
- a semiconductor device for high-temperature and high-humidity test was produced in the same manner as in the high-temperature and high-humidity test (1) except that an adhesive composition which had been allowed to stand at 25 ° C. for 72 hours was used instead of the adhesive composition immediately after preparation, and the resistance was measured. It was confirmed that there was no electrical connection failure such as disconnection. Thereafter, these test semiconductor devices were subjected to a high temperature and high humidity treatment in the same manner as in the high temperature and high humidity test (1), and the resistance of the test semiconductor device was measured again. The increase rate of the resistance value after the treatment was in the range of 0 to 20%, and it was confirmed that the electrical connection was good.
- Example 1-1 A liquid adhesive composition was obtained in the same manner as in Example 1 except that the compounds A1 to A3, the solvent, the compound Z3 and the phosphorus catalyst were blended in the proportions (unit: parts by mass) shown in Table 1. When the viscosity of the obtained adhesive composition was measured in the same manner as in Example 1, it was 5 Pa ⁇ s.
- a semiconductor device for a high temperature and high humidity test was produced in the same manner as in Example 1, and the resistance was measured. It was confirmed that there was no electrical connection failure such as disconnection. Thereafter, these test semiconductor devices were subjected to a high-temperature and high-humidity treatment in the same manner as in Example 1, and the resistance of the test semiconductor device was measured again.
- the increase rate of the resistance value after the treatment with respect to the resistance value before the high-temperature and high-humidity treatment was in the range of 0 to 20%, and it was confirmed that the electrical connection was good.
- Example 1-2 A liquid adhesive composition was obtained in the same manner as in Example 1 except that the compounds A1 to A3, the solvent, the compound Z1, the compound Z3, and the phosphorus catalyst were blended in the proportions (unit: parts by mass) shown in Table 1. .
- the viscosity of the obtained adhesive composition was measured in the same manner as in Example 1, it was 5 Pa ⁇ s.
- Example 1-3 A liquid adhesive composition was obtained in the same manner as in Example 1 except that the compounds A1 to A3, the solvent, the compound Z1, the compound Z3, and the phosphorus catalyst were blended in the proportions (unit: parts by mass) shown in Table 1. .
- the viscosity of the obtained adhesive composition was measured in the same manner as in Example 1, it was 5 Pa ⁇ s.
- the compound B1 having a sulfide bond and an alkoxysilyl group having a content of 0.11% by mass of the component represented by the formula (2) according to the present invention was used.
- the adhesive composition immediately after preparation and after standing was excellent in solder reflow resistance and high temperature and high humidity resistance, and the adhesive composition for semiconductors of the present invention was confirmed to have excellent storage stability at room temperature.
- the compound Z1 having a sulfide bond and an alkoxysilyl group having a content of the component represented by the formula (2) of 0.70% by mass and the compound B1 of Example 1 When the same amount was used (Comparative Example 1-2), the adhesive composition immediately after the preparation was excellent in solder reflow resistance, but the adhesive composition after standing was excellent in solder reflow resistance.
- the adhesive composition of Comparative Example 1-2 was inferior in storage stability at room temperature. In addition, both the adhesive compositions immediately after preparation and after standing were inferior in resistance to high temperature and high humidity.
- Example 2-1 Compound A4 and Compound A5 were charged into a separable flask at the ratio (unit: part by mass) shown in Table 2, and stirred at 150 ° C. for 30 minutes. After confirming that there was no remaining solid matter and became light brown and transparent, the mixture was cooled to room temperature, and the ratios (unit: parts by mass) of Compound A6, Compound A7, Compound A15, polymerization initiator and Compound Z4 are shown in Table 2. And stirred at room temperature for 30 minutes. Thereafter, this mixture was passed through a ceramic three roll to obtain a liquid resin composition which was uniformly clouded.
- PC-4000 automatic adhesive force measuring device
- Rate of change (%) ⁇ Adhesive strength (1) ⁇ Adhesive strength (2) ⁇ / Adhesive strength (1) ⁇ 100 Calculated by
- ⁇ Hot water extraction chloride ion concentration> The adhesive composition was cured at 175 ° C. for 30 minutes on a Teflon (registered trademark) sheet, and then pulverized. 2 g of this pulverized cured product and 40 g of distilled water were placed in an extraction kettle and subjected to extraction treatment at 125 ° C. for 20 hours. The chlorine ion concentration (unit: ppm) in the supernatant after cooling was measured by ion chromatography.
- Example 2-2 to 2-4 An adhesive composition was prepared in the same manner as in Example 2-1, except that Compound B2 to Compound B4 were added in the proportions (unit: parts by mass) shown in Table 2 instead of Compound B1, respectively.
- the adhesive strength and hot water extraction chlorine ion concentration of the obtained adhesive composition were measured in the same manner as in Example 2-1. The results are shown in Table 2.
- the compound B1 having a sulfide bond and an alkoxysilyl group having a content of the component represented by the formula (2) according to the present invention of 0.11% by mass was used.
- Example 2-1 it was confirmed that both of the adhesive compositions immediately after preparation and after standing were excellent in adhesiveness and excellent in the maintenance ratio of adhesive strength.
- Example 2-2 in the case of using Compound B2 obtained by treating Compound B1 at 50 ° C. for 168 hours (Example 2-2), compared with the case of using Compound B1 (Example 2-1), it was immediately after preparation and statically.
- Adhesive composition after installation was not significantly reduced in adhesiveness, showed excellent adhesiveness, the rate of change in adhesive strength did not increase significantly, and the adhesive strength maintenance rate was also excellent It was confirmed that. Further, it was confirmed that the adhesive compositions of Examples 2-1 and 2-2 had a low hot water extraction chlorine ion concentration and a high purity.
- Example 2-3 When the compound B3 having a sulfide bond and an alkoxysilyl group having a content of the component represented by the formula (2) according to the present invention of 0.59% by mass is used (Example 2-3), the preparation is performed. Both of the adhesive compositions immediately after and after standing exhibited relatively good adhesion, and it was confirmed that the adhesive strength maintenance rate was slightly large but within an acceptable range. Moreover, although the hot water extraction chlorine ion concentration was a little high, it was confirmed that it was an acceptable range.
- Example 2-4 When the compound B4 having a sulfide bond and an alkoxysilyl group having a content of the component represented by the formula (2) according to the present invention having a content of 0.33% by mass is used (Example 2-4), It was confirmed that any of the adhesive compositions immediately after and after standing exhibited a relatively good adhesive property and an excellent adhesive strength maintenance rate. Although the hot water extraction chlorine ion concentration was a little high, it was confirmed that it was within an acceptable range.
- Example 2-1 when the compound Z1 having a sulfide bond and an alkoxysilyl group having a content of the component represented by the formula (2) of 0.70% by mass is used instead of the compound (B) according to the present invention (comparison) In Example 2-1), the rate of change in adhesive strength was significantly increased. Further, in the case of using Compound Z2 obtained by treating Compound Z1 at 50 ° C. for 168 hours (Comparative Example 2-2), compared with the case of using Compound Z1 (Comparative Example 2-1), it was immediately after For any of the adhesive compositions after placement, the adhesiveness was greatly reduced, and the rate of change in adhesive strength was also greatly increased.
- Comparative Example 2-3 when the amount of the compound Z2 was increased, a significant decrease in adhesion as in Comparative Example 2-2 was suppressed, but an increase in the rate of change in adhesive strength was It was not improved. Furthermore, the adhesive compositions of Comparative Examples 2-1 to 2-3 have a relatively high hot water extraction chlorine ion concentration, and in particular, the adhesive composition of Comparative Example 2-3 has a very low purity. there were.
- Example 3-1 Compound A8, Compound 13 to Compound A15, polymerization initiator, Compound B1, Compound Z4 and particles C2 were blended in the proportions (unit: parts by mass) shown in Table 3, kneaded using three rolls, and defoamed. An adhesive composition was obtained. The storage stability, adhesive strength, storage elastic modulus and reflow resistance of the obtained adhesive composition were evaluated by the following methods. The results are shown in Table 3.
- PC-4000 automatic adhesive force measuring device
- Rate of change (%) ⁇ Adhesive strength (1) ⁇ Adhesive strength (2) ⁇ / Adhesive strength (1) ⁇ 100 Calculated by
- ⁇ Storage modulus> Using the prepared adhesive composition, a film-like test piece of 4 mm ⁇ 20 mm ⁇ 0.1 mm was prepared (curing conditions: 175 ° C., 30 minutes), and the following using a dynamic viscoelasticity measuring machine (DMA) The storage elastic modulus (unit: MPa) was measured under the conditions. Measurement temperature: -100 to 300 ° C Temperature increase rate: 5 ° C / min Frequency: 10Hz Load: 100mN Measurement mode: Tensile mode The case where the storage elastic modulus in 25 degreeC was 5000 Mpa or less was set as the pass.
- DMA dynamic viscoelasticity measuring machine
- a sealing material (“Sumicon EME-G700” manufactured by Sumitomo Bakelite Co., Ltd.)
- the peeled area (unit:%) of the die attach part of the semiconductor device after the treatment was measured using a transmission ultrasonic flaw detector.
- Semiconductor device QFP (14 mm x 20 mm x 2.0 mm)
- Lead frame Silver-plated copper frame (silver-plated surface) Chip size: 6mm x 6mm The case where the peeling area of the die attach part was less than 10% was regarded as acceptable.
- ⁇ Reflow resistance (2)> A semiconductor device was prepared in the same manner as in the reflow resistance (1) except that the adhesive composition after standing at 25 ° C. for 72 hours was used, and the peeled area (unit:%) of the die attach part was measured. . The case where the peeling area of the die attach part was less than 10% was regarded as acceptable.
- Examples 3-2 to 3-5 An adhesive composition was prepared in the same manner as in Example 3-1, except that compound A9 to compound A15 were blended in the proportions (unit: parts by mass) shown in Table 3 instead of compound A8 and compound 13 to compound A15. Preservability, adhesive strength, storage modulus and reflow resistance were evaluated. The results are shown in Table 3.
- Example 3-1 except that compound A9, compound A10, compound A13 to compound A15, polymerization initiator, compound Z1, compound Z4, compound Z5 and particle C2 were blended in the proportions (unit: parts by mass) shown in Table 3 Similarly, adhesive compositions were prepared and evaluated for storage stability, adhesive strength, storage modulus and reflow resistance. The results are shown in Table 3.
- the compound B1 having a sulfide bond and an alkoxysilyl group having a content of the component represented by the formula (2) according to the present invention of 0.11% by mass was used.
- the viscosity and adhesive strength of the adhesive composition were good, and the adhesive composition of the present invention hardly changed after standing. It was confirmed that the product was excellent in storage stability at room temperature. Moreover, it was confirmed that the storage elastic modulus is also good. Furthermore, it was confirmed that both of the adhesive compositions immediately after preparation and after standing were excellent in reflow resistance.
- Example 3-4 when the same amount of the compound Z1 having a sulfide bond and an alkoxysilyl group having a content of the component represented by the formula (2) of 0.70% by mass as the compound B1 of Example 3-2 was used (comparison) In Example 3-4), the adhesive composition immediately after preparation had good viscosity and adhesive strength and excellent reflow resistance, but the adhesive composition after standing had a viscosity. As a result, the adhesive strength and reflow resistance decreased, and the storage stability at room temperature was poor.
- the adhesive composition for a semiconductor that is superior in adhesive properties and storage stability at room temperature, particularly, adhesion that has a small increase in viscosity and excellent adhesive properties even when stored for a long time at room temperature. It becomes possible to provide an adhesive composition for a semiconductor that maintains its properties.
- the adhesive composition for a semiconductor of the present invention is useful as a die attach paste or an adhesive for a heat radiation member used for a highly reliable semiconductor device having excellent reflow resistance.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Die Bonding (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
X-(CH2)m-SiR1R2R3 (2)
(式(2)中、R1~R3はそれぞれ独立に炭素数1~10のアルキル基または炭素数1~10のアルコキシ基を表し、R1~R3のうちの少なくとも1つは炭素数1~10のアルコキシ基であり、Xはハロゲン原子を表し、mは1~10の整数である。)
で表される成分にあることを見出し、本発明を完成するに至った。
-(S)n- (1)
(式(1)中、nは1以上の整数である。)
で表されるスルフィド結合とアルコキシシリル基とを有する化合物(B)を含有するものである。前記化合物(B)において、下記式(2):
X-(CH2)m-SiR1R2R3 (2)
(式(2)中、R1~R3はそれぞれ独立に炭素数1~10のアルキル基または炭素数1~10のアルコキシ基を表し、R1~R3のうちの少なくとも1つは炭素数1~10のアルコキシ基であり、Xはハロゲン原子を表し、mは1~10の整数である。)
で表される成分の含有率は0.6質量%以下である。
-(S)n- (1)
(式(1)中、nは1以上の整数である。)
で表されるスルフィド結合とアルコキシシリル基とを有する化合物(B)を含有するものである。前記化合物(B)には、下記式(2):
X-(CH2)m-SiR1R2R3 (2)
(式(2)中、R1~R3はそれぞれ独立に炭素数1~10のアルキル基または炭素数1~10のアルコキシ基を表し、R1~R3のうちの少なくとも1つは炭素数1~10のアルコキシ基であり、Xはハロゲン原子を表し、mは1~10の整数である。)
で表される成分が含まれ、その含有率は0.6質量%以下である。
本発明に用いられる熱硬化性樹脂(A)は、加熱により3次元的網目構造を形成し、硬化する樹脂である。このような熱硬化性樹脂(A)は、特に限定されるものではないが、ペースト状の接着剤樹脂組成物を得るためには室温で液状であることが好ましい。
本発明に用いられる化合物(B)は、下記式(1):
-(S)n- (1)
(式(1)中、nは1以上の整数である。)
で表されるスルフィド結合とアルコキシシリル基とを有するものである。
X-(CH2)m-SiR1R2R3 (2)
(式(2)中、R1~R3はそれぞれ独立に炭素数1~10のアルキル基または炭素数1~10のアルコキシ基を表し、R1~R3のうちの少なくとも1つは炭素数1~10のアルコキシ基であり、Xはハロゲン原子を表し、mは1~10の整数である。)
で表される成分が含まれていることがある。
本発明の接着剤組成物においては、必要に応じて充填材粒子(C)が含まれていてもよい。このような充填材粒子(C)としては、特に限定されず、種々の目的に応じて種々の粒子を使用することができ、例えば、銀粉、金粉、銅粉、アルミニウム粉、ニッケル粉、パラジウム粉などの金属粉、シリカ粉末、アルミナ粉末、チタニア粉末、アルミニウムナイトライド粉末、ボロンナイトライド粉末などのセラミック粉末、ポリエチレン粉末、ポリアクリル酸エステル粉末、ポリテトラフルオロエチレン粉末、ポリアミド粉末、ポリウレタン粉末、ポリシロキサン粉末などの高分子粉末が挙げられる。
本発明の半導体用接着剤組成物は、例えば、前記各成分を予備混合した後、3本ロールを用いて混練し、その後、真空下で脱泡処理を施すことにより製造することができる。製造条件は、使用する成分の種類や配合量などに応じて適宜設定することができる。
本発明の半導体装置は、本発明の半導体用接着剤組成物を用いて製造されるものであり、以下の方法により製造することができるが、本発明ではこれに限定されるものではない。例えば、市販のダイボンダーを用いて、支持体の所定の部位に本発明の接着剤組成物をディスペンス塗布した後、チップなどの半導体素子をマウントし、接着剤組成物を加熱硬化させることによって接着剤層を形成させる。その後、ワイヤーボンディングを施し、エポキシ樹脂を用いてトランスファー成形することによって本発明の半導体装置を製造することができる。また、フリップチップ接合した後、アンダーフィル材で封止したフリップチップBGA(Ball Grid Array)などのチップ裏面に本発明の接着剤組成物をディスペンス塗布し、ヒートスプレッダーやリッドといった放熱部品を搭載して加熱硬化することによっても製造することができる。
ガスクロマトグラフ法(装置:(株)島津製作所製「GC-14B」、カラム:TC-5(直径0.25mm×30m)、検出器:FID、キャリアーガス:He、温度プログラム:50℃×2分→6.5℃/分→260℃×15分、内部標準物質:ウンデカンを20質量%添加、測定試料:0.5μl)により測定した。
熱硬化性樹脂(A):
(化合物A1)オルソクレゾールノボラック型エポキシ樹脂(軟化点70℃、エポキシ当量210)。
(化合物A2)フェノールアラルキル樹脂(分子量612、軟化点75℃、水酸基当量175)。
(化合物A3)ポリヒドロキシスチレン(分子量2080、分散度1.26)。
(化合物A4)ビスフェノールAとエピクロルヒドリンとの反応により得られるジグリシジルビスフェノールA(エポキシ当量180、常温で液体)。
(化合物A5)ビスフェノールF(大日本インキ工業(株)製「DIC-BPF」、水酸基当量100)。
(化合物A6)ジシアンジアミド。
(化合物A7)2-メチルイミダゾールと2,4-ジアミノ-6-ビニルトリアジンとの付加物(四国化成工業(株)製「キュアゾール2MZ-A」)。
(化合物A8)ポリテトラメチレングリコールとイソホロンジイソシアネートと2-ヒドロキシメチルメタクリレートとの反応により得られたウレタンジメタクリレート化合物(分子量約1600)。
(化合物A9)ポリテトラメチレングリコールとマレイミド化酢酸の反応により得られたビスマレイミド化合物(分子量580)。
(化合物A10)シクロヘキサンジカルボン酸のジアリルエステルとポリプロピレングリコールとの反応により得られたジアリルエステル化合物(分子量1000、ただし原料として用いたシクロヘキサンジカルボン酸のジアリルエステルを約15%含む)。
(化合物A11)1,4-シクロヘキサンジメタノール/1,6-ヘキサンジオール(=3/1(質量比))と炭酸ジメチルの反応により得られたポリカーボネートジオールとメチルメタクリレートの反応により得られたポリカーボネートジメタクリレート化合物(分子量1000)。
(化合物A12)酸価108mgKOH/gで分子量4600のアクリルオリゴマーと2-ヒドロキシメタクリレート/ブチルアルコール(=1/2(モル比))との反応により得られたメタクリル化アクリルオリゴマー(分子量5000)。
(化合物A13)1,4-シクロヘキサンジメタノールモノアクリレート(日本化成(株)製「CHDMMA」)。
(化合物A14)2-メタクリロイルオキシエチルコハク酸(共栄社化学(株)製「ライトエステルHO-MS」)。
(化合物A15)1,6-ヘキサンジオールジメタクリレート(共栄社化学(株)製「ライトエステル1,6HX」)。
(重合開始剤)ジクミルパーオキサイド(日本油脂(株)製「パークミルD」、急速加熱試験における分解温度:126℃)。
(リン系触媒)攪拌装置付きのセパラプルフラスコに4,4’-ビスフェノールS(日華化学工業(株)製「BPS-N」)37.5g(0.15モル)、テトラフェニルホスホニウムプロマイド41.9g(0.1モル)およびイオン交換水100mlを仕込み、100℃で攪拌した。次いで、固形分が不溶な状態のこの溶液に、50mlのイオン交換水に水酸化ナトリウム4.0g(0.1モル)を予め溶解した溶液を、攪拌しながら添加した。その後、しばらく攪拌を継続して白色沈殿を得た。この沈殿をろ過により回収し、乾燥した。得られた白色結晶(収量:68.5g)をリン系触媒として使用した。
(化合物B1)カブラス4(商品名、ダイソー(株)製、前記式(1)中のnの平均値:約3.8、3-クロロプロピルトリエトキシシラン(前記式(2)中のR1~R3がすべてエトキシ基であり、Xが塩素であり、mが3であるもの)の含有率:0.11質量%)
(化合物B2)前記カブラス4を50℃で168時間処理したもの。
(化合物B3)Si-69(商品名、デグサ社製、前記式(1)中のnの平均値:約3.7、3-クロロプロピルトリエトキシシラン(前記式(2)中のR1~R3がすべてエトキシ基であり、Xが塩素であり、mが3であるもの)の含有率:0.59質量%)。
(化合物B4)Si-75(商品名、デグサ社製、前記式(1)中のnの平均値:約2.4、3-クロロプロピルトリエトキシシラン(前記式(2)中のR1~R3がすべてエトキシ基であり、Xが塩素であり、mが3であるもの)の含有率:0.33質量%)。
(粒子C1)平均粒径1.5μm、比表面積約5m2/gの球状シリカ粉末。
(粒子C2)平均粒径8μm、最大粒径30μmのフレーク状銀粉。
(化合物Z1)A-1289(商品名、日本ユニカー(株)製、前記式(1)中のnの平均値:約3.8、3-クロロプロピルトリエトキシシラン(前記式(2)中のR1~R3がすべてエトキシ基であり、Xが塩素であり、mが3であるもの)の含有率:0.70質量%)。
(化合物Z2)前記A-1289を50℃で168時間処理したもの。
(化合物Z3)3-グリシジルプロピルトリメトキシシラン(信越化学工業(株)製「KBM-403E」)。
(化合物Z4)3-メルカプトプロピルトリメトキシシラン(信越化学工業(株)製「KBM-803P」)。
化合物A1~化合物A3および溶媒を表1に示す割合(単位:質量部)でセパラブルフラスコに仕込み、150℃で1時間攪拌して淡黄色透明の液体を得た。これを室温まで冷却した後、化合物B1、化合物Z3およびリン系触媒を表1に示す割合(単位:質量部)で添加し、室温で30分間攪拌した。この液体を1μmのメッシュでろ過して液状の接着剤組成物を得た。
調製直後(4時間以内)の接着剤組成物を8インチウエハ(銅0.5%のアルミパッドを有し、パッシベーションがSiNであり、厚みが350μmのもの。)に、塗布後の膜厚が50±5μmになるようにスピンコート条件を適宜設定し、スピンコーター(ミカサ(株)製「1H-DX」)を用いてスピンコートし、120℃に調整した乾燥機中で10分間加熱処理して接着剤層付きウエハを得た。なお、スピンコート後の膜厚は非接触の厚み計で測定した。
調製直後の接着剤組成物の代わりに25℃で72時間静置したものを用いた以外は前記半田リフロー試験(1)と同様にして半田リフロー試験用半導体装置を作製し、透過型超音波探傷装置により観察し、接着剤層にボイドおよび剥離が発生していないことを確認した。その後、これらの試験用半導体装置に前記半田リフロー試験(1)と同様にして吸湿・リフロー処理を施し、透過型超音波探傷装置により観察したところ、接着剤層のクラックおよび剥離の発生は見られなかった。
調製直後(4時間以内)の接着剤組成物を6インチウエハ(回路が形成されていないベアシリコンからなり、厚みが625μmのもの。)に、塗布後の膜厚が120±10μmになるようにスピンコート条件を適宜設定し、スピンコーター(ミカサ(株)製「1H-DX」)を用いてスピンコートし、120℃に調整した乾燥機中で30分間加熱処理して接着剤層付きウエハを得た。なお、スピンコート後の膜厚は非接触の厚み計で測定した。
調製直後の接着剤組成物の代わりに25℃で72時間静置したものを用いた以外は前記高温高湿試験(1)と同様にして高温高湿試験用半導体装置を作製し、抵抗を測定して、断線等の電気的な接続不良がないことを確認した。その後、これらの試験用半導体装置に前記高温高湿試験(1)と同様にして高温高湿処理を施し、再度、試験用半導体装置の抵抗を測定したところ、高温高湿処理前の抵抗値に対する処理後の抵抗値の上昇率が0~20%の範囲内にあり、電気的に良好に接続されていることが確認された。
化合物A1~化合物A3、溶媒、化合物Z3およびリン系触媒を表1に示す割合(単位:質量部)で配合した以外は実施例1と同様にして液状の接着剤組成物を得た。得られた接着剤組成物の粘度を実施例1と同様にして測定したところ、5Pa・sであった。
化合物A1~化合物A3、溶媒、化合物Z1、化合物Z3およびリン系触媒を表1に示す割合(単位:質量部)で配合した以外は実施例1と同様にして液状の接着剤組成物を得た。得られた接着剤組成物の粘度を実施例1と同様にして測定したところ、5Pa・sであった。
化合物A1~化合物A3、溶媒、化合物Z1、化合物Z3およびリン系触媒を表1に示す割合(単位:質量部)で配合した以外は実施例1と同様にして液状の接着剤組成物を得た。得られた接着剤組成物の粘度を実施例1と同様にして測定したところ、5Pa・sであった。
化合物A4および化合物A5を表2に示す割合(単位:質量部)でセパラブルフラスコに仕込み、150℃で30分間攪拌した。固形分の残存がなく淡褐色透明になったことを確認した後、室温まで冷却し、化合物A6、化合物A7、化合物A15、重合開始剤および化合物Z4を表2に示す割合(単位:質量部)で添加し、室温で30分間攪拌した。その後、この混合物をセラミック製の3本ロールに通して均質に白濁した液状の樹脂組成物を得た。
調製直後(4時間以内)の接着剤組成物を用いて、銀めっきした銅フレームに6mm×6mmのシリコンチップをマウントし、175℃のオーブン中で30分間加熱して接着剤組成物を硬化させた。硬化後、85℃、85%で72時間吸湿処理を施し、自動接着力測定装置(dage社製「PC-4000」)を用いて260℃での熱時ダイシェア強度(単位:N/チップ)を測定した。
調製直後の接着剤組成物の代わりに25℃で72時間静置した後の接着剤組成物を用いた以外は前記接着強度(1)と同様にして260℃での熱時ダイシェア強度(単位:N/チップ)を測定した。
変化率(%)={接着強度(1)-接着強度(2)}/接着強度(1)×100
により算出した。
テフロン(登録商標)製のシート上で接着剤組成物を175℃で30分間硬化させた後、粉砕した。この粉砕した硬化物2gと蒸留水40gとを抽出釜に入れ、125℃で20時間抽出処理を施した。冷却後の上澄み液中の塩素イオン濃度(単位:ppm)をイオンクロマトグラフ法により測定した。
化合物B1の代わりにそれぞれ化合物B2~化合物B4を表2に示す割合(単位:質量部)で添加した以外は実施例2-1と同様にして接着剤組成物を調製した。得られた接着剤組成物の接着強度および熱水抽出塩素イオン濃度を実施例2-1と同様にして測定した。その結果を表2に示す。
化合物B1の代わりにそれぞれ化合物Z1または化合物Z2を表2に示す割合(単位:質量部)で添加した以外は実施例2-1と同様にして接着剤組成物を調製した。得られた接着剤組成物の接着強度および熱水抽出塩素イオン濃度を実施例2-1と同様にして測定した。その結果を表2に示す。
化合物A8、化合物13~化合物A15、重合開始剤、化合物B1、化合物Z4および粒子C2を表3に示す割合(単位:質量部)で配合し、3本ロールを用いて混練し、脱泡して接着剤組成物を得た。得られた接着剤組成物の保存性、接着強度、貯蔵弾性率および耐リフロー性を以下の方法により評価した。その結果を表3に示す。
調製直後(初期)および25℃で72時間静置後の接着剤組成物の粘度(単位:Pa・s)を、E型粘度計(3°コーン)を用いて25℃、2.5rpmで測定した。また、初期粘度に対する72時間静置後の粘度の変化率(単位:%)を算出した。粘度が15~25Pa・s、粘度の変化率が20%以下の場合を合格とした。
調製直後(3時間以内)の接着剤組成物を用いて、銀めっきした銅フレームに6mm×6mmのシリコンチップをマウントし、175℃のオーブン中で30分間加熱して接着剤組成物を硬化させた。硬化後、85℃、85%で72時間吸湿処理を施し、自動接着力測定装置(dage社製「PC-4000」)を用いて260℃での熱時ダイシェア強度(単位:N/チップ)を測定した。260℃での熱時ダイシェア強度が30N/チップ以上の場合を合格とした。
25℃で72時間静置した後の接着剤組成物を用いた以外は前記接着強度(3)と同様にして260℃での熱時ダイシェア強度(単位:N/チップ)を測定した。260℃での熱時ダイシェア強度が30N/チップ以上の場合を合格とした。
変化率(%)={接着強度(1)-接着強度(2)}/接着強度(1)×100
により算出した。
調製した接着剤組成物を用いて4mm×20mm×0.1mmのフィルム状の試験片を作製し(硬化条件:175℃、30分)、動的粘弾性測定機(DMA)を用いて以下の条件で貯蔵弾性率(単位:MPa)を測定した。
測定温度:-100~300℃
昇温速度:5℃/分
周波数:10Hz
荷重:100mN
測定モード:引っ張りモード
25℃における貯蔵弾性率が5000MPa以下の場合を合格とした。
接着剤組成物の調製直後(3時間以内)に、この接着剤組成物を用いて、下記のリードフレームにシリコンチップをマウントし、175℃のオーブン中で30分間加熱して接着剤組成物を硬化させて接着した。硬化後のリードフレームを封止材料(住友ベークライト(株)製「スミコンEME-G700」)を用いて封止し、半導体装置を作製した。この半導体装置を85℃、相対湿度60%で160時間吸湿処理した後、IRリフロー処理(260℃、10秒、3回リフロー)を施した。処理後の半導体装置のダイアタッチ部の剥離面積(単位:%)を、透過型超音波探傷装置を用いて測定した。
半導体装置:QFP(14mm×20mm×2.0mm)
リードフレーム:銀メッキした銅フレーム(被着部分が銀メッキ表面)
チップサイズ:6mm×6mm
ダイアタッチ部の剥離面積が10%未満の場合を合格とした。
25℃で72時間静置した後の接着剤組成物を用いた以外は前記耐リフロー性(1)と同様にして半導体装置を作製し、ダイアタッチ部の剥離面積(単位:%)を測定した。ダイアタッチ部の剥離面積が10%未満の場合を合格とした。
化合物A8および化合物13~化合物A15の代わりに化合物A9~化合物A15を表3に示す割合(単位:質量部)で配合した以外は実施例3-1と同様にして接着剤組成物を調製し、保存性、接着強度、貯蔵弾性率および耐リフロー性を評価した。その結果を表3に示す。
化合物A9、化合物A10、化合物A13~化合物A15、重合開始剤、化合物Z1、化合物Z4、化合物Z5および粒子C2を表3に示す割合(単位:質量部)で配合した以外は実施例3-1と同様にして接着剤組成物を調製し、保存性、接着強度、貯蔵弾性率および耐リフロー性を評価した。その結果を表3に示す。
Claims (5)
- 熱硬化性樹脂(A)、および下記式(1):
-(S)n- (1)
(式(1)中、nは1以上の整数である。)
で表されるスルフィド結合とアルコキシシリル基とを有する化合物(B)を含有し、
前記化合物(B)中の下記式(2):
X-(CH2)m-SiR1R2R3 (2)
(式(2)中、R1~R3はそれぞれ独立に炭素数1~10のアルキル基または炭素数1~10のアルコキシ基を表し、R1~R3のうちの少なくとも1つは炭素数1~10のアルコキシ基であり、Xはハロゲン原子を表し、mは1~10の整数である。)
で表される成分の含有率が0.6質量%以下である、半導体接着剤組成物。 - 充填材粒子(C)をさらに含有する請求項1に記載の半導体接着剤組成物。
- 前記化合物(B)が、前記式(1)中のnの平均値が2.0~4.5の化合物である、請求項1に記載の半導体接着剤組成物。
- 硬化物の熱水抽出ハロゲンイオン濃度が30ppm以下である、請求項1に記載の半導体接着剤組成物。
- 半導体素子が、請求項1~4のうちのいずれか一項に記載の半導体用接着剤組成物により接着されている半導体装置。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008800098163A CN101778919B (zh) | 2008-10-24 | 2008-10-24 | 半导体用粘着剂组合物及使用该粘着剂组合物制造的半导体装置 |
PCT/JP2008/069358 WO2010046996A1 (ja) | 2008-10-24 | 2008-10-24 | 半導体用接着剤組成物およびそれを用いて製造した半導体装置 |
JP2008554353A JP4352282B1 (ja) | 2008-10-24 | 2008-10-24 | 半導体用接着剤組成物およびそれを用いて製造した半導体装置 |
KR1020097019989A KR20100049499A (ko) | 2008-10-24 | 2008-10-24 | 반도체용 접착제 조성물 및 그것을 이용하여 제조한 반도체 장치 |
TW097141644A TW201016734A (en) | 2008-10-24 | 2008-10-29 | Adhesive composition for semiconductor and semiconductor device manufactured using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2008/069358 WO2010046996A1 (ja) | 2008-10-24 | 2008-10-24 | 半導体用接着剤組成物およびそれを用いて製造した半導体装置 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010046996A1 true WO2010046996A1 (ja) | 2010-04-29 |
Family
ID=41314396
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2008/069358 WO2010046996A1 (ja) | 2008-10-24 | 2008-10-24 | 半導体用接着剤組成物およびそれを用いて製造した半導体装置 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP4352282B1 (ja) |
KR (1) | KR20100049499A (ja) |
CN (1) | CN101778919B (ja) |
TW (1) | TW201016734A (ja) |
WO (1) | WO2010046996A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011052043A (ja) * | 2009-08-31 | 2011-03-17 | Sumitomo Bakelite Co Ltd | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
KR20170084287A (ko) * | 2015-08-03 | 2017-07-19 | 후루카와 덴키 고교 가부시키가이샤 | 도전성 조성물 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI488345B (zh) * | 2010-12-03 | 2015-06-11 | Hon Hai Prec Ind Co Ltd | 發光二極管導線架 |
US9034695B2 (en) | 2012-04-11 | 2015-05-19 | Taiwan Semiconductor Manufacturing Company, Ltd. | Integrated thermal solutions for packaging integrated circuits |
US9391000B2 (en) | 2012-04-11 | 2016-07-12 | Taiwan Semiconductor Manufacturing Company, Ltd. | Methods for forming silicon-based hermetic thermal solutions |
KR101395322B1 (ko) * | 2012-07-18 | 2014-05-16 | 도레이첨단소재 주식회사 | 고전압에서 전기적 신뢰성이 향상된 접착제 조성물 및 이를 이용한 반도체 패키지용 접착 테이프 |
JP6413249B2 (ja) * | 2014-02-03 | 2018-10-31 | 住友ベークライト株式会社 | 熱伝導性シートおよび半導体装置 |
CN107075258B (zh) * | 2014-10-01 | 2020-03-06 | 纳美仕有限公司 | 树脂组合物 |
CN109777342A (zh) * | 2018-12-29 | 2019-05-21 | 江苏创景科技有限公司 | 一种用于双组分有机硅灌封胶的固化促进剂及其应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03105932A (ja) * | 1989-09-20 | 1991-05-02 | Hitachi Ltd | シート状接着剤並びに当該接着剤を用いた半導体装置 |
JPH11335631A (ja) * | 1998-04-28 | 1999-12-07 | Degussa Huels Ag | 2つの固体を結合させる方法および得られる構造部材 |
JP2001257219A (ja) * | 2000-03-13 | 2001-09-21 | Sumitomo Bakelite Co Ltd | ダイアタッチペースト及び半導体装置 |
JP2007262243A (ja) * | 2006-03-28 | 2007-10-11 | Sumitomo Bakelite Co Ltd | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3311340A1 (de) * | 1983-03-29 | 1984-10-11 | Degussa Ag, 6000 Frankfurt | Verfahren zur herstellung von schwefelhaltigen organosiliciumverbindungen |
US6884854B2 (en) * | 2000-04-10 | 2005-04-26 | Henkel Kommanditgesellschaft Auf Aktien | Composition of epoxy resin, low glass transition temperature copolymer, latent hardener and carboxy-terminated polyamide and/or polyamide |
-
2008
- 2008-10-24 CN CN2008800098163A patent/CN101778919B/zh active Active
- 2008-10-24 JP JP2008554353A patent/JP4352282B1/ja active Active
- 2008-10-24 KR KR1020097019989A patent/KR20100049499A/ko not_active Application Discontinuation
- 2008-10-24 WO PCT/JP2008/069358 patent/WO2010046996A1/ja active Application Filing
- 2008-10-29 TW TW097141644A patent/TW201016734A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03105932A (ja) * | 1989-09-20 | 1991-05-02 | Hitachi Ltd | シート状接着剤並びに当該接着剤を用いた半導体装置 |
JPH11335631A (ja) * | 1998-04-28 | 1999-12-07 | Degussa Huels Ag | 2つの固体を結合させる方法および得られる構造部材 |
JP2001257219A (ja) * | 2000-03-13 | 2001-09-21 | Sumitomo Bakelite Co Ltd | ダイアタッチペースト及び半導体装置 |
JP2007262243A (ja) * | 2006-03-28 | 2007-10-11 | Sumitomo Bakelite Co Ltd | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011052043A (ja) * | 2009-08-31 | 2011-03-17 | Sumitomo Bakelite Co Ltd | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
KR20170084287A (ko) * | 2015-08-03 | 2017-07-19 | 후루카와 덴키 고교 가부시키가이샤 | 도전성 조성물 |
EP3333856A4 (en) * | 2015-08-03 | 2018-12-26 | Furukawa Electric Co., Ltd. | Conductive composition |
KR102019761B1 (ko) | 2015-08-03 | 2019-09-09 | 후루카와 덴키 고교 가부시키가이샤 | 도전성 조성물 |
US10689550B2 (en) | 2015-08-03 | 2020-06-23 | Furukawa Electric Co., Ltd. | Electrically conductive composition |
Also Published As
Publication number | Publication date |
---|---|
TW201016734A (en) | 2010-05-01 |
CN101778919A (zh) | 2010-07-14 |
CN101778919B (zh) | 2012-09-05 |
TWI322821B (ja) | 2010-04-01 |
JP4352282B1 (ja) | 2009-10-28 |
KR20100049499A (ko) | 2010-05-12 |
JPWO2010046996A1 (ja) | 2012-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5266719B2 (ja) | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 | |
JP4352282B1 (ja) | 半導体用接着剤組成物およびそれを用いて製造した半導体装置 | |
KR101195693B1 (ko) | 반도체용 접착제 조성물 및 그것을 이용하여 제조한 반도체 장치 | |
JP5428134B2 (ja) | 液状樹脂組成物および該液状樹脂組成物を使用して作製した半導体装置 | |
JP5555990B2 (ja) | 樹脂組成物、および樹脂組成物を用いて作製した半導体装置 | |
JP5266797B2 (ja) | 樹脂組成物、接着剤層、及びそれらを用いて作製した半導体装置 | |
JP5061939B2 (ja) | 熱伝導性樹脂組成物、接着剤層、及びそれらを用いて作製した半導体装置。 | |
JP5880450B2 (ja) | 樹脂組成物および半導体装置 | |
JP6119603B2 (ja) | 半導体装置 | |
WO2018079533A1 (ja) | 熱伝導性ペーストおよび電子装置 | |
JP5396914B2 (ja) | 樹脂組成物、および樹脂組成物を用いて作製した半導体装置 | |
JP6244124B2 (ja) | ダイアタッチ用樹脂組成物 | |
JP5423262B2 (ja) | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 | |
JP6420121B2 (ja) | 半導体接着用樹脂組成物及び半導体装置 | |
JP5577845B2 (ja) | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 | |
JP4857574B2 (ja) | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 | |
JP5589337B2 (ja) | 積層構造体の製造方法 | |
JP5482077B2 (ja) | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 | |
JP5857410B2 (ja) | 半導体装置の製造方法 | |
JP5392990B2 (ja) | 液状樹脂組成物および該液状樹脂組成物を使用して作製した半導体装置 | |
JP2011073405A (ja) | 積層構造体の製造方法 | |
JP5625430B2 (ja) | 半導体用接着剤および半導体装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880009816.3 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008554353 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020097019989 Country of ref document: KR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08877562 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 08877562 Country of ref document: EP Kind code of ref document: A1 |