WO2011129272A1 - Attachment material for semiconductor chip bonding, attachment film for semiconductor chip bonding, semiconductor device manufacturing method, and semiconductor device - Google Patents

Attachment material for semiconductor chip bonding, attachment film for semiconductor chip bonding, semiconductor device manufacturing method, and semiconductor device Download PDF

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Publication number
WO2011129272A1
WO2011129272A1 PCT/JP2011/058883 JP2011058883W WO2011129272A1 WO 2011129272 A1 WO2011129272 A1 WO 2011129272A1 JP 2011058883 W JP2011058883 W JP 2011058883W WO 2011129272 A1 WO2011129272 A1 WO 2011129272A1
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WIPO (PCT)
Prior art keywords
semiconductor chip
bonding
adhesive material
semiconductor
semiconductor device
Prior art date
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PCT/JP2011/058883
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French (fr)
Japanese (ja)
Inventor
幸平 竹田
石澤　英亮
千鶴 金
畠井　宗宏
善雄 西村
久敏 岡山
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201180018592.4A priority Critical patent/CN102834907B/en
Priority to JP2011522345A priority patent/JP4922474B2/en
Priority to KR1020127024134A priority patent/KR20130064043A/en
Publication of WO2011129272A1 publication Critical patent/WO2011129272A1/en

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    • H—ELECTRICITY
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    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • 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
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    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
    • H—ELECTRICITY
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    • H01L2924/01—Chemical elements
    • H01L2924/01004—Beryllium [Be]
    • 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]
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    • 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
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2924/01—Chemical elements
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    • H01L2924/01—Chemical elements
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    • H01L2924/013—Alloys
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    • H01L2924/0665—Epoxy resin

Definitions

  • the present invention relates to an adhesive material for bonding a semiconductor chip that can manufacture a highly reliable semiconductor device by controlling the fillet shape so that it does not become a convex shape.
  • the present invention also provides a semiconductor chip bonding adhesive film made of the semiconductor chip bonding adhesive material, a method of manufacturing a semiconductor device using the semiconductor chip bonding adhesive material or the semiconductor chip bonding adhesive film, and the semiconductor.
  • the present invention relates to a semiconductor device obtained by a device manufacturing method.
  • connection terminals pads made of solder or the like
  • a method is used in which a semiconductor chip having a plurality of bumps is connected to another semiconductor chip or a substrate through the bumps and then filled with an underfill.
  • undercuring under shrinkage or under reflow test or thermal cycle test for example, due to a difference in coefficient of linear expansion between the semiconductor chip and the substrate, Stress may concentrate on the interface of the fill and cracks may occur.
  • Patent Document 1 discloses a semiconductor element, a substrate on which the semiconductor element is mounted, and a sealing resin that seals a circuit formation surface formed on the semiconductor element.
  • a side surface covering portion that covers the outer peripheral side surface of the semiconductor element is provided.
  • Such a side surface covering portion covering the outer peripheral side surface of the semiconductor element is generally called a fillet.
  • the height of the side surface covering portion from the circuit formation surface is within a predetermined range in order to more reliably suppress the occurrence of cracks.
  • Patent Document 2 discloses a specific flip in which a sealing resin is injected between a circuit board and a semiconductor chip, and a sealing resin is applied to an outer peripheral side portion of the semiconductor chip to form a fillet portion.
  • a chip semiconductor package is described.
  • the fillet portion has a structure in which the surface forms an inclined surface extending outward from the upper edge of the outer peripheral side portion of the semiconductor chip toward the substrate.
  • Patent Document 2 discloses that the inclination angle formed between the inclined surface and the outer peripheral side portion of the semiconductor chip is 50 degrees or less in the vicinity of the upper edge of the outer peripheral side portion of the semiconductor chip. It is described that semiconductor chip breakage is reduced and reduced.
  • the conventional method has a problem that the process of forming the fillet is complicated, and the occurrence of cracks is not sufficiently suppressed by the formation of the fillet.
  • An object of the present invention is to provide an adhesive material for bonding a semiconductor chip that can control a fillet shape so as not to be a convex shape and can manufacture a highly reliable semiconductor device.
  • the present invention also provides a semiconductor chip bonding adhesive film made of the semiconductor chip bonding adhesive material, a method of manufacturing a semiconductor device using the semiconductor chip bonding adhesive material or the semiconductor chip bonding adhesive film, and the semiconductor. It is an object of the present invention to provide a semiconductor device obtained by a device manufacturing method.
  • the 25 ° C. shear modulus Gr measured with a viscoelasticity measuring apparatus is 1 ⁇ 10 6 Pa or more, and the lowest complex viscosity ⁇ * min up to the solder melting point measured with a rheometer is 5 ⁇ 10 1 Pa ⁇ s or less.
  • the complex viscosity ⁇ * (1 Hz) measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 1 Hz is 0.5-4 of the complex viscosity ⁇ * (10 Hz) measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 10 Hz.
  • the shape of the cross-sectional view of the fillet is 2 tends to be convex.
  • the angle formed by the side wall of the semiconductor chip and the fillet tends to be 70 ° or more.
  • the inventors tend to cause stress concentration on the convex portion and easily cause peeling or cracking of the semiconductor chip, while forming a non-convex fillet as shown in FIG.
  • a highly reliable semiconductor device can be manufactured by suppressing the concentration of stress.
  • the present inventors can form a non-convex fillet by setting the 25 ° C. shear modulus and the viscosity characteristic of the adhesive material for semiconductor chip bonding to a predetermined range, thereby providing high reliability.
  • the present inventors have found that a semiconductor device can be manufactured and have completed the present invention.
  • a convex fillet means a fillet having an inverted U-shaped bulge as shown in FIG. 2 at the end when a cross section of the fillet is observed.
  • a non-convex fillet means a fillet that does not have an inverted U-shaped bulge as shown in FIG. 2 when the cross section of the fillet is observed.
  • 1 and 2 are cross-sectional views showing an example of a state in which the semiconductor chip 2 is bonded onto the substrate 1 via the bumps 4 using the semiconductor chip bonding adhesive material 3.
  • FIG. 1 shows a state in which a non-convex fillet is formed
  • FIG. 2 shows a state in which a convex fillet is formed.
  • the non-convex shape preferably has an angle ⁇ formed by the side wall of the semiconductor chip and the fillet of less than 70 °.
  • the lower limit of the 25 ° C. shear modulus Gr measured with a viscoelasticity measuring device is 1 ⁇ 10 6 Pa.
  • the 25 ° C. shear modulus Gr measured by the viscoelasticity measuring device is less than 1 ⁇ 10 6 Pa, the resulting semiconductor chip bonding adhesive material is likely to be tacky.
  • the semiconductor chip bonding adhesive material during dicing There is a problem such as cutting scraps adhering to the surface.
  • a preferable lower limit of the 25 ° C. shear modulus Gr measured by the viscoelasticity measuring device is 3 ⁇ 10 6 Pa, and a more preferable lower limit is 5 ⁇ 10 6 Pa.
  • the upper limit of the 25 degreeC shear modulus Gr measured with the said viscoelasticity measuring apparatus is not specifically limited, A preferable upper limit is 1 * 10 ⁇ 8 > Pa.
  • a preferable upper limit of the 25 ° C. shear modulus Gr measured by the viscoelasticity measuring device exceeds 1 ⁇ 10 8 Pa, a part of the adhesive material for bonding a semiconductor chip may be peeled off during dicing.
  • a more preferable upper limit of the 25 ° C. shear modulus Gr measured by the viscoelasticity measuring device is 5 ⁇ 10 7 Pa.
  • the 25 ° C. shear modulus Gr measured with a viscoelasticity measuring device means a value obtained by measuring the adhesive material for bonding a semiconductor chip of the present invention in the form of a film.
  • the method for measuring the 25 ° C. shear modulus Gr with the viscoelasticity measuring device is not particularly limited. For example, using a viscoelasticity measuring device such as a dynamic viscoelasticity measuring device DVA-200 (manufactured by IT Meter Co., Ltd.). And a method of measuring the shear of a film having a thickness of 600 ⁇ m, a width of 6 mm, and a length of 10 mm.
  • the upper limit of the lowest complex viscosity ⁇ * min up to the solder melting point measured with a rheometer is 5 ⁇ 10 1 Pa ⁇ s.
  • the minimum complex viscosity ⁇ * min up to the solder melting point measured with the rheometer exceeds 5 ⁇ 10 1 Pa ⁇ s, the solder is easily washed away by the adhesive material for bonding the semiconductor chip during bonding, and stable conduction is obtained. Absent.
  • the preferable upper limit of the minimum complex viscosity ⁇ * min up to the solder melting point measured with the rheometer is 4.5 ⁇ 10 1 Pa ⁇ s, the more preferable upper limit is 4 ⁇ 10 1 Pa ⁇ s, and the more preferable upper limit is 3.0 ⁇ . 10 1 Pa ⁇ s.
  • the lower limit of the lowest complex viscosity ⁇ * min up to the solder melting point measured with the rheometer is not particularly limited, but the preferred lower limit is 5 ⁇ 10 ⁇ 1 Pa ⁇ s. If the minimum complex viscosity ⁇ * min up to the solder melting point measured with the rheometer is less than 5 ⁇ 10 ⁇ 1 Pa ⁇ s, voids bitten during bonding may remain in the adhesive layer. A more preferable lower limit of the lowest complex viscosity ⁇ * min up to the solder melting point measured with the rheometer is 1 Pa ⁇ s.
  • the lowest complex viscosity ⁇ * min up to the solder melting point measured with a rheometer means a value obtained by measuring the adhesive material for bonding a semiconductor chip of the present invention in the form of a film.
  • the method of measuring the lowest complex viscosity ⁇ * min up to the solder melting point with the rheometer is not particularly limited.
  • the sample thickness is 600 ⁇ m
  • the strain control (1 rad ) A frequency of 10 Hz, a temperature rising rate of 20 ° C./min, a measurement temperature range of 60 ° C. to 300 ° C. and the like.
  • the solder melting point is, for example, a temperature in the range of 230 to 320 ° C.
  • the adhesive material for semiconductor chip bonding of the present invention has a complex viscosity ⁇ * (1 Hz) measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 1 Hz, and a complex viscosity ⁇ * (measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 10 Hz). 10 Hz) to 0.5 to 4.5 times.
  • the semiconductor chip bonding adhesive material of the present invention can form a non-convex fillet by its own weight by heating during bonding, and the reliability of the obtained semiconductor device can be improved. Moreover, even if it is applied to other processes such as dicing, there is no problem.
  • the complex viscosity ⁇ * (1 Hz) is less than 0.5 times the complex viscosity ⁇ * (10 Hz)
  • the fluidity of the adhesive material for bonding a semiconductor chip is lowered during bonding, and, for example, bump contact is hindered.
  • Such problems occur.
  • the complex viscosity ⁇ * (1 Hz) exceeds 4.5 times the complex viscosity ⁇ * (10 Hz)
  • a non-convex fillet cannot be formed, and the angle formed between the side wall of the semiconductor chip and the fillet is When it is 70 ° or more, stress concentrates on the convex portion, and the reliability of the obtained semiconductor device is lowered.
  • the complex viscosity ⁇ * (1 Hz) is preferably 0.7 times or more, more preferably 0.9 times or more of the complex viscosity ⁇ * (10 Hz). Preferably, it is 1.0 times or more, more preferably 4.3 times or less, and even more preferably 4.0 times or less.
  • the complex viscosity ⁇ * (1 Hz) and the complex viscosity ⁇ * (10 Hz) mean values obtained by measuring the adhesive material for semiconductor chip bonding of the present invention in the form of a film.
  • the method for measuring the complex viscosity ⁇ * (1 Hz) and the complex viscosity ⁇ * (10 Hz) is not particularly limited.
  • the sample thickness is 600 ⁇ m
  • Examples include a strain control (1 rad), a method of measuring at a frequency of 1 Hz or 10 Hz, and a temperature of 140 ° C.
  • the method for achieving the shear modulus and viscosity characteristics in the above-mentioned ranges is not particularly limited.
  • an epoxy compound, a polymer compound having a functional group capable of reacting with the epoxy compound (Hereinafter, it is also simply referred to as a polymer compound having a functional group capable of reacting) and a method of adjusting the shear modulus and viscosity characteristics by appropriately blending other additive components as necessary is preferable.
  • the type and blending amount of the epoxy compound and the molecular weight and blending amount of the polymer compound having a functional group capable of reacting by controlling the type and blending amount of the epoxy compound and the molecular weight and blending amount of the polymer compound having a functional group capable of reacting, the interaction of each component or the molecular chain of the adhesive material for semiconductor chip bonding is controlled. It is preferable to reduce the entanglement to the limit.
  • an insoluble component such as an inorganic filler, it is possible to increase the affinity for an epoxy compound or the like, or to control the particle size and blending amount of the inorganic filler, thereby adhering for bonding a semiconductor chip. It is preferable to suppress formation of a network structure such as aggregation in the material.
  • the epoxy compound is not particularly limited, and examples thereof include an epoxy resin having a softening point of 150 ° C. or lower, an epoxy resin that is liquid or crystalline solid at room temperature, and the like. These epoxy compounds may be used independently and 2 or more types may be used together.
  • the epoxy resin having a softening point of 150 ° C. or lower include a phenol novolac epoxy resin, a bisphenol A novolac epoxy resin, a cresol novolac epoxy resin, a dicyclopentadienephenol novolac epoxy resin, and a biphenylphenol novolac epoxy resin. Of these, dicyclopentadienephenol novolac type epoxy resin is preferable.
  • Examples of the epoxy resin that is liquid or crystalline solid at room temperature include, for example, bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, and bisphenol S type, dicyclopentadiene type epoxy resins, resorcinol type epoxy resins, and biphenyl.
  • bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, and bisphenol S type
  • dicyclopentadiene type epoxy resins dicyclopentadiene type epoxy resins
  • resorcinol type epoxy resins and biphenyl.
  • Type epoxy resin, anthracene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin and the like Of these, anthracene type epoxy resins are preferable.
  • the cured product of the adhesive material for bonding a semiconductor chip of the present invention has toughness and can exhibit excellent impact resistance.
  • the polymer compound having a reactive functional group is not particularly limited, and examples thereof include a polymer compound having an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group, and the like. Among these, a polymer compound having an epoxy group is preferable.
  • cured material of the adhesive material for semiconductor chip joining obtained expresses the outstanding toughness.
  • the cured product of the adhesive material for bonding semiconductor chips obtained has excellent mechanical strength, heat resistance and moisture resistance derived from the epoxy compound, and excellent toughness derived from the polymer compound having the epoxy group. By having both, high joint reliability and connection reliability can be expressed.
  • the polymer compound having an epoxy group is not particularly limited as long as it is a polymer compound having an epoxy group at the terminal and / or side chain (pendant position).
  • an epoxy group-containing acrylic rubber, an epoxy group-containing butadiene rubber examples thereof include bisphenol type high molecular weight epoxy resin, epoxy group-containing phenoxy resin, epoxy group-containing acrylic resin, epoxy group-containing urethane resin, and epoxy group-containing polyester resin.
  • an epoxy group-containing acrylic resin is preferable because it contains a large amount of epoxy groups and the cured product of the obtained adhesive material for joining semiconductor chips can exhibit excellent mechanical strength, heat resistance, toughness, and the like.
  • These polymer compounds having an epoxy group may be used alone or in combination of two or more.
  • the preferred upper limit of the weight average molecular weight of the polymer compound having an epoxy group is 200,000, and the preferred lower limit is 10,000.
  • the weight average molecular weight is less than 10,000, the film-forming property at the time of producing a film using a semiconductor chip bonding adhesive material may be insufficient, and the shape may not be maintained as a film.
  • the weight average molecular weight exceeds 200,000, in the obtained adhesive material for bonding a semiconductor chip, the ratio of the shear elastic modulus and the complex viscosity in the above range may not be achieved.
  • the weight average molecular weight is less than 10,000, since there are many low molecular weight compounds in the obtained adhesive material for bonding a semiconductor chip, voids may easily occur during bonding.
  • the upper limit of the weight average molecular weight of the polymer compound having an epoxy group is more preferably 150,000, still more preferably 100,000, still more preferably 50,000, and particularly preferably 20,000.
  • the said high molecular compound which has an epoxy group may be used independently, and 2 or more types which have a different weight average molecular weight may be used together.
  • a polymer compound having a weight average molecular weight of 50,000 or less and a polymer compound having a weight average molecular weight exceeding 50,000 may be used in combination.
  • the content of the polymer compound having a weight average molecular weight of more than 50,000 has a preferable upper limit of 20 in a total of 100 parts by weight of the epoxy compound and the polymer compound having a reactive functional group. Parts by weight.
  • the content of the polymer compound having a weight average molecular weight exceeding 50,000 exceeds 20 parts by weight, the ratio of the lowest complex viscosity and the complex viscosity described above may be too large in the obtained adhesive material for semiconductor chip bonding. .
  • the preferred lower limit of the epoxy equivalent of the polymer compound having an epoxy group is 200, and the preferred upper limit is 1000.
  • the epoxy equivalent is less than 200, the cured product of the obtained adhesive material for semiconductor chip bonding may be hard and brittle.
  • the epoxy equivalent exceeds 1000, the mechanical strength, heat resistance, and the like of the obtained cured product of the adhesive material for bonding a semiconductor chip may be insufficient.
  • the content of the polymer compound having a functional group capable of reacting is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the epoxy compound is 1 part by weight, and a preferable upper limit is 500 parts by weight.
  • a preferable lower limit with respect to 100 parts by weight of the epoxy compound is 1 part by weight, and a preferable upper limit is 500 parts by weight.
  • the content of the polymer compound having a functional group capable of reacting is less than 1 part by weight, the cured product of the obtained adhesive material for bonding a semiconductor chip has insufficient toughness when strain due to heat occurs. Bonding reliability may be inferior.
  • the content of the polymer compound having a reactive functional group exceeds 500 parts by weight, the above-described complex viscosity ratio may be too large in the obtained adhesive material for bonding a semiconductor chip, and a cured product The heat resistance of may decrease.
  • the content of the polymer compound having a functional group capable of reacting is preferably 400 parts by weight with respect to 100 parts by weight of the
  • the adhesive material for bonding a semiconductor chip of the present invention preferably contains a curing agent.
  • curing agent is not specifically limited, For example, an amine type hardening
  • the acid anhydride curing agent is not particularly limited, but a bifunctional acid anhydride curing agent is preferable.
  • the bifunctional acid anhydride curing agent is not particularly limited, and examples thereof include phthalic acid derivative anhydrides and maleic anhydride.
  • trifunctional or higher functional acid anhydride curing agent particles may be used as the curing agent.
  • the trifunctional or higher functional acid anhydride curing agent particles are not particularly limited.
  • particles composed of trifunctional acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, methylcyclohexene tetracarboxylic acid.
  • examples thereof include particles composed of tetrafunctional or higher functional acid anhydrides such as acid anhydrides and polyazeline acid anhydrides.
  • the average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles is not particularly limited, but a preferable lower limit is 0.1 ⁇ m and a preferable upper limit is 5 ⁇ m. If the average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles is less than 0.1 ⁇ m, aggregation of the curing agent particles occurs, and the adhesive material for bonding the semiconductor chip thickens to form a convex fillet. There are things that cannot be done. When the average particle diameter of the above-mentioned trifunctional or higher acid anhydride curing agent particles exceeds 5 ⁇ m, in the obtained adhesive material for bonding a semiconductor chip, the curing agent particles cannot be sufficiently diffused during curing, resulting in curing failure. Sometimes.
  • the content of the curing agent is not particularly limited, but a total of 100 of the epoxy compound and the polymer compound having a reactive functional group.
  • a preferred lower limit relative to parts by weight is 5 parts by weight, and a preferred upper limit is 150 parts by weight. If the content of the curing agent is less than 5 parts by weight, the resulting semiconductor chip bonding adhesive material may not be sufficiently cured. When content of the said hardening
  • the content of the curing agent is preferably 10 parts by weight and more preferably 140 parts by weight with respect to a total of 100 parts by weight of the epoxy compound and the polymer compound having a reactive functional group.
  • curing agent contains the said bifunctional acid anhydride hardening
  • these compounding ratios are not specifically limited,
  • the value is less than 0.1, the effect of adding the trifunctional or higher functional acid anhydride curing agent particles may not be sufficiently obtained.
  • the above value exceeds 10 the cured product of the obtained adhesive material for semiconductor chip bonding becomes fragile, and sufficient adhesion reliability may not be obtained.
  • a more preferred lower limit of the above value is 0.2, and a more preferred upper limit is 8.
  • the adhesive material for bonding a semiconductor chip of the present invention may contain a curing accelerator.
  • the said hardening accelerator is not specifically limited, An imidazole compound is preferable. Since the said imidazole compound has high reactivity with the said epoxy compound, quick curing property improves the adhesive material for semiconductor chip joining obtained by containing the said imidazole compound.
  • the imidazole compound is not particularly limited.
  • 1-cyanoethyl-2-phenylimidazole in which the 1-position of imidazole is protected with a cyanoethyl group an imidazole compound in which basicity is protected with isocyanuric acid (trade name “2MA-OK”, Shikoku, Japan) Kasei Kogyo Co., Ltd.), 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name “2MZ-A”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole (trade name “2P4MHZ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), Fuji Cure 7000 (Fuji Kasei Kogyo Co., Ltd.), and the like.
  • These imidazole compounds may be used independently and 2 or more
  • the content of the curing accelerator is not particularly limited, but the epoxy compound and the polymer compound having the reactive functional group A preferable lower limit with respect to 100 parts by weight in total is 0.3 part by weight, and a preferable upper limit is 8 parts by weight.
  • the content of the curing accelerator is less than 0.3 parts by weight, the obtained adhesive material for joining a semiconductor chip may not be sufficiently cured.
  • the content of the curing accelerator is more than 8 parts by weight, in the obtained adhesive material for bonding a semiconductor chip, unreacted curing accelerator oozes out to the adhesive interface, which may reduce the bonding reliability.
  • the adhesive material for joining a semiconductor chip of the present invention may contain an inorganic filler.
  • an inorganic filler By containing the inorganic filler, it is possible to reduce the linear expansion coefficient of the cured product of the obtained adhesive material for bonding semiconductor chips, and to generate stress on the bonded semiconductor chips and cracks in conductive parts such as solder. Can be satisfactorily prevented.
  • the inorganic filler is not particularly limited, and examples thereof include silica such as fumed silica and colloidal silica, alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, and glass frit.
  • the inorganic filler preferably has a hydrocarbon-containing group having 1 to 10 carbon atoms on the surface.
  • the minimum complex viscosity can be increased even if the amount of the inorganic filler is increased in the obtained adhesive material for semiconductor chip bonding. Can be reduced. It is also easy to achieve a complex viscosity ratio in the range described above.
  • the reliability of the obtained semiconductor device can be further improved by blending the semiconductor chip bonding adhesive material with the inorganic filler having the hydrocarbon-containing group having 1 to 10 carbon atoms on the surface.
  • the above-mentioned range can be obtained by adjusting the blending amount or the blending ratio with other components. If the ratio of the lowest complex viscosity to the complex viscosity can be achieved, it can be used.
  • the hydrocarbon-containing group having 1 to 10 carbon atoms is not particularly limited, but a hexyl group, a methyl group, a phenyl group and the like are preferable.
  • the hydrocarbon-containing group having 1 to 10 carbon atoms is formed on the surface of the inorganic filler using a coupling agent such as a silane coupling agent having the hydrocarbon-containing group having 1 to 10 carbon atoms in the skeleton. It can be introduced by processing.
  • the preferred lower limit of the average particle diameter is 1 nm, and the preferred upper limit is 5 ⁇ m.
  • the average particle diameter of the particulate inorganic filler is less than 1 nm, aggregation of the inorganic filler is likely to occur in the obtained semiconductor chip bonding adhesive material, and the ratio of complex viscosity in the above range cannot be achieved.
  • an adhesive material for joining a semiconductor chip that easily forms a convex fillet may be obtained.
  • the inorganic filler When the average particle diameter of the particulate inorganic filler exceeds 5 ⁇ m, the inorganic filler may be bitten between the electrodes when pressure bonding is performed using the obtained adhesive material for semiconductor chip bonding.
  • the more preferable lower limit of the average particle diameter of the particulate inorganic filler is 5 nm, the more preferable upper limit is 3 ⁇ m, the particularly preferable lower limit is 10 nm, and the particularly preferable upper limit is 1 ⁇ m.
  • the average particle diameter means a particle diameter having a 50% integrated diameter measured by a laser diffraction / scattering particle size distribution measuring apparatus.
  • the semiconductor chip bonding adhesive material of the present invention contains an inorganic filler having a hydrocarbon-containing group having 1 to 10 carbon atoms on the surface
  • the content of the inorganic filler is not particularly limited, but the epoxy compound and The preferable lower limit with respect to 100 parts by weight in total with the polymer compound having a functional group capable of reacting is 5 parts by weight, and the preferable upper limit is 500 parts by weight. If the content of the inorganic filler is less than 5 parts by weight, the effect of adding the inorganic filler may be hardly obtained.
  • the content of the inorganic filler exceeds 500 parts by weight, the linear expansion coefficient of the cured product of the obtained adhesive material for semiconductor chip bonding decreases, but at the same time, the shear elastic modulus increases to form a non-convex fillet. There are things you can't do. As a result, stress on the bonded semiconductor chips and cracks in the conductive portion such as solder may easily occur.
  • the content of the inorganic filler having a hydrocarbon-containing group having 1 to 10 carbon atoms on the surface is more preferably lower limit with respect to 100 parts by weight in total of the epoxy compound and the polymer compound having a reactive functional group. 10 parts by weight, a more preferred upper limit is 400 parts by weight, a still more preferred lower limit is 15 parts by weight, and a still more preferred upper limit is 300 parts by weight.
  • the adhesive material for bonding a semiconductor chip of the present invention contains an inorganic filler having no hydrocarbon-containing group having 1 to 10 carbon atoms on its surface
  • the content of the inorganic filler is not particularly limited
  • the preferable lower limit with respect to a total of 100 parts by weight of the epoxy compound and the polymer compound having a reactive functional group is 5 parts by weight
  • the preferable upper limit is 200 parts by weight.
  • the semiconductor chip bonding adhesive material of the present invention contains an inorganic filler having an average particle diameter of 10 nm or less
  • the content of the inorganic filler is not particularly limited, but the above-mentioned regardless of the presence or absence of surface treatment.
  • the amount is preferably 50 parts by weight or less based on 100 parts by weight of the total of the epoxy compound and the polymer compound having a functional group capable of reacting.
  • the adhesive material for bonding a semiconductor chip of the present invention may contain a diluent as long as the effects of the present invention are not impaired.
  • the said diluent is not specifically limited,
  • cured material at the time of heat-hardening of the adhesive material for semiconductor chip joining is preferable.
  • a reactive diluent having two or more functional groups in one molecule is more preferable in order not to deteriorate the adhesion reliability of the obtained adhesive material for bonding a semiconductor chip.
  • Examples of the reactive diluent having two or more functional groups in one molecule include aliphatic epoxy, ethylene oxide modified epoxy, propylene oxide modified epoxy, cyclohexane epoxy, dicyclopentadiene epoxy, phenol epoxy and the like. Can be mentioned.
  • the content of the diluent is not particularly limited, but a total of 100 of the epoxy compound and the polymer compound having a reactive functional group.
  • the preferable lower limit with respect to parts by weight is 1 part by weight, and the preferable upper limit is 300 parts by weight. If the content of the diluent is less than 1 part by weight, the effect of adding the diluent may be hardly obtained. If the content of the diluent exceeds 300 parts by weight, the cured product of the obtained adhesive material for joining semiconductor chips becomes hard and brittle, and thus the adhesion reliability may be inferior.
  • the content of the diluent is more preferably a lower limit of 5 parts by weight and a more preferable upper limit of 200 parts by weight with respect to a total of 100 parts by weight of the epoxy compound and the polymer compound having a reactive functional group.
  • the semiconductor chip bonding adhesive material of the present invention may contain an inorganic ion exchanger, if necessary.
  • inorganic ion exchangers examples of commercially available products include IXE series (manufactured by Toagosei Co., Ltd.).
  • the adhesive material for bonding a semiconductor chip of the present invention contains the inorganic ion exchanger
  • the content of the inorganic ion exchanger is not particularly limited, but the preferred lower limit in the adhesive material for bonding a semiconductor chip of the present invention is 1 weight. %, And a preferred upper limit is 10% by weight.
  • the adhesive material for semiconductor chip bonding of the present invention may contain additives such as an anti-bleeding agent, a silane coupling agent, an adhesion imparting agent such as an imidazole silane coupling agent, and a thickener as necessary. Good.
  • the method for producing the semiconductor chip bonding adhesive material of the present invention is not particularly limited. For example, a predetermined amount of the epoxy compound, the polymer compound having a reactive functional group, the curing agent, the inorganic filler, and the like is blended. And a method of mixing them.
  • the method of mixing is not particularly limited, and examples thereof include a method of mixing using a homodisper, a universal mixer, a Banbury mixer, a kneader, and the like.
  • the adhesive material for bonding a semiconductor chip of the present invention is not particularly limited. For example, it is used when a wafer or a semiconductor chip is mounted on another wafer, another semiconductor chip or a substrate.
  • the adhesive material for bonding a semiconductor chip of the present invention is preferably used for flip chip mounting, and an adhesive layer is pre-mounted on a wafer, a semiconductor chip or a substrate rather than flip chip mounting in which an underfill is filled after electrode bonding. More preferably, it is used for flip chip mounting.
  • a method for manufacturing a semiconductor device using the semiconductor chip bonding adhesive material of the present invention is not particularly limited. For example, an adhesive solution prepared by adding a solvent to the semiconductor chip bonding adhesive material of the present invention is applied to a wafer. And a method of drying the solvent to form a film. Such a method of manufacturing a semiconductor device is also one aspect of the present invention.
  • the solvent examples include medium-boiling solvents or high-boiling solvents having a boiling point of about 120 to 250 ° C. such as propylene glycol methyl ether acetate.
  • a method of applying an adhesive solution prepared by adding a solvent to the adhesive material for bonding semiconductor chips of the present invention to a wafer is not particularly limited, and examples thereof include spin coating and screen printing.
  • the adhesive material for bonding a semiconductor chip of the present invention when the adhesive material for bonding a semiconductor chip of the present invention does not contain a solvent, for example, the adhesive material for bonding a semiconductor chip of the present invention
  • coat to a wafer and make into a film by B staging agent or exposure, etc. are also mentioned.
  • the adhesive film for joining semiconductor chips comprising the adhesive material for joining semiconductor chips of the present invention is also one aspect of the present invention.
  • the thickness of the adhesive film for bonding a semiconductor chip of the present invention is not particularly limited, but a preferable lower limit is 2 ⁇ m and a preferable upper limit is 500 ⁇ m. If the thickness is less than 2 ⁇ m, a smooth film may not be obtained due to the inclusion of foreign matter. When the thickness exceeds 500 ⁇ m, the solvent tends to remain in the obtained adhesive film for semiconductor chip bonding, and bubbles may be generated during pressure bonding and curing.
  • the method for producing the adhesive film for semiconductor chip bonding of the present invention is not particularly limited.
  • a method of forming a film after preparing an adhesive solution by quantitatively blending and mixing is mentioned.
  • the method of mixing is not particularly limited, and examples thereof include a method of mixing using a homodisper, a universal mixer, a Banbury mixer, a kneader, and the like.
  • the method for forming the film is not particularly limited.
  • the adhesive solution is applied onto the separator using a die coater, bar coater, gravure coater, slit coater, or the like.
  • a die coater bar coater, gravure coater, slit coater, or the like.
  • the method include drying the solvent by heating and the like after the processing.
  • the adhesive film for bonding a semiconductor chip of the present invention is not particularly limited. For example, it is used when a wafer or a semiconductor chip is mounted on another wafer, another semiconductor chip or a substrate.
  • the adhesive film for bonding a semiconductor chip of the present invention is preferably used for flip chip mounting, and an adhesive layer is previously mounted on a wafer, a semiconductor chip or a substrate rather than flip chip mounting in which an underfill is filled after electrode bonding. More preferably, it is used for flip chip mounting.
  • the adhesive film for bonding a semiconductor chip of the present invention can control the fillet shape so that it does not become a convex shape, a highly reliable semiconductor device is manufactured by using the adhesive film for bonding a semiconductor chip of the present invention. can do.
  • the manufacturing method of the semiconductor device using the adhesive film for semiconductor chip bonding of the present invention is not particularly limited.
  • the method for supplying the adhesive film for semiconductor chip bonding of the present invention to a wafer or a semiconductor chip by laminating, the semiconductor of the present invention A method of cutting an adhesive film for chip bonding in accordance with the chip size of the semiconductor chip and supplying it to another semiconductor chip or substrate can be mentioned.
  • Such a method of manufacturing a semiconductor device is also one aspect of the present invention.
  • a semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention wherein a semiconductor chip and another semiconductor chip or a substrate are bonded via an adhesive layer, and a fillet that rises up to a side wall of the semiconductor chip.
  • a semiconductor device which is formed and an angle formed between the side wall of the semiconductor chip and the fillet is less than 70 ° is also one aspect of the present invention. When the angle formed between the side wall of the semiconductor chip and the fillet is 70 ° or more, stress concentrates on the convex portion and the reliability of the semiconductor device is lowered.
  • the adhesive material for semiconductor chip joining which can control a fillet shape so that it may not become convex shape, and can manufacture a highly reliable semiconductor device can be provided.
  • a semiconductor chip bonding adhesive film made of the semiconductor chip bonding adhesive material a method of manufacturing a semiconductor device using the semiconductor chip bonding adhesive material or the semiconductor chip bonding adhesive film, and A semiconductor device obtained by the method for manufacturing the semiconductor device can be provided.
  • Examples 1 to 31 and Comparative Examples 1 to 18 According to the compositions shown in Tables 1 to 5, the following materials were stirred and mixed using a homodisper to prepare an adhesive solution. The adhesive solution was applied onto a release-treated PET film by an applicator, and the solvent was dried to obtain a 100 ⁇ m-thick adhesive film for bonding a semiconductor chip.
  • Epoxy compound / biphenyl type epoxy resin (trade name “YX-4000”, manufactured by Japan Epoxy Resin Co., Ltd.) ⁇ Bisphenol A type epoxy resin (trade name “1004AF”, manufactured by Japan Epoxy Resin Co., Ltd.) ⁇ Dicyclopentadiene type epoxy resin (trade name “HP-7200HH”, manufactured by DIC Corporation) ⁇ Dicyclopentadiene type epoxy resin (trade name “EP-4088S”, manufactured by ADEKA)
  • Inorganic filler / surface phenyl-treated inorganic filler (silica) (trade name “SE-1050-SPT”, manufactured by Admatechs, average particle diameter of 300 nm) ⁇ Surface phenyl-treated inorganic filler (silica) (trade name “SE-2050-SPJ”, manufactured by Admatechs, average particle size 500 nm) ⁇ Surface phenyl-treated inorganic filler (silica) (trade name “SS-01”, manufactured by Tokuyama Corporation, average particle size 100 nm) ⁇ Surface phenyl-treated inorganic filler (silica) (trade name “YA050-MJF”, manufactured by Admatechs, average particle size 50 nm) Surface-untreated inorganic filler (silica) (trade name “SE-1050”, manufactured by Admatechs, average particle size 300 nm) Surface-untreated inorganic filler (silica) (trade name “SE-2050”, manufactured by Admatechs, average particle diameter of 500 nm) ⁇ Un
  • the conduction resistance value (hereinafter referred to as initial resistance) is measured in advance, and moisture absorption is performed at 60 ° C. and 60% RH for 40 hours. After conducting a reflow test by passing through a reflow oven at 260 ° C. three times, the conduction resistance value was measured again. A case where the conduction resistance value after the reflow test was changed by 10% or more from the initial resistance value was regarded as defective, and eight laminates were produced and the number of defects was evaluated.
  • Thermal cycle test 1 The laminate subjected to the reflow test in (5) above was subjected to 1000 cycles of a thermal cycle test at ⁇ 55 to 125 ° C. (30 minutes / 1 cycle), and then the conduction resistance value was measured. The case where the conduction resistance value after the thermal cycle test was changed by 10% or more from the initial resistance value was regarded as defective, and eight laminates were produced and the number of defects was evaluated. The case where the number of defects was 0 was marked as ⁇ , the case where it was 1 as ⁇ , and the case where it was 2 or more as x.
  • Thermal cycle test 2 The laminate subjected to the reflow test in (5) above was subjected to a thermal cycle test of ⁇ 55 to 125 ° C. (30 minutes / 1 cycle) and 3000 cycles, and then the conduction resistance value was measured. The case where the conduction resistance value after the thermal cycle test was changed by 10% or more from the initial resistance value was regarded as defective, and eight laminates were produced and the number of defects was evaluated. When the number of defects was 2 or less, ⁇ , when 3-4, ⁇ , when 5-6, ⁇ , when 7 or more, x.
  • the adhesive material for semiconductor chip joining which can control a fillet shape so that it may not become convex shape, and can manufacture a highly reliable semiconductor device can be provided.
  • a semiconductor chip bonding adhesive film made of the semiconductor chip bonding adhesive material a method of manufacturing a semiconductor device using the semiconductor chip bonding adhesive material or the semiconductor chip bonding adhesive film, and A semiconductor device obtained by the method for manufacturing the semiconductor device can be provided.

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Abstract

Disclosed is an attachment material for semiconductor chip bonding, whereby manufacturing a highly reliable semiconductor device, controlling such that a fillet shape does not take on a convex shape, is possible. The disclosed attachment material for semiconductor chip bonding has a shear modulus (Gr) as measured with a viscoelasticity measurement device that is greater than or equal to 1*106 Pa at 25 degrees C; a minimum complex viscosity (η*min) up to the melting point of solder as measured by a rheometer that is less than or equal to 5x101 Pa•s; and the complex viscosity (η*(1Hz)) when measured at 140 degrees C, 1 rad distortion, and a frequency of 1Hz is 0.5-4.5 times the complex viscosity (η*(10Hz)) when measured at 140 degrees C, 1 rad distortion, and a frequency of 10Hz.

Description

半導体チップ接合用接着材料、半導体チップ接合用接着フィルム、半導体装置の製造方法、及び、半導体装置Semiconductor chip bonding adhesive material, semiconductor chip bonding adhesive film, semiconductor device manufacturing method, and semiconductor device
本発明は、フィレット形状を、凸形状にならないように制御し、信頼性の高い半導体装置を製造することのできる半導体チップ接合用接着材料に関する。また、本発明は、該半導体チップ接合用接着材料からなる半導体チップ接合用接着フィルム、該半導体チップ接合用接着材料又は該半導体チップ接合用接着フィルムを用いた半導体装置の製造方法、及び、該半導体装置の製造方法により得られる半導体装置に関する。 The present invention relates to an adhesive material for bonding a semiconductor chip that can manufacture a highly reliable semiconductor device by controlling the fillet shape so that it does not become a convex shape. The present invention also provides a semiconductor chip bonding adhesive film made of the semiconductor chip bonding adhesive material, a method of manufacturing a semiconductor device using the semiconductor chip bonding adhesive material or the semiconductor chip bonding adhesive film, and the semiconductor. The present invention relates to a semiconductor device obtained by a device manufacturing method.
近年、ますます進展する半導体装置の小型化、高集積化に対応するために、ハンダ等からなる接続端子（バンプ）を有する半導体チップを用いたフリップチップ実装が多用されている。 2. Description of the Related Art In recent years, flip-chip mounting using a semiconductor chip having connection terminals (bumps) made of solder or the like has been widely used in order to cope with the further miniaturization and higher integration of semiconductor devices.
フリップチップ実装においては、一般的に、複数のバンプを有する半導体チップを、バンプを介して他の半導体チップ又は基板に接続した後、アンダーフィルを充填する方法が用いられている。このようなアンダーフィルを充填する方法においては、アンダーフィルの硬化収縮時、又は、リフロー試験若しくは冷熱サイクル試験時、例えば半導体チップと基板との間の線膨張係数の差等に起因して、アンダーフィルの界面等に応力が集中し、クラックが発生することがある。 In flip-chip mounting, generally, a method is used in which a semiconductor chip having a plurality of bumps is connected to another semiconductor chip or a substrate through the bumps and then filled with an underfill. In such a method of filling underfill, undercuring under shrinkage or under reflow test or thermal cycle test, for example, due to a difference in coefficient of linear expansion between the semiconductor chip and the substrate, Stress may concentrate on the interface of the fill and cracks may occur.
そこで、クラックの発生を抑制するために、例えば、特許文献１には、半導体素子と、該半導体素子を搭載する基板と、前記半導体素子に形成された回路形成面を封止する封止樹脂と、を具備する半導体装置において、半導体素子の外周側面を覆う側面被覆部を設けることが記載されている。このような半導体素子の外周側面を覆う側面被覆部は、一般にフィレットと呼ばれている。
更に、特許文献１に記載の半導体装置においては、クラックの発生をより確実に抑制するために、側面被覆部の回路形成面からの高さを所定範囲とすることが提案されている。 Therefore, in order to suppress the occurrence of cracks, for example, Patent Document 1 discloses a semiconductor element, a substrate on which the semiconductor element is mounted, and a sealing resin that seals a circuit formation surface formed on the semiconductor element. In the semiconductor device having the above, it is described that a side surface covering portion that covers the outer peripheral side surface of the semiconductor element is provided. Such a side surface covering portion covering the outer peripheral side surface of the semiconductor element is generally called a fillet.
Furthermore, in the semiconductor device described in Patent Document 1, it has been proposed that the height of the side surface covering portion from the circuit formation surface is within a predetermined range in order to more reliably suppress the occurrence of cracks.
また、特許文献２には、回路基板と半導体チップとの間に封止樹脂が注入されると共に、半導体チップの外周側部に封止樹脂が付与されてフィレット部が形成されてなる特定のフリップチップ半導体パッケージが記載されている。特許文献２に記載のフリップチップ半導体パッケージにおいて、フィレット部は、表面が半導体チップの外周側部の上縁から基板に向けて外方に延びる傾斜面をなす構造を有している。
更に、特許文献２には、傾斜面と半導体チップの外周側部のなす傾斜角が半導体チップの外周側部の上縁近傍において５０度以下であることにより、応力集中によるクラックの発生が抑制もしくは低減され半導体チップ破損が抑制されることが記載されている。 Patent Document 2 discloses a specific flip in which a sealing resin is injected between a circuit board and a semiconductor chip, and a sealing resin is applied to an outer peripheral side portion of the semiconductor chip to form a fillet portion. A chip semiconductor package is described. In the flip chip semiconductor package described in Patent Document 2, the fillet portion has a structure in which the surface forms an inclined surface extending outward from the upper edge of the outer peripheral side portion of the semiconductor chip toward the substrate.
Further, Patent Document 2 discloses that the inclination angle formed between the inclined surface and the outer peripheral side portion of the semiconductor chip is 50 degrees or less in the vicinity of the upper edge of the outer peripheral side portion of the semiconductor chip. It is described that semiconductor chip breakage is reduced and reduced.
しかしながら、従来の方法では、フィレットを形成する工程が煩雑であったり、フィレットの形成によってもクラックの発生が充分に抑制されなかったりすることが問題であった。 However, the conventional method has a problem that the process of forming the fillet is complicated, and the occurrence of cracks is not sufficiently suppressed by the formation of the fillet.
一方、近年、半導体チップの小型化が進行するとともにバンプ間のピッチもますます狭くなっており、また、これらに伴って半導体チップ同士又は半導体チップと基板との間のギャップもますます狭くなっていることから、アンダーフィルが充填されないか、又は、充填に長時間を要したり、充填時に空気が巻き込まれやすく、ボイドが発生しやすかったりすることも問題である。
そこで、例えば、接着剤又は接着フィルムにより、複数のバンプを有するウエハ上のバンプが形成された面に接着剤層を形成した後、ウエハを接着剤層ごとダイシングして個々の半導体チップとし、これをバンプを介して他の半導体チップ又は基板にボンディングする先塗布型の実装方法が提案されており、このような先塗布型の実装方法にも適用することができ、かつ、クラックの発生を充分に抑制することのできる新たな接着剤又は接着フィルムが求められている。 On the other hand, in recent years, semiconductor chips have been miniaturized, and the pitch between bumps has become increasingly narrow. In addition, the gap between semiconductor chips or between a semiconductor chip and a substrate has also become narrower. Therefore, the underfill is not filled, or it takes a long time for filling, or air is easily caught during filling, and voids are easily generated.
Therefore, for example, an adhesive layer is formed on the surface of the wafer having a plurality of bumps with an adhesive or an adhesive film, and then the wafer is diced together with the adhesive layer to form individual semiconductor chips. A pre-application type mounting method has been proposed in which a semiconductor chip or a substrate is bonded via a bump, and can be applied to such a pre-application type mounting method. There is a need for new adhesives or adhesive films that can be suppressed.
特開２０００－４０７７５号公報Japanese Patent Laid-Open No. 2000-40775 国際公開第０８／０１８５５７号パンフレットInternational Publication No. 08/018557 Pamphlet
本発明は、フィレット形状を、凸形状にならないように制御し、信頼性の高い半導体装置を製造することのできる半導体チップ接合用接着材料を提供することを目的とする。また、本発明は、該半導体チップ接合用接着材料からなる半導体チップ接合用接着フィルム、該半導体チップ接合用接着材料又は該半導体チップ接合用接着フィルムを用いた半導体装置の製造方法、及び、該半導体装置の製造方法により得られる半導体装置を提供することを目的とする。 An object of the present invention is to provide an adhesive material for bonding a semiconductor chip that can control a fillet shape so as not to be a convex shape and can manufacture a highly reliable semiconductor device. The present invention also provides a semiconductor chip bonding adhesive film made of the semiconductor chip bonding adhesive material, a method of manufacturing a semiconductor device using the semiconductor chip bonding adhesive material or the semiconductor chip bonding adhesive film, and the semiconductor. It is an object of the present invention to provide a semiconductor device obtained by a device manufacturing method.
本発明は、粘弾性測定装置で測定した２５℃せん断弾性率Ｇｒが１×１０６Ｐａ以上、レオメーターで測定したハンダ融点までの最低複素粘度η＊ｍｉｎが５×１０１Ｐａ・ｓ以下であり、温度１４０℃、歪量１ｒａｄ、周波数１Ｈｚで測定した複素粘度η＊（１Ｈｚ）が温度１４０℃、歪量１ｒａｄ、周波数１０Ｈｚで測定した複素粘度η＊（１０Ｈｚ）の０．５～４．５倍である半導体チップ接合用接着材料である。
以下、本発明を詳述する。 In the present invention, the 25 ° C. shear modulus Gr measured with a viscoelasticity measuring apparatus is 1 × 10 6 Pa or more, and the lowest complex viscosity η * min up to the solder melting point measured with a rheometer is 5 × 10 1 Pa · s or less. Yes, the complex viscosity η * (1 Hz) measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 1 Hz is 0.5-4 of the complex viscosity η * (10 Hz) measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 10 Hz. It is an adhesive material for semiconductor chip bonding that is 5 times.
The present invention is described in detail below.
通常、接着剤又は接着フィルムを用いて、予め接着剤層が形成された半導体チップを他の半導体チップ又は基板にボンディングする際、フィレットを形成しようとすると、該フィレットの断面図の形状は、図２に示すような凸形状になりやすい。そして、凸形状のフィレットにおいては、半導体チップの側壁とフィレットとが成す角度が７０°以上になりやすい。本発明者らは、このような凸形状のフィレットにおいては、凸部に応力が集中して半導体チップの剥離又は割れが発生しやすく、一方、図１に示すような非凸形状のフィレットを形成することで、応力の集中を抑制して信頼性の高い半導体装置を製造できることを見出した。
即ち、本発明者らは、半導体チップ接合用接着材料の２５℃せん断弾性率及び粘度特性を所定範囲とすることにより、非凸形状のフィレットを形成することができ、これにより、信頼性の高い半導体装置を製造できることを見出し、本発明を完成させるに至った。 Usually, when bonding a semiconductor chip on which an adhesive layer has been formed in advance to another semiconductor chip or a substrate by using an adhesive or an adhesive film, when trying to form a fillet, the shape of the cross-sectional view of the fillet is 2 tends to be convex. In a convex fillet, the angle formed by the side wall of the semiconductor chip and the fillet tends to be 70 ° or more. In such a convex fillet, the inventors tend to cause stress concentration on the convex portion and easily cause peeling or cracking of the semiconductor chip, while forming a non-convex fillet as shown in FIG. Thus, it has been found that a highly reliable semiconductor device can be manufactured by suppressing the concentration of stress.
That is, the present inventors can form a non-convex fillet by setting the 25 ° C. shear modulus and the viscosity characteristic of the adhesive material for semiconductor chip bonding to a predetermined range, thereby providing high reliability. The present inventors have found that a semiconductor device can be manufactured and have completed the present invention.
本明細書中、凸形状のフィレットとは、フィレットの断面を観察した場合に、端部に図２に示すような逆Ｕ字状のふくらみ部を有するフィレットを意味する。一方、非凸形状のフィレットとは、フィレットの断面を観察した場合に、端部に図２に示すような逆Ｕ字状のふくらみ部を有しないフィレットを意味する。
なお、図１及び図２は、半導体チップ接合用接着材料３を用いて、バンプ４を介して基板１上に半導体チップ２をボンディングした状態の一例を示す断面図である。図１は非凸形状のフィレットを形成した状態を示し、図２は凸形状のフィレットを形成した状態を示す。 In the present specification, a convex fillet means a fillet having an inverted U-shaped bulge as shown in FIG. 2 at the end when a cross section of the fillet is observed. On the other hand, a non-convex fillet means a fillet that does not have an inverted U-shaped bulge as shown in FIG. 2 when the cross section of the fillet is observed.
1 and 2 are cross-sectional views showing an example of a state in which the semiconductor chip 2 is bonded onto the substrate 1 via the bumps 4 using the semiconductor chip bonding adhesive material 3. FIG. 1 shows a state in which a non-convex fillet is formed, and FIG. 2 shows a state in which a convex fillet is formed.
上記非凸形状は、図３に示すように、半導体チップの側壁とフィレットとが成す角度θが７０°未満であることが好ましい。 As shown in FIG. 3, the non-convex shape preferably has an angle θ formed by the side wall of the semiconductor chip and the fillet of less than 70 °.
本発明の半導体チップ接合用接着材料は、粘弾性測定装置で測定した２５℃せん断弾性率Ｇｒの下限が１×１０６Ｐａである。上記粘弾性測定装置で測定した２５℃せん断弾性率Ｇｒが１×１０６Ｐａ未満であると、得られる半導体チップ接合用接着材料にはタックが生じやすく、例えば、ダイシング時に半導体チップ接合用接着材料に切削クズが付着する等の不具合が生じる。
上記粘弾性測定装置で測定した２５℃せん断弾性率Ｇｒの好ましい下限は３×１０６Ｐａ、より好ましい下限は５×１０６Ｐａである。 In the adhesive material for bonding a semiconductor chip of the present invention, the lower limit of the 25 ° C. shear modulus Gr measured with a viscoelasticity measuring device is 1 × 10 6 Pa. When the 25 ° C. shear modulus Gr measured by the viscoelasticity measuring device is less than 1 × 10 6 Pa, the resulting semiconductor chip bonding adhesive material is likely to be tacky. For example, the semiconductor chip bonding adhesive material during dicing There is a problem such as cutting scraps adhering to the surface.
A preferable lower limit of the 25 ° C. shear modulus Gr measured by the viscoelasticity measuring device is 3 × 10 6 Pa, and a more preferable lower limit is 5 × 10 6 Pa.
上記粘弾性測定装置で測定した２５℃せん断弾性率Ｇｒの上限は特に限定されないが、好ましい上限は１×１０８Ｐａである。上記粘弾性測定装置で測定した２５℃せん断弾性率Ｇｒが１×１０８Ｐａを超えると、ダイシング時に半導体チップ接合用接着材料の一部が剥がれ飛ぶことがある。
上記粘弾性測定装置で測定した２５℃せん断弾性率Ｇｒのより好ましい上限は５×１０７Ｐａである。 Although the upper limit of the 25 degreeC shear modulus Gr measured with the said viscoelasticity measuring apparatus is not specifically limited, A preferable upper limit is 1 * 10 < 8 > Pa. When the 25 ° C. shear modulus Gr measured by the viscoelasticity measuring device exceeds 1 × 10 8 Pa, a part of the adhesive material for bonding a semiconductor chip may be peeled off during dicing.
A more preferable upper limit of the 25 ° C. shear modulus Gr measured by the viscoelasticity measuring device is 5 × 10 7 Pa.
本明細書中、粘弾性測定装置で測定した２５℃せん断弾性率Ｇｒとは、本発明の半導体チップ接合用接着材料をフィルム状にして測定した値を意味する。上記粘弾性測定装置で２５℃せん断弾性率Ｇｒを測定する方法は特に限定されず、例えば、動的粘弾性測定装置ＤＶＡ－２００（アイティー計測器社製）等の粘弾性測定装置を用いて、厚み６００μｍ、幅６ｍｍ、長さ１０ｍｍのフィルムをせん断測定する方法等が挙げられる。 In the present specification, the 25 ° C. shear modulus Gr measured with a viscoelasticity measuring device means a value obtained by measuring the adhesive material for bonding a semiconductor chip of the present invention in the form of a film. The method for measuring the 25 ° C. shear modulus Gr with the viscoelasticity measuring device is not particularly limited. For example, using a viscoelasticity measuring device such as a dynamic viscoelasticity measuring device DVA-200 (manufactured by IT Meter Co., Ltd.). And a method of measuring the shear of a film having a thickness of 600 μm, a width of 6 mm, and a length of 10 mm.
本発明の半導体チップ接合用接着材料は、レオメーターで測定したハンダ融点までの最低複素粘度η＊ｍｉｎの上限が５×１０１Ｐａ・ｓである。上記レオメーターで測定したハンダ融点までの最低複素粘度η＊ｍｉｎが５×１０１Ｐａ・ｓを超えると、ボンディング時に半導体チップ接合用接着材料によりハンダが押し流されやすくなり、安定した導通が得られない。
上記レオメーターで測定したハンダ融点までの最低複素粘度η＊ｍｉｎの好ましい上限は４．５×１０１Ｐａ・ｓ、より好ましい上限は４×１０１Ｐａ・ｓ、更に好ましい上限は３．０×１０１Ｐａ・ｓである。 In the adhesive material for bonding a semiconductor chip of the present invention, the upper limit of the lowest complex viscosity η * min up to the solder melting point measured with a rheometer is 5 × 10 1 Pa · s. When the minimum complex viscosity η * min up to the solder melting point measured with the rheometer exceeds 5 × 10 1 Pa · s, the solder is easily washed away by the adhesive material for bonding the semiconductor chip during bonding, and stable conduction is obtained. Absent.
The preferable upper limit of the minimum complex viscosity η * min up to the solder melting point measured with the rheometer is 4.5 × 10 1 Pa · s, the more preferable upper limit is 4 × 10 1 Pa · s, and the more preferable upper limit is 3.0 ×. 10 1 Pa · s.
上記レオメーターで測定したハンダ融点までの最低複素粘度η＊ｍｉｎの下限は特に限定されないが、好ましい下限は５×１０－１Ｐａ・ｓである。上記レオメーターで測定したハンダ融点までの最低複素粘度η＊ｍｉｎが５×１０－１Ｐａ・ｓ未満であると、ボンディング時に噛みこんだボイドが接着剤層に残ることがある。
上記レオメーターで測定したハンダ融点までの最低複素粘度η＊ｍｉｎのより好ましい下限は１Ｐａ・ｓである。 The lower limit of the lowest complex viscosity η * min up to the solder melting point measured with the rheometer is not particularly limited, but the preferred lower limit is 5 × 10 −1 Pa · s. If the minimum complex viscosity η * min up to the solder melting point measured with the rheometer is less than 5 × 10 −1 Pa · s, voids bitten during bonding may remain in the adhesive layer.
A more preferable lower limit of the lowest complex viscosity η * min up to the solder melting point measured with the rheometer is 1 Pa · s.
本明細書中、レオメーターで測定したハンダ融点までの最低複素粘度η＊ｍｉｎとは、本発明の半導体チップ接合用接着材料をフィルム状にして測定した値を意味する。上記レオメーターでハンダ融点までの最低複素粘度η＊ｍｉｎを測定する方法は特に限定されず、例えば、ＳＴＲＥＳＳＴＥＣＨ（ＲＥＯＬＯＧＩＣＡ社製）等の通常のレオメーターを用いて、サンプル厚み６００μｍ、歪制御（１ｒａｄ）、周波数１０Ｈｚ、昇温速度２０℃／ｍｉｎ、測定温度範囲６０℃から３００℃まで測定を行う方法等が挙げられる。
なお、上記ハンダ融点は、例えば、２３０～３２０℃の範囲の温度である。 In the present specification, the lowest complex viscosity η * min up to the solder melting point measured with a rheometer means a value obtained by measuring the adhesive material for bonding a semiconductor chip of the present invention in the form of a film. The method of measuring the lowest complex viscosity η * min up to the solder melting point with the rheometer is not particularly limited. For example, using a normal rheometer such as STRESSTECH (REOLOGICA), the sample thickness is 600 μm, and the strain control (1 rad ), A frequency of 10 Hz, a temperature rising rate of 20 ° C./min, a measurement temperature range of 60 ° C. to 300 ° C. and the like.
The solder melting point is, for example, a temperature in the range of 230 to 320 ° C.
本発明の半導体チップ接合用接着材料は、温度１４０℃、歪量１ｒａｄ、周波数１Ｈｚで測定した複素粘度η＊（１Ｈｚ）が温度１４０℃、歪量１ｒａｄ、周波数１０Ｈｚで測定した複素粘度η＊（１０Ｈｚ）の０．５～４．５倍である。このような複素粘度の比を有することにより、本発明の半導体チップ接合用接着材料は、ボンディング時の加熱により自重によって非凸形状のフィレットを形成することができ、得られる半導体装置の信頼性を高めることができ、また、ダイシング等の他の工程に適用されても不具合を生じさせることがない。 The adhesive material for semiconductor chip bonding of the present invention has a complex viscosity η * (1 Hz) measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 1 Hz, and a complex viscosity η * (measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 10 Hz). 10 Hz) to 0.5 to 4.5 times. By having such a complex viscosity ratio, the semiconductor chip bonding adhesive material of the present invention can form a non-convex fillet by its own weight by heating during bonding, and the reliability of the obtained semiconductor device can be improved. Moreover, even if it is applied to other processes such as dicing, there is no problem.
上記複素粘度η＊（１Ｈｚ）が上記複素粘度η＊（１０Ｈｚ）の０．５倍未満であると、ボンディング時に半導体チップ接合用接着材料の流動性が低くなり、例えば、バンプの接触が妨げられる等の不具合が生じる。上記複素粘度η＊（１Ｈｚ）が上記複素粘度η＊（１０Ｈｚ）の４．５倍を超えると、非凸形状のフィレットを形成することができず、半導体チップの側壁とフィレットとが成す角度が７０°以上になると、凸部に応力が集中して、得られる半導体装置の信頼性が低下する。
本発明の半導体チップ接合用接着材料は、上記複素粘度η＊（１Ｈｚ）が上記複素粘度η＊（１０Ｈｚ）の０．７倍以上であることが好ましく、０．９倍以上であることがより好ましく、１．０倍以上であることが更に好ましく、また、４．３倍以下であることが好ましく、４．０倍以下であることがより好ましい。 When the complex viscosity η * (1 Hz) is less than 0.5 times the complex viscosity η * (10 Hz), the fluidity of the adhesive material for bonding a semiconductor chip is lowered during bonding, and, for example, bump contact is hindered. Such problems occur. If the complex viscosity η * (1 Hz) exceeds 4.5 times the complex viscosity η * (10 Hz), a non-convex fillet cannot be formed, and the angle formed between the side wall of the semiconductor chip and the fillet is When it is 70 ° or more, stress concentrates on the convex portion, and the reliability of the obtained semiconductor device is lowered.
In the adhesive material for bonding a semiconductor chip of the present invention, the complex viscosity η * (1 Hz) is preferably 0.7 times or more, more preferably 0.9 times or more of the complex viscosity η * (10 Hz). Preferably, it is 1.0 times or more, more preferably 4.3 times or less, and even more preferably 4.0 times or less.
本明細書中、複素粘度η＊（１Ｈｚ）及び上記複素粘度η＊（１０Ｈｚ）とは、本発明の半導体チップ接合用接着材料をフィルム状にして測定した値を意味する。上記複素粘度η＊（１Ｈｚ）及び上記複素粘度η＊（１０Ｈｚ）を測定する方法は特に限定されず、例えば、ＳＴＲＥＳＳＴＥＣＨ（ＲＥＯＬＯＧＩＣＡ社製）等の通常の粘度測定装置を用いて、サンプル厚み６００μｍ、歪制御（１ｒａｄ）、周波数１Ｈｚ又は１０Ｈｚ、温度１４０℃で測定を行う方法等が挙げられる。 In the present specification, the complex viscosity η * (1 Hz) and the complex viscosity η * (10 Hz) mean values obtained by measuring the adhesive material for semiconductor chip bonding of the present invention in the form of a film. The method for measuring the complex viscosity η * (1 Hz) and the complex viscosity η * (10 Hz) is not particularly limited. For example, using a normal viscosity measuring device such as STRESSTECH (REOLOGICA), the sample thickness is 600 μm, Examples include a strain control (1 rad), a method of measuring at a frequency of 1 Hz or 10 Hz, and a temperature of 140 ° C.
本発明の半導体チップ接合用接着材料において、上述した範囲のせん断弾性率及び粘度特性を達成する方法は特に限定されないが、例えば、エポキシ化合物、該エポキシ化合物と反応可能な官能基を有する高分子化合物（以下、単に、反応可能な官能基を有する高分子化合物ともいう）、及び、必要に応じて他の添加成分を適宜配合することにより、せん断弾性率及び粘度特性を調整する方法が好ましい。
なかでも、エポキシ化合物の種類及び配合量、並びに、反応可能な官能基を有する高分子化合物の分子量及び配合量を制御することにより、半導体チップ接合用接着材料における各成分の相互作用又は分子鎖の絡み合いを極限にまで低減することが好ましい。また、無機充填材等の非溶解性成分を加える場合には、エポキシ化合物等に対する親和性を高くしたり、無機充填材の粒子径及び配合量を制御したりすることにより、半導体チップ接合用接着材料における凝集等のネットワーク構造の形成を抑制することが好ましい。 In the adhesive material for semiconductor chip bonding of the present invention, the method for achieving the shear modulus and viscosity characteristics in the above-mentioned ranges is not particularly limited. For example, an epoxy compound, a polymer compound having a functional group capable of reacting with the epoxy compound (Hereinafter, it is also simply referred to as a polymer compound having a functional group capable of reacting) and a method of adjusting the shear modulus and viscosity characteristics by appropriately blending other additive components as necessary is preferable.
Among these, by controlling the type and blending amount of the epoxy compound and the molecular weight and blending amount of the polymer compound having a functional group capable of reacting, the interaction of each component or the molecular chain of the adhesive material for semiconductor chip bonding is controlled. It is preferable to reduce the entanglement to the limit. In addition, when adding an insoluble component such as an inorganic filler, it is possible to increase the affinity for an epoxy compound or the like, or to control the particle size and blending amount of the inorganic filler, thereby adhering for bonding a semiconductor chip. It is preferable to suppress formation of a network structure such as aggregation in the material.
上記エポキシ化合物は特に限定されず、例えば、軟化点が１５０℃以下のエポキシ樹脂、常温で液体又は結晶性固体のエポキシ樹脂等が挙げられる。これらのエポキシ化合物は、単独で用いられてもよく、二種以上が併用されてもよい。
上記軟化点が１５０℃以下のエポキシ樹脂として、例えば、フェノールノボラックエポキシ樹脂、ビスフェノールＡノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ジシクロペンタジエンフェノールノボラック型エポキシ樹脂、ビフェニルフェノールノボラックエポキシ樹脂等が挙げられる。なかでも、ジシクロペンタジエンフェノールノボラック型エポキシ樹脂が好ましい。 The epoxy compound is not particularly limited, and examples thereof include an epoxy resin having a softening point of 150 ° C. or lower, an epoxy resin that is liquid or crystalline solid at room temperature, and the like. These epoxy compounds may be used independently and 2 or more types may be used together.
Examples of the epoxy resin having a softening point of 150 ° C. or lower include a phenol novolac epoxy resin, a bisphenol A novolac epoxy resin, a cresol novolac epoxy resin, a dicyclopentadienephenol novolac epoxy resin, and a biphenylphenol novolac epoxy resin. Of these, dicyclopentadienephenol novolac type epoxy resin is preferable.
上記常温で液体又は結晶性固体のエポキシ樹脂として、例えば、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＡＤ型、ビスフェノールＳ型等のビスフェノール型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、アントラセン型エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオレン型エポキシ樹脂等が挙げられる。なかでも、アントラセン型エポキシ樹脂が好ましい。 Examples of the epoxy resin that is liquid or crystalline solid at room temperature include, for example, bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD type, and bisphenol S type, dicyclopentadiene type epoxy resins, resorcinol type epoxy resins, and biphenyl. Type epoxy resin, anthracene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin and the like. Of these, anthracene type epoxy resins are preferable.
上記反応可能な官能基を有する高分子化合物を含有することで、本発明の半導体チップ接合用接着材料の硬化物は靭性をもち、優れた耐衝撃性を発現することができる。
上記反応可能な官能基を有する高分子化合物は特に限定されず、例えば、アミノ基、ウレタン基、イミド基、水酸基、カルボキシル基、エポキシ基等を有する高分子化合物等が挙げられる。なかでも、エポキシ基を有する高分子化合物が好ましい。
上記エポキシ基を有する高分子化合物を含有することで、得られる半導体チップ接合用接着材料の硬化物は優れた靭性を発現する。即ち、得られる半導体チップ接合用接着材料の硬化物は、上記エポキシ化合物に由来する優れた機械的強度、耐熱性及び耐湿性と、上記エポキシ基を有する高分子化合物に由来する優れた靭性とを兼備することにより、高い接合信頼性及び接続信頼性を発現することができる。 By containing the polymer compound having a functional group capable of reacting, the cured product of the adhesive material for bonding a semiconductor chip of the present invention has toughness and can exhibit excellent impact resistance.
The polymer compound having a reactive functional group is not particularly limited, and examples thereof include a polymer compound having an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group, and the like. Among these, a polymer compound having an epoxy group is preferable.
By containing the high molecular compound which has the said epoxy group, the hardened | cured material of the adhesive material for semiconductor chip joining obtained expresses the outstanding toughness. That is, the cured product of the adhesive material for bonding semiconductor chips obtained has excellent mechanical strength, heat resistance and moisture resistance derived from the epoxy compound, and excellent toughness derived from the polymer compound having the epoxy group. By having both, high joint reliability and connection reliability can be expressed.
上記エポキシ基を有する高分子化合物は、末端及び／又は側鎖（ペンダント位）にエポキシ基を有する高分子化合物であれば特に限定されず、例えば、エポキシ基含有アクリルゴム、エポキシ基含有ブタジエンゴム、ビスフェノール型高分子量エポキシ樹脂、エポキシ基含有フェノキシ樹脂、エポキシ基含有アクリル樹脂、エポキシ基含有ウレタン樹脂、エポキシ基含有ポリエステル樹脂等が挙げられる。なかでも、エポキシ基を多く含み、得られる半導体チップ接合用接着材料の硬化物が優れた機械的強度、耐熱性、靭性等を発現できることから、エポキシ基含有アクリル樹脂が好ましい。これらのエポキシ基を有する高分子化合物は、単独で用いられてもよく、二種以上が併用されてもよい。 The polymer compound having an epoxy group is not particularly limited as long as it is a polymer compound having an epoxy group at the terminal and / or side chain (pendant position). For example, an epoxy group-containing acrylic rubber, an epoxy group-containing butadiene rubber, Examples thereof include bisphenol type high molecular weight epoxy resin, epoxy group-containing phenoxy resin, epoxy group-containing acrylic resin, epoxy group-containing urethane resin, and epoxy group-containing polyester resin. Among these, an epoxy group-containing acrylic resin is preferable because it contains a large amount of epoxy groups and the cured product of the obtained adhesive material for joining semiconductor chips can exhibit excellent mechanical strength, heat resistance, toughness, and the like. These polymer compounds having an epoxy group may be used alone or in combination of two or more.
上記エポキシ基を有する高分子化合物、特にエポキシ基含有アクリル樹脂を用いる場合、該エポキシ基を有する高分子化合物の重量平均分子量の好ましい上限は２０万、好ましい下限は１万である。上記重量平均分子量が１万未満であると、半導体チップ接合用接着材料を用いてフィルムを製造する際の造膜性が不充分となり、フィルムとして形状を保持することができないことがある。上記重量平均分子量が２０万を超えると、得られる半導体チップ接合用接着材料において、上述した範囲のせん断弾性率及び複素粘度の比を達成することができないことがある。
また、上記重量平均分子量が１万未満であると、得られる半導体チップ接合用接着材料には低分子量化合物が多く存在するため、ボンディング時にボイドが発生しやすくなることがある。
上記エポキシ基を有する高分子化合物の重量平均分子量のより好ましい上限は１５万、更に好ましい上限は１０万、更により好ましい上限は５万、特に好ましい上限は２万である。 In the case of using the above-mentioned polymer compound having an epoxy group, particularly an epoxy group-containing acrylic resin, the preferred upper limit of the weight average molecular weight of the polymer compound having an epoxy group is 200,000, and the preferred lower limit is 10,000. When the weight average molecular weight is less than 10,000, the film-forming property at the time of producing a film using a semiconductor chip bonding adhesive material may be insufficient, and the shape may not be maintained as a film. When the weight average molecular weight exceeds 200,000, in the obtained adhesive material for bonding a semiconductor chip, the ratio of the shear elastic modulus and the complex viscosity in the above range may not be achieved.
Further, when the weight average molecular weight is less than 10,000, since there are many low molecular weight compounds in the obtained adhesive material for bonding a semiconductor chip, voids may easily occur during bonding.
The upper limit of the weight average molecular weight of the polymer compound having an epoxy group is more preferably 150,000, still more preferably 100,000, still more preferably 50,000, and particularly preferably 20,000.
上記エポキシ基を有する高分子化合物は、単独で用いられてもよく、異なる重量平均分子量を有する二種以上が併用されてもよい。例えば、重量平均分子量が５万以下の高分子化合物と、重量平均分子量が５万を超える高分子化合物とが併用されてもよい。このような場合、上記重量平均分子量が５万を超える高分子化合物の含有量は、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に占める好ましい上限が２０重量部である。上記重量平均分子量が５万を超える高分子化合物の含有量が２０重量部を超えると、得られる半導体チップ接合用接着材料において、上述した最低複素粘度及び複素粘度の比が大きくなりすぎることがある。 The said high molecular compound which has an epoxy group may be used independently, and 2 or more types which have a different weight average molecular weight may be used together. For example, a polymer compound having a weight average molecular weight of 50,000 or less and a polymer compound having a weight average molecular weight exceeding 50,000 may be used in combination. In such a case, the content of the polymer compound having a weight average molecular weight of more than 50,000 has a preferable upper limit of 20 in a total of 100 parts by weight of the epoxy compound and the polymer compound having a reactive functional group. Parts by weight. When the content of the polymer compound having a weight average molecular weight exceeding 50,000 exceeds 20 parts by weight, the ratio of the lowest complex viscosity and the complex viscosity described above may be too large in the obtained adhesive material for semiconductor chip bonding. .
上記エポキシ基を有する高分子化合物、特にエポキシ基含有アクリル樹脂を用いる場合、該エポキシ基を有する高分子化合物のエポキシ当量の好ましい下限は２００、好ましい上限は１０００である。上記エポキシ当量が２００未満であると、得られる半導体チップ接合用接着材料の硬化物が堅く、脆くなることがある。上記エポキシ当量が１０００を超えると、得られる半導体チップ接合用接着材料の硬化物の機械的強度、耐熱性等が不充分となることがある。 When using the polymer compound having an epoxy group, particularly an epoxy group-containing acrylic resin, the preferred lower limit of the epoxy equivalent of the polymer compound having an epoxy group is 200, and the preferred upper limit is 1000. When the epoxy equivalent is less than 200, the cured product of the obtained adhesive material for semiconductor chip bonding may be hard and brittle. When the epoxy equivalent exceeds 1000, the mechanical strength, heat resistance, and the like of the obtained cured product of the adhesive material for bonding a semiconductor chip may be insufficient.
上記反応可能な官能基を有する高分子化合物の含有量は特に限定されないが、上記エポキシ化合物１００重量部に対する好ましい下限が１重量部、好ましい上限が５００重量部である。上記反応可能な官能基を有する高分子化合物の含有量が１重量部未満であると、得られる半導体チップ接合用接着材料の硬化物は、熱によるひずみが発生する際、靭性が不充分となり、接合信頼性が劣ることがある。上記反応可能な官能基を有する高分子化合物の含有量が５００重量部を超えると、得られる半導体チップ接合用接着材料において、上述した複素粘度の比が大きくなりすぎることがあり、また、硬化物の耐熱性が低下することがある。
上記反応可能な官能基を有する高分子化合物の含有量は、上述した範囲の複素粘度の比を達成する観点から、上記エポキシ化合物１００重量部に対するより好ましい上限が４００重量部である。 The content of the polymer compound having a functional group capable of reacting is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the epoxy compound is 1 part by weight, and a preferable upper limit is 500 parts by weight. When the content of the polymer compound having a functional group capable of reacting is less than 1 part by weight, the cured product of the obtained adhesive material for bonding a semiconductor chip has insufficient toughness when strain due to heat occurs. Bonding reliability may be inferior. When the content of the polymer compound having a reactive functional group exceeds 500 parts by weight, the above-described complex viscosity ratio may be too large in the obtained adhesive material for bonding a semiconductor chip, and a cured product The heat resistance of may decrease.
The content of the polymer compound having a functional group capable of reacting is preferably 400 parts by weight with respect to 100 parts by weight of the epoxy compound from the viewpoint of achieving the complex viscosity ratio in the above-described range.
本発明の半導体チップ接合用接着材料は、硬化剤を含有することが好ましい。
上記硬化剤は特に限定されず、例えば、アミン系硬化剤、酸無水物硬化剤、フェノール系硬化剤等が挙げられる。なかでも、酸無水物硬化剤が好ましい。
上記酸無水物硬化剤は特に限定されないが、２官能の酸無水物硬化剤が好ましい。上記２官能の酸無水物硬化剤は特に限定されず、例えば、フタル酸誘導体の無水物、無水マレイン酸等が挙げられる。 The adhesive material for bonding a semiconductor chip of the present invention preferably contains a curing agent.
The said hardening | curing agent is not specifically limited, For example, an amine type hardening | curing agent, an acid anhydride hardening | curing agent, a phenol type hardening | curing agent etc. are mentioned. Of these, acid anhydride curing agents are preferred.
The acid anhydride curing agent is not particularly limited, but a bifunctional acid anhydride curing agent is preferable. The bifunctional acid anhydride curing agent is not particularly limited, and examples thereof include phthalic acid derivative anhydrides and maleic anhydride.
また、上記硬化剤として、３官能以上の酸無水物硬化剤粒子を用いてもよい。上記３官能以上の酸無水物硬化剤粒子は特に限定されず、例えば、無水トリメリット酸等の３官能の酸無水物からなる粒子、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸、メチルシクロヘキセンテトラカルボン酸無水物、ポリアゼライン酸無水物等の４官能以上の酸無水物からなる粒子等が挙げられる。 In addition, trifunctional or higher functional acid anhydride curing agent particles may be used as the curing agent. The trifunctional or higher functional acid anhydride curing agent particles are not particularly limited. For example, particles composed of trifunctional acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, methylcyclohexene tetracarboxylic acid. Examples thereof include particles composed of tetrafunctional or higher functional acid anhydrides such as acid anhydrides and polyazeline acid anhydrides.
上記３官能以上の酸無水物硬化剤粒子の平均粒子径は特に限定されないが、好ましい下限が０．１μｍ、好ましい上限が５μｍである。上記３官能以上の酸無水物硬化剤粒子の平均粒子径が０．１μｍ未満であると、硬化剤粒子の凝集が生じ、半導体チップ接合用接着材料が増粘して、凸形状のフィレットを形成できないことがある。上記３官能以上の酸無水物硬化剤粒子の平均粒子径が５μｍを超えると、得られる半導体チップ接合用接着材料において、硬化時に硬化剤粒子が充分に拡散することができず、硬化不良となることがある。 The average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles is not particularly limited, but a preferable lower limit is 0.1 μm and a preferable upper limit is 5 μm. If the average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles is less than 0.1 μm, aggregation of the curing agent particles occurs, and the adhesive material for bonding the semiconductor chip thickens to form a convex fillet. There are things that cannot be done. When the average particle diameter of the above-mentioned trifunctional or higher acid anhydride curing agent particles exceeds 5 μm, in the obtained adhesive material for bonding a semiconductor chip, the curing agent particles cannot be sufficiently diffused during curing, resulting in curing failure. Sometimes.
本発明の半導体チップ接合用接着材料が上記硬化剤を含有する場合、上記硬化剤の含有量は特に限定されないが、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に対する好ましい下限が５重量部、好ましい上限が１５０重量部である。上記硬化剤の含有量が５重量部未満であると、得られる半導体チップ接合用接着材料が充分に硬化しないことがある。上記硬化剤の含有量が１５０重量部を超えると、得られる半導体チップ接合用接着材料の接続信頼性が低下することがある。
上記硬化剤の含有量は、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に対するより好ましい下限が１０重量部、より好ましい上限が１４０重量部である。 When the adhesive material for semiconductor chip bonding of the present invention contains the curing agent, the content of the curing agent is not particularly limited, but a total of 100 of the epoxy compound and the polymer compound having a reactive functional group. A preferred lower limit relative to parts by weight is 5 parts by weight, and a preferred upper limit is 150 parts by weight. If the content of the curing agent is less than 5 parts by weight, the resulting semiconductor chip bonding adhesive material may not be sufficiently cured. When content of the said hardening | curing agent exceeds 150 weight part, the connection reliability of the adhesive material for semiconductor chip joining obtained may fall.
The content of the curing agent is preferably 10 parts by weight and more preferably 140 parts by weight with respect to a total of 100 parts by weight of the epoxy compound and the polymer compound having a reactive functional group.
また、上記硬化剤が、上記２官能の酸無水物硬化剤と上記３官能以上の酸無水物硬化剤粒子とを含有する場合、これらの配合比は特に限定されないが、上記３官能以上の酸無水物硬化剤粒子の含有量（重量）を上記２官能の酸無水物硬化剤の含有量（重量）で除した値［＝（３官能以上の酸無水物硬化剤粒子の含有量）／（２官能の酸無水物硬化剤の含有量）］の好ましい下限が０．１、好ましい上限が１０である。上記値が０．１未満であると、上記３官能以上の酸無水物硬化剤粒子を添加する効果が充分に得られないことがある。上記値が１０を超えると、得られる半導体チップ接合用接着材料の硬化物が脆くなり、充分な接着信頼性が得られないことがある。上記値のより好ましい下限は０．２、より好ましい上限は８である。 Moreover, when the said hardening | curing agent contains the said bifunctional acid anhydride hardening | curing agent and the said trifunctional or more acid anhydride hardening | curing agent particle | grains, these compounding ratios are not specifically limited, The said trifunctional or more acid Value obtained by dividing the content (weight) of anhydride curing agent particles by the content (weight) of the above bifunctional acid anhydride curing agent [= (content of trifunctional or higher functional acid anhydride curing agent particles) / ( The preferable lower limit of the content of the bifunctional acid anhydride curing agent]] is 0.1, and the preferable upper limit is 10. When the value is less than 0.1, the effect of adding the trifunctional or higher functional acid anhydride curing agent particles may not be sufficiently obtained. When the above value exceeds 10, the cured product of the obtained adhesive material for semiconductor chip bonding becomes fragile, and sufficient adhesion reliability may not be obtained. A more preferred lower limit of the above value is 0.2, and a more preferred upper limit is 8.
本発明の半導体チップ接合用接着材料は、硬化促進剤を含有してもよい。
上記硬化促進剤は特に限定されないが、イミダゾール化合物が好ましい。上記イミダゾール化合物は上記エポキシ化合物との反応性が高いことから、上記イミダゾール化合物を含有することで、得られる半導体チップ接合用接着材料は速硬化性が向上する。 The adhesive material for bonding a semiconductor chip of the present invention may contain a curing accelerator.
Although the said hardening accelerator is not specifically limited, An imidazole compound is preferable. Since the said imidazole compound has high reactivity with the said epoxy compound, quick curing property improves the adhesive material for semiconductor chip joining obtained by containing the said imidazole compound.
上記イミダゾール化合物は特に限定されず、例えば、イミダゾールの１位をシアノエチル基で保護した１－シアノエチル－２－フェニルイミダゾール、イソシアヌル酸で塩基性を保護したイミダゾール化合物（商品名「２ＭＡ－ＯＫ」、四国化成工業社製）、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン（商品名「２ＭＺ－Ａ」、四国化成工業社製）、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール（商品名「２Ｐ４ＭＨＺ」、四国化成工業社製）、フジキュア７０００（富士化成工業）等が挙げられる。これらのイミダゾール化合物は、単独で用いられてもよく、二種以上が併用されてもよい。 The imidazole compound is not particularly limited. For example, 1-cyanoethyl-2-phenylimidazole in which the 1-position of imidazole is protected with a cyanoethyl group, an imidazole compound in which basicity is protected with isocyanuric acid (trade name “2MA-OK”, Shikoku, Japan) Kasei Kogyo Co., Ltd.), 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (trade name “2MZ-A”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole (trade name “2P4MHZ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), Fuji Cure 7000 (Fuji Kasei Kogyo Co., Ltd.), and the like. These imidazole compounds may be used independently and 2 or more types may be used together.
本発明の半導体チップ接合用接着材料が上記硬化促進剤を含有する場合、上記硬化促進剤の含有量は特に限定されないが、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に対する好ましい下限が０．３重量部、好ましい上限が８重量部である。上記硬化促進剤の含有量が０．３重量部未満であると、得られる半導体チップ接合用接着材料が充分に硬化しないことがある。上記硬化促進剤の含有量が８重量部を超えると、得られる半導体チップ接合用接着材料において、未反応の硬化促進剤が接着界面に染み出すことにより、接合信頼性が低下することがある。 When the adhesive material for semiconductor chip bonding of the present invention contains the curing accelerator, the content of the curing accelerator is not particularly limited, but the epoxy compound and the polymer compound having the reactive functional group A preferable lower limit with respect to 100 parts by weight in total is 0.3 part by weight, and a preferable upper limit is 8 parts by weight. When the content of the curing accelerator is less than 0.3 parts by weight, the obtained adhesive material for joining a semiconductor chip may not be sufficiently cured. When the content of the curing accelerator is more than 8 parts by weight, in the obtained adhesive material for bonding a semiconductor chip, unreacted curing accelerator oozes out to the adhesive interface, which may reduce the bonding reliability.
本発明の半導体チップ接合用接着材料は、無機充填材を含有してもよい。
上記無機充填材を含有することで、得られる半導体チップ接合用接着材料の硬化物の線膨張率を低下させることができ、接合された半導体チップへの応力の発生及びハンダ等の導通部分のクラックの発生を良好に防止することができる。
上記無機充填材は特に限定されず、例えば、ヒュームドシリカ、コロイダルシリカ等のシリカ、アルミナ、窒化アルミニウム、窒化ホウ素、窒化ケイ素、ガラスパウダー、ガラスフリット等が挙げられる。 The adhesive material for joining a semiconductor chip of the present invention may contain an inorganic filler.
By containing the inorganic filler, it is possible to reduce the linear expansion coefficient of the cured product of the obtained adhesive material for bonding semiconductor chips, and to generate stress on the bonded semiconductor chips and cracks in conductive parts such as solder. Can be satisfactorily prevented.
The inorganic filler is not particularly limited, and examples thereof include silica such as fumed silica and colloidal silica, alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, and glass frit.
上記無機充填材は、炭素数１～１０の炭化水素含有基を表面に有することが好ましい。
上記無機充填材が上記炭素数１～１０の炭化水素含有基を表面に有することにより、得られる半導体チップ接合用接着材料において、上記無機充填材の配合量が増えても最低複素粘度の上昇を低減することができる。また、上述した範囲の複素粘度の比を達成することも容易となる。更に、半導体チップ接合用接着材料に上記炭素数１～１０の炭化水素含有基を表面に有する無機充填材を配合することにより、得られる半導体装置の信頼性をより向上させることができる。
なお、上記炭素数１～１０の炭化水素含有基を表面に有さない無機充填材であっても、配合量を調整したり他の成分との配合比を調整したりすることにより上述した範囲の最低複素粘度及び複素粘度の比を達成できれば用いることができる。 The inorganic filler preferably has a hydrocarbon-containing group having 1 to 10 carbon atoms on the surface.
When the inorganic filler has the hydrocarbon-containing group having 1 to 10 carbon atoms on the surface, the minimum complex viscosity can be increased even if the amount of the inorganic filler is increased in the obtained adhesive material for semiconductor chip bonding. Can be reduced. It is also easy to achieve a complex viscosity ratio in the range described above. Furthermore, the reliability of the obtained semiconductor device can be further improved by blending the semiconductor chip bonding adhesive material with the inorganic filler having the hydrocarbon-containing group having 1 to 10 carbon atoms on the surface.
Even in the case of the inorganic filler having no hydrocarbon-containing group having 1 to 10 carbon atoms on the surface, the above-mentioned range can be obtained by adjusting the blending amount or the blending ratio with other components. If the ratio of the lowest complex viscosity to the complex viscosity can be achieved, it can be used.
上記炭素数１～１０の炭化水素含有基は特に限定されないが、ヘキシル基、メチル基、フェニル基等が好ましい。上記炭素数１～１０の炭化水素含有基は、例えば、上記炭素数１～１０の炭化水素含有基を骨格中に有するシランカップリング剤等のカップリング剤を用いて、上記無機充填材に表面処理を施すことにより導入することができる。 The hydrocarbon-containing group having 1 to 10 carbon atoms is not particularly limited, but a hexyl group, a methyl group, a phenyl group and the like are preferable. The hydrocarbon-containing group having 1 to 10 carbon atoms is formed on the surface of the inorganic filler using a coupling agent such as a silane coupling agent having the hydrocarbon-containing group having 1 to 10 carbon atoms in the skeleton. It can be introduced by processing.
上記無機充填材として粒子状の無機充填材を用いる場合、平均粒子径の好ましい下限は１ｎｍ、好ましい上限は５μｍである。上記粒子状の無機充填材の平均粒子径が１ｎｍ未満であると、得られる半導体チップ接合用接着材料において上記無機充填材の凝集が生じやすく、上述した範囲の複素粘度の比を達成できず、凸形状のフィレットを形成しやすい半導体チップ接合用接着材料が得られることがある。上記粒子状の無機充填材の平均粒子径が５μｍを超えると、得られる半導体チップ接合用接着材料を用いて圧接合する際に、電極間で上記無機充填材を噛みこむことがある。
上記粒子状の無機充填材の平均粒子径のより好ましい下限は５ｎｍ、より好ましい上限は３μｍであり、特に好ましい下限は１０ｎｍ、特に好ましい上限は１μｍである。
本明細書中、平均粒子径とは、レーザー回折／散乱式粒子径分布測定装置で測定される％積算径が５０％の粒子径を意味する。 When a particulate inorganic filler is used as the inorganic filler, the preferred lower limit of the average particle diameter is 1 nm, and the preferred upper limit is 5 μm. When the average particle diameter of the particulate inorganic filler is less than 1 nm, aggregation of the inorganic filler is likely to occur in the obtained semiconductor chip bonding adhesive material, and the ratio of complex viscosity in the above range cannot be achieved. In some cases, an adhesive material for joining a semiconductor chip that easily forms a convex fillet may be obtained. When the average particle diameter of the particulate inorganic filler exceeds 5 μm, the inorganic filler may be bitten between the electrodes when pressure bonding is performed using the obtained adhesive material for semiconductor chip bonding.
The more preferable lower limit of the average particle diameter of the particulate inorganic filler is 5 nm, the more preferable upper limit is 3 μm, the particularly preferable lower limit is 10 nm, and the particularly preferable upper limit is 1 μm.
In the present specification, the average particle diameter means a particle diameter having a 50% integrated diameter measured by a laser diffraction / scattering particle size distribution measuring apparatus.
本発明の半導体チップ接合用接着材料が上記炭素数１～１０の炭化水素含有基を表面に有する無機充填材を含有する場合、上記無機充填材の含有量は特に限定されないが、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に対する好ましい下限は５重量部、好ましい上限は５００重量部である。上記無機充填材の含有量が５重量部未満であると、上記無機充填材を添加する効果をほとんど得ることができないことがある。上記無機充填材の含有量が５００重量部を超えると、得られる半導体チップ接合用接着材料の硬化物の線膨張率は低下するものの、同時にせん断弾性率が上昇して非凸形状のフィレットを形成することができないことがある。これにより、接合された半導体チップへの応力及びハンダ等の導通部分のクラックが発生しやすくなることがある。
上記炭素数１～１０の炭化水素含有基を表面に有する無機充填材の含有量は、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に対するより好ましい下限は１０重量部、より好ましい上限は４００重量部、更に好ましい下限は１５重量部、更に好ましい上限は３００重量部である。 When the semiconductor chip bonding adhesive material of the present invention contains an inorganic filler having a hydrocarbon-containing group having 1 to 10 carbon atoms on the surface, the content of the inorganic filler is not particularly limited, but the epoxy compound and The preferable lower limit with respect to 100 parts by weight in total with the polymer compound having a functional group capable of reacting is 5 parts by weight, and the preferable upper limit is 500 parts by weight. If the content of the inorganic filler is less than 5 parts by weight, the effect of adding the inorganic filler may be hardly obtained. When the content of the inorganic filler exceeds 500 parts by weight, the linear expansion coefficient of the cured product of the obtained adhesive material for semiconductor chip bonding decreases, but at the same time, the shear elastic modulus increases to form a non-convex fillet. There are things you can't do. As a result, stress on the bonded semiconductor chips and cracks in the conductive portion such as solder may easily occur.
The content of the inorganic filler having a hydrocarbon-containing group having 1 to 10 carbon atoms on the surface is more preferably lower limit with respect to 100 parts by weight in total of the epoxy compound and the polymer compound having a reactive functional group. 10 parts by weight, a more preferred upper limit is 400 parts by weight, a still more preferred lower limit is 15 parts by weight, and a still more preferred upper limit is 300 parts by weight.
また、本発明の半導体チップ接合用接着材料が上記炭素数１～１０の炭化水素含有基を表面に有さない無機充填材を含有する場合、上記無機充填材の含有量は特に限定されないが、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に対する好ましい下限は５重量部、好ましい上限は２００重量部である。
また、本発明の半導体チップ接合用接着材料が上記平均粒子径が１０ｎｍ以下の無機充填材を含有する場合、上記無機充填材の含有量は特に限定されないが、表面処理の有無にかかわらず、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に対して５０重量部以下であることが好ましい。 Further, when the adhesive material for bonding a semiconductor chip of the present invention contains an inorganic filler having no hydrocarbon-containing group having 1 to 10 carbon atoms on its surface, the content of the inorganic filler is not particularly limited, The preferable lower limit with respect to a total of 100 parts by weight of the epoxy compound and the polymer compound having a reactive functional group is 5 parts by weight, and the preferable upper limit is 200 parts by weight.
When the semiconductor chip bonding adhesive material of the present invention contains an inorganic filler having an average particle diameter of 10 nm or less, the content of the inorganic filler is not particularly limited, but the above-mentioned regardless of the presence or absence of surface treatment. The amount is preferably 50 parts by weight or less based on 100 parts by weight of the total of the epoxy compound and the polymer compound having a functional group capable of reacting.
本発明の半導体チップ接合用接着材料は、本発明の効果を阻害しない範囲内で希釈剤を含有してもよい。
上記希釈剤は特に限定されないが、半導体チップ接合用接着材料の加熱硬化時に硬化物に取り込まれる反応性希釈剤が好ましい。なかでも、得られる半導体チップ接合用接着材料の接着信頼性を悪化させないために、１分子中に２以上の官能基を有する反応性希釈剤がより好ましい。
上記１分子中に２以上の官能基を有する反応性希釈剤として、例えば、脂肪族型エポキシ、エチレンオキサイド変性エポキシ、プロピレンオキサイド変性エポキシ、シクロヘキサン型エポキシ、ジシクロペンタジエン型エポキシ、フェノール型エポキシ等が挙げられる。 The adhesive material for bonding a semiconductor chip of the present invention may contain a diluent as long as the effects of the present invention are not impaired.
Although the said diluent is not specifically limited, The reactive diluent taken in into hardened | cured material at the time of heat-hardening of the adhesive material for semiconductor chip joining is preferable. Among these, a reactive diluent having two or more functional groups in one molecule is more preferable in order not to deteriorate the adhesion reliability of the obtained adhesive material for bonding a semiconductor chip.
Examples of the reactive diluent having two or more functional groups in one molecule include aliphatic epoxy, ethylene oxide modified epoxy, propylene oxide modified epoxy, cyclohexane epoxy, dicyclopentadiene epoxy, phenol epoxy and the like. Can be mentioned.
本発明の半導体チップ接合用接着材料が上記希釈剤を含有する場合、上記希釈剤の含有量は特に限定されないが、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に対する好ましい下限は１重量部、好ましい上限は３００重量部である。上記希釈剤の含有量が１重量部未満であると、上記希釈剤を添加する効果をほとんど得ることができないことがある。上記希釈剤の含有量が３００重量部を超えると、得られる半導体チップ接合用接着材料の硬化物が硬く脆くなるため、接着信頼性が劣ることがある。
上記希釈剤の含有量は、上記エポキシ化合物と、上記反応可能な官能基を有する高分子化合物との合計１００重量部に対するより好ましい下限が５重量部、より好ましい上限が２００重量部である。 When the adhesive material for bonding a semiconductor chip of the present invention contains the diluent, the content of the diluent is not particularly limited, but a total of 100 of the epoxy compound and the polymer compound having a reactive functional group. The preferable lower limit with respect to parts by weight is 1 part by weight, and the preferable upper limit is 300 parts by weight. If the content of the diluent is less than 1 part by weight, the effect of adding the diluent may be hardly obtained. If the content of the diluent exceeds 300 parts by weight, the cured product of the obtained adhesive material for joining semiconductor chips becomes hard and brittle, and thus the adhesion reliability may be inferior.
The content of the diluent is more preferably a lower limit of 5 parts by weight and a more preferable upper limit of 200 parts by weight with respect to a total of 100 parts by weight of the epoxy compound and the polymer compound having a reactive functional group.
本発明の半導体チップ接合用接着材料は、必要に応じて、無機イオン交換体を含有してもよい。上記無機イオン交換体のうち、市販品として、例えば、ＩＸＥシリーズ（東亞合成社製）等が挙げられる。本発明の半導体チップ接合用接着材料が上記無機イオン交換体を含有する場合、上記無機イオン交換体の含有量は特に限定されないが、本発明の半導体チップ接合用接着材料中の好ましい下限が１重量％、好ましい上限が１０重量％である。 The semiconductor chip bonding adhesive material of the present invention may contain an inorganic ion exchanger, if necessary. Among the inorganic ion exchangers, examples of commercially available products include IXE series (manufactured by Toagosei Co., Ltd.). When the adhesive material for bonding a semiconductor chip of the present invention contains the inorganic ion exchanger, the content of the inorganic ion exchanger is not particularly limited, but the preferred lower limit in the adhesive material for bonding a semiconductor chip of the present invention is 1 weight. %, And a preferred upper limit is 10% by weight.
本発明の半導体チップ接合用接着材料は、その他必要に応じて、ブリード防止剤、シランカップリング剤、イミダゾールシランカップリング剤等の接着性付与剤、増粘剤等の添加剤を含有してもよい。 The adhesive material for semiconductor chip bonding of the present invention may contain additives such as an anti-bleeding agent, a silane coupling agent, an adhesion imparting agent such as an imidazole silane coupling agent, and a thickener as necessary. Good.
本発明の半導体チップ接合用接着材料を製造する方法は特に限定されず、例えば、上記エポキシ化合物、上記反応可能な官能基を有する高分子化合物、上記硬化剤、上記無機充填材等を所定量配合して混合する方法等が挙げられる。
上記混合する方法は特に限定されず、例えば、ホモディスパー、万能ミキサー、バンバリーミキサー、ニーダー等を用いて混合する方法等が挙げられる。 The method for producing the semiconductor chip bonding adhesive material of the present invention is not particularly limited. For example, a predetermined amount of the epoxy compound, the polymer compound having a reactive functional group, the curing agent, the inorganic filler, and the like is blended. And a method of mixing them.
The method of mixing is not particularly limited, and examples thereof include a method of mixing using a homodisper, a universal mixer, a Banbury mixer, a kneader, and the like.
本発明の半導体チップ接合用接着材料の用途は特に限定されず、例えば、ウエハ又は半導体チップを、他のウエハ、他の半導体チップ又は基板に実装する際に用いられる。なかでも、本発明の半導体チップ接合用接着材料はフリップチップ実装に用いられることが好ましく、電極接合後にアンダーフィルを充填するフリップチップ実装よりも、ウエハ、半導体チップ又は基板に接着剤層を予め搭載するフリップチップ実装に用いられることがより好ましい。 The use of the adhesive material for bonding a semiconductor chip of the present invention is not particularly limited. For example, it is used when a wafer or a semiconductor chip is mounted on another wafer, another semiconductor chip or a substrate. Among them, the adhesive material for bonding a semiconductor chip of the present invention is preferably used for flip chip mounting, and an adhesive layer is pre-mounted on a wafer, a semiconductor chip or a substrate rather than flip chip mounting in which an underfill is filled after electrode bonding. More preferably, it is used for flip chip mounting.
本発明の半導体チップ接合用接着材料は、フィレット形状を、凸形状にならないように制御することができることから、本発明の半導体チップ接合用接着材料を用いることで、信頼性の高い半導体装置を製造することができる。
本発明の半導体チップ接合用接着材料を用いた半導体装置の製造方法は特に限定されず、例えば、本発明の半導体チップ接合用接着材料に溶剤を添加して調製した接着剤溶液をウエハに塗布し、前記溶剤を乾燥してフィルム化する方法等が挙げられる。このような半導体装置の製造方法もまた、本発明の１つである。 Since the semiconductor chip bonding adhesive material of the present invention can control the fillet shape so as not to be a convex shape, a highly reliable semiconductor device is manufactured by using the semiconductor chip bonding adhesive material of the present invention. can do.
A method for manufacturing a semiconductor device using the semiconductor chip bonding adhesive material of the present invention is not particularly limited. For example, an adhesive solution prepared by adding a solvent to the semiconductor chip bonding adhesive material of the present invention is applied to a wafer. And a method of drying the solvent to form a film. Such a method of manufacturing a semiconductor device is also one aspect of the present invention.
上記溶剤として、例えば、プロピレングリコールメチルエーテルアセテート等の１２０～２５０℃程度の沸点を有する中沸点溶剤又は高沸点溶剤等が挙げられる。本発明の半導体チップ接合用接着材料に溶剤を添加して調製した接着剤溶液をウエハに塗布する方法は特に限定されず、例えば、スピンコート、スクリーン印刷等が挙げられる。 Examples of the solvent include medium-boiling solvents or high-boiling solvents having a boiling point of about 120 to 250 ° C. such as propylene glycol methyl ether acetate. A method of applying an adhesive solution prepared by adding a solvent to the adhesive material for bonding semiconductor chips of the present invention to a wafer is not particularly limited, and examples thereof include spin coating and screen printing.
また、本発明の半導体チップ接合用接着材料を用いた半導体装置の製造方法として、本発明の半導体チップ接合用接着材料が溶剤を含有しない場合には、例えば、本発明の半導体チップ接合用接着材料をウエハに塗布し、Ｂステージ化剤又は露光によってフィルム化する方法等も挙げられる。 In addition, as a method for manufacturing a semiconductor device using the adhesive material for bonding a semiconductor chip of the present invention, when the adhesive material for bonding a semiconductor chip of the present invention does not contain a solvent, for example, the adhesive material for bonding a semiconductor chip of the present invention The method etc. which apply | coat to a wafer and make into a film by B staging agent or exposure, etc. are also mentioned.
本発明の半導体チップ接合用接着材料からなる半導体チップ接合用接着フィルムもまた、本発明の１つである。
本発明の半導体チップ接合用接着フィルムの厚みは特に限定されないが、好ましい下限は２μｍ、好ましい上限は５００μｍである。上記厚みが２μｍ未満であると、異物の混入によって平滑なフィルムが得られないことがある。上記厚みが５００μｍを超えると、得られる半導体チップ接合用接着フィルム中に溶剤が残留しやすく、圧接合時及び硬化時に気泡が発生することがある。 The adhesive film for joining semiconductor chips comprising the adhesive material for joining semiconductor chips of the present invention is also one aspect of the present invention.
The thickness of the adhesive film for bonding a semiconductor chip of the present invention is not particularly limited, but a preferable lower limit is 2 μm and a preferable upper limit is 500 μm. If the thickness is less than 2 μm, a smooth film may not be obtained due to the inclusion of foreign matter. When the thickness exceeds 500 μm, the solvent tends to remain in the obtained adhesive film for semiconductor chip bonding, and bubbles may be generated during pressure bonding and curing.
本発明の半導体チップ接合用接着フィルムを製造する方法は特に限定されず、例えば、上記エポキシ化合物、上記反応可能な官能基を有する高分子化合物、上記硬化剤、上記無機充填材、溶剤等を所定量配合して混合し、接着剤溶液を調製した後、フィルム化する方法等が挙げられる。
上記混合する方法は特に限定されず、例えば、ホモディスパー、万能ミキサー、バンバリーミキサー、ニーダー等を用いて混合する方法等が挙げられる。上記フィルム化する方法は特に限定されず、例えば、溶剤としてメチルエチルケトン等の低沸点溶剤を用いて、ダイコーター、バーコーター、グラビアコーター、スリットコーター等を使用して上記接着剤溶液をセパレーター上に塗工した後、加熱等により溶剤を乾燥する方法等が挙げられる。 The method for producing the adhesive film for semiconductor chip bonding of the present invention is not particularly limited. For example, the epoxy compound, the polymer compound having a reactive functional group, the curing agent, the inorganic filler, the solvent, etc. A method of forming a film after preparing an adhesive solution by quantitatively blending and mixing is mentioned.
The method of mixing is not particularly limited, and examples thereof include a method of mixing using a homodisper, a universal mixer, a Banbury mixer, a kneader, and the like. The method for forming the film is not particularly limited. For example, using a low boiling point solvent such as methyl ethyl ketone as a solvent, the adhesive solution is applied onto the separator using a die coater, bar coater, gravure coater, slit coater, or the like. Examples of the method include drying the solvent by heating and the like after the processing.
本発明の半導体チップ接合用接着フィルムの用途は特に限定されず、例えば、ウエハ又は半導体チップを、他のウエハ、他の半導体チップ又は基板に実装する際に用いられる。なかでも、本発明の半導体チップ接合用接着フィルムはフリップチップ実装に用いられることが好ましく、電極接合後にアンダーフィルを充填するフリップチップ実装よりも、ウエハ、半導体チップ又は基板に接着剤層を予め搭載するフリップチップ実装に用いられることがより好ましい。 The use of the adhesive film for bonding a semiconductor chip of the present invention is not particularly limited. For example, it is used when a wafer or a semiconductor chip is mounted on another wafer, another semiconductor chip or a substrate. Among them, the adhesive film for bonding a semiconductor chip of the present invention is preferably used for flip chip mounting, and an adhesive layer is previously mounted on a wafer, a semiconductor chip or a substrate rather than flip chip mounting in which an underfill is filled after electrode bonding. More preferably, it is used for flip chip mounting.
本発明の半導体チップ接合用接着フィルムは、フィレット形状を、凸形状にならないように制御することができることから、本発明の半導体チップ接合用接着フィルムを用いることで、信頼性の高い半導体装置を製造することができる。
本発明の半導体チップ接合用接着フィルムを用いた半導体装置の製造方法は特に限定されず、例えば、本発明の半導体チップ接合用接着フィルムをラミネートによってウエハ又は半導体チップに供給する方法、本発明の半導体チップ接合用接着フィルムを半導体チップのチップサイズに合わせて裁断し、他の半導体チップ又は基板に供給する方法等が挙げられる。このような半導体装置の製造方法もまた、本発明の１つである。 Since the adhesive film for bonding a semiconductor chip of the present invention can control the fillet shape so that it does not become a convex shape, a highly reliable semiconductor device is manufactured by using the adhesive film for bonding a semiconductor chip of the present invention. can do.
The manufacturing method of the semiconductor device using the adhesive film for semiconductor chip bonding of the present invention is not particularly limited. For example, the method for supplying the adhesive film for semiconductor chip bonding of the present invention to a wafer or a semiconductor chip by laminating, the semiconductor of the present invention A method of cutting an adhesive film for chip bonding in accordance with the chip size of the semiconductor chip and supplying it to another semiconductor chip or substrate can be mentioned. Such a method of manufacturing a semiconductor device is also one aspect of the present invention.
本発明の半導体装置の製造方法により得られる半導体装置であって、半導体チップと、他の半導体チップ又は基板とが接着剤層を介してボンディングされており、前記半導体チップの側壁に這い上がるフィレットが形成されており、前記半導体チップの側壁と前記フィレットとが成す角度が７０°未満である半導体装置もまた、本発明の１つである。
上記半導体チップの側壁と上記フィレットとが成す角度が７０°以上であると、凸部に応力が集中して、半導体装置の信頼性が低下する。 A semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention, wherein a semiconductor chip and another semiconductor chip or a substrate are bonded via an adhesive layer, and a fillet that rises up to a side wall of the semiconductor chip. A semiconductor device which is formed and an angle formed between the side wall of the semiconductor chip and the fillet is less than 70 ° is also one aspect of the present invention.
When the angle formed between the side wall of the semiconductor chip and the fillet is 70 ° or more, stress concentrates on the convex portion and the reliability of the semiconductor device is lowered.
本発明によれば、フィレット形状を、凸形状にならないように制御し、信頼性の高い半導体装置を製造することのできる半導体チップ接合用接着材料を提供することができる。また、本発明によれば、該半導体チップ接合用接着材料からなる半導体チップ接合用接着フィルム、該半導体チップ接合用接着材料又は該半導体チップ接合用接着フィルムを用いた半導体装置の製造方法、及び、該半導体装置の製造方法により得られる半導体装置を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the adhesive material for semiconductor chip joining which can control a fillet shape so that it may not become convex shape, and can manufacture a highly reliable semiconductor device can be provided. Further, according to the present invention, a semiconductor chip bonding adhesive film made of the semiconductor chip bonding adhesive material, a method of manufacturing a semiconductor device using the semiconductor chip bonding adhesive material or the semiconductor chip bonding adhesive film, and A semiconductor device obtained by the method for manufacturing the semiconductor device can be provided.
本発明の半導体チップ接合用接着材料を用いて基板上に半導体チップをボンディングし、非凸形状のフィレットを形成した状態の一例を示す断面図である。It is sectional drawing which shows an example of the state which bonded the semiconductor chip on the board | substrate using the adhesive material for semiconductor chip bonding of this invention, and formed the non-convex-shaped fillet. 従来の半導体チップ接合用接着材料を用いて基板上に半導体チップをボンディングし、凸形状のフィレットを形成した状態の一例を示す断面図である。It is sectional drawing which shows an example of the state which bonded the semiconductor chip on the board | substrate using the conventional adhesive material for semiconductor chip bonding, and formed the convex-shaped fillet. 本発明の半導体チップ接合用接着材料を用いて基板上に半導体チップをボンディングし、半導体チップの側壁とフィレットとが成す角度θが７０°未満のフィレットを形成した状態の一例を示す断面図である。It is sectional drawing which shows an example of the state which bonded the semiconductor chip on the board | substrate using the adhesive material for semiconductor chip bonding of this invention, and formed the fillet whose angle (theta) which the side wall and fillet of a semiconductor chip comprise is less than 70 degrees. .
以下に実施例を掲げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 The embodiments of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
（実施例１～３１及び比較例１～１８）
表１～５の組成に従って、ホモディスパーを用いて下記に示す各材料を攪拌混合し、接着剤溶液を調製した。アプリケーターによって接着剤溶液を離型処理されたペットフィルム上に塗工し、溶剤を乾燥して１００μｍ厚の半導体チップ接合用接着フィルムを得た。 (Examples 1 to 31 and Comparative Examples 1 to 18)
According to the compositions shown in Tables 1 to 5, the following materials were stirred and mixed using a homodisper to prepare an adhesive solution. The adhesive solution was applied onto a release-treated PET film by an applicator, and the solvent was dried to obtain a 100 μm-thick adhesive film for bonding a semiconductor chip.
（１）エポキシ化合物
・ビフェニル型エポキシ樹脂（商品名「ＹＸ－４０００」、ジャパンエポキシレジン社製）
・ビスフェノールＡ型エポキシ樹脂（商品名「１００４ＡＦ」、ジャパンエポキシレジン社製）
・ジシクロペンタジエン型エポキシ樹脂（商品名「ＨＰ－７２００ＨＨ」、ＤＩＣ社製）
・ジシクロペンタジエン型エポキシ樹脂（商品名「ＥＰ－４０８８Ｓ」、アデカ社製） (1) Epoxy compound / biphenyl type epoxy resin (trade name “YX-4000”, manufactured by Japan Epoxy Resin Co., Ltd.)
・ Bisphenol A type epoxy resin (trade name “1004AF”, manufactured by Japan Epoxy Resin Co., Ltd.)
・ Dicyclopentadiene type epoxy resin (trade name “HP-7200HH”, manufactured by DIC Corporation)
・ Dicyclopentadiene type epoxy resin (trade name “EP-4088S”, manufactured by ADEKA)
（２）反応可能な官能基を有する高分子化合物
・グリシジル基含有アクリル樹脂（重量平均分子量２０万、商品名「Ｇ－２０５０Ｍ」、日油社製）、
・グリシジル基含有アクリル樹脂（重量平均分子量２万、商品名「Ｇ－０２５０ＳＰ」、日油社製）
・グリシジル基含有アクリル樹脂（重量平均分子量８千、商品名「Ｇ－０１３０Ｓ」、日油社製）
・グリシジル基含有アクリル化合物（重量平均分子量１０万、商品名「Ｇ－１０１０Ｓ」、日油社製） (2) Polymer compound having a functional group capable of reacting, glycidyl group-containing acrylic resin (weight average molecular weight 200,000, trade name “G-2050M”, manufactured by NOF Corporation),
・ Glycidyl group-containing acrylic resin (weight average molecular weight 20,000, trade name “G-0250SP”, manufactured by NOF Corporation)
・ Glycidyl group-containing acrylic resin (weight average molecular weight 8,000, trade name “G-0130S”, manufactured by NOF Corporation)
・ Glycidyl group-containing acrylic compound (weight average molecular weight 100,000, trade name “G-1010S”, manufactured by NOF Corporation)
（３）硬化剤
・トリアルキルテトラヒドロ無水フタル酸（商品名「ＹＨ－３０６」、ＪＥＲ社製） (3) Curing agent: Trialkyltetrahydrophthalic anhydride (trade name “YH-306”, manufactured by JER)
（４）硬化促進剤
・２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン　イソシアヌル酸付加塩（商品名「２ＭＡ－ＯＫ」、四国化成工業社製） (4) Curing accelerator: 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid addition salt (trade name “2MA-OK”, Shikoku Kasei Kogyo Co., Ltd. Made)
（５）無機充填材
・表面フェニル処理無機フィラー（シリカ）（商品名「ＳＥ－１０５０－ＳＰＴ」、アドマテックス社製、平均粒子径３００ｎｍ）
・表面フェニル処理無機フィラー（シリカ）（商品名「ＳＥ－２０５０－ＳＰＪ」、アドマテックス社製、平均粒子径５００ｎｍ）
・表面フェニル処理無機フィラー（シリカ）（商品名「ＳＳ－０１」、トクヤマ社製、平均粒子径１００ｎｍ）
・表面フェニル処理無機フィラー（シリカ）（商品名「ＹＡ０５０－ＭＪＦ」、アドマテックス社製、平均粒子径５０ｎｍ）
・表面無処理無機フィラー（シリカ）（商品名「ＳＥ－１０５０」、アドマテックス社製、平均粒子径３００ｎｍ）
・表面無処理無機フィラー（シリカ）（商品名「ＳＥ－２０５０」、アドマテックス社製、平均粒子径５００ｎｍ）
・表面無処理無機フィラー（シリカ）（商品名「ＱＳ－４０」、トクヤマ社製、平均粒子径７ｎｍ）
・表面にＣＨ３－Ｓｉ－Ｏ－基を有するシリカ粒子（商品名「ＭＴ－１０」、トクヤマ社製、平均粒子径１５ｎｍ）
・表面にＣＨ３－Ｓｉ－Ｏ－基を有するシリカ粒子（商品名「ＳＥ－２０５０－ＳＴＪ」、アドマテックス社製、平均粒子径５００ｎｍ）
・表面にＣＨ３－Ｓｉ－Ｏ－基を有するシリカ粒子（商品名「ＳＥ－１０５０－ＳＴＴ」、アドマテックス社製、平均粒子径３００ｎｍ）
・表面ヘキサメチルジシラザン処理無機フィラー（シリカ）（商品名「ＨＭ－２０Ｌ」、トクヤマ社製、平均粒子径１２ｎｍ）
・表面シリコーンオイル処理無機フィラー（シリカ）（商品名「ＰＭ－２０Ｌ」、トクヤマ社製、平均粒子径１２ｎｍ）
・表面エポキシシラン処理無機フィラー（シリカ）（商品名「ＳＥ－１０５０－ＳＥＴ」、アドマテックス社製、平均粒子径３００ｎｍ）
・表面メタクリル処理無機フィラー（シリカ）（商品名「ＳＥ－１０５０－ＳＭＴ」、アドマテックス社製、平均粒子径３００ｎｍ） (5) Inorganic filler / surface phenyl-treated inorganic filler (silica) (trade name “SE-1050-SPT”, manufactured by Admatechs, average particle diameter of 300 nm)
・ Surface phenyl-treated inorganic filler (silica) (trade name “SE-2050-SPJ”, manufactured by Admatechs, average particle size 500 nm)
・ Surface phenyl-treated inorganic filler (silica) (trade name “SS-01”, manufactured by Tokuyama Corporation, average particle size 100 nm)
・ Surface phenyl-treated inorganic filler (silica) (trade name “YA050-MJF”, manufactured by Admatechs, average particle size 50 nm)
Surface-untreated inorganic filler (silica) (trade name “SE-1050”, manufactured by Admatechs, average particle size 300 nm)
Surface-untreated inorganic filler (silica) (trade name “SE-2050”, manufactured by Admatechs, average particle diameter of 500 nm)
・ Untreated surface inorganic filler (silica) (trade name “QS-40”, manufactured by Tokuyama Corporation, average particle size 7 nm)
Silica particles having a CH 3 —Si—O— group on the surface (trade name “MT-10”, manufactured by Tokuyama, average particle diameter of 15 nm)
Silica particles having a CH 3 —Si—O— group on the surface (trade name “SE-2050-STJ”, manufactured by Admatechs, average particle diameter of 500 nm)
Silica particles having CH 3 —Si—O— groups on the surface (trade name “SE-1050-STT”, manufactured by Admatechs, average particle diameter of 300 nm)
・ Surface hexamethyldisilazane-treated inorganic filler (silica) (trade name “HM-20L”, manufactured by Tokuyama Corporation, average particle size 12 nm)
・ Surface silicone oil-treated inorganic filler (silica) (trade name “PM-20L”, manufactured by Tokuyama Corporation, average particle size 12 nm)
・ Surface epoxy silane-treated inorganic filler (silica) (trade name “SE-1050-SET”, manufactured by Admatechs, average particle size 300 nm)
・ Surface methacrylic treated inorganic filler (silica) (trade name “SE-1050-SMT”, manufactured by Admatechs, average particle size 300 nm)
（６）その他
シランカップリング剤（商品名「ＫＢＭ－５７３」、信越化学工業社製）
溶剤　メチルエチルケトン（ＭＥＫ、和光純薬工業社製） (6) Other silane coupling agents (trade name “KBM-573”, manufactured by Shin-Etsu Chemical Co., Ltd.)
Solvent Methyl ethyl ketone (MEK, Wako Pure Chemical Industries, Ltd.)
＜評価＞
実施例及び比較例で得られた半導体チップ接合用接着フィルムについて、以下の評価を行った。結果を表１～５に示す。 <Evaluation>
The following evaluation was performed about the adhesive film for semiconductor chip bonding obtained by the Example and the comparative example. The results are shown in Tables 1-5.
（１）２５℃せん断弾性率Ｇｒの測定
得られた半導体チップ接合用接着フィルムについて、動的粘弾性測定装置（ＤＶＡ－２００、アイティー計測器社製）を用いて、厚み６００μｍ、幅６ｍｍ、長さ１０ｍｍの半導体チップ接合用接着剤フィルムについて、－２０℃から８０℃までせん断測定することにより、２５℃せん断弾性率Ｇｒ（ＭＰａ）を求めた。 (1) Measurement of 25 ° C. shear modulus Gr With respect to the obtained adhesive film for bonding a semiconductor chip, using a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Meter Co., Ltd.), a thickness of 600 μm, a width of 6 mm, With respect to the adhesive film for bonding a semiconductor chip having a length of 10 mm, a shear elastic modulus Gr (MPa) at 25 ° C. was obtained by measuring the shear from −20 ° C. to 80 ° C.
（２）ハンダ融点までの最低複素粘度η＊ｍｉｎの測定
得られた半導体チップ接合用接着フィルムについて、レオメーター（ＳＴＲＥＳＳＴＥＣＨ、ＲＥＯＬＯＧＩＣＡ社製）を用いて、サンプル厚み６００μｍ、歪制御（１ｒａｄ）、周波数１０Ｈｚ、昇温速度２０℃／ｍｉｎ、測定温度範囲６０℃から３００℃まで測定を行い、測定中に最も複素粘度が低下した値をハンダ融点までの最低複素粘度η＊ｍｉｎ（Ｐａ・ｓ）とした。 (2) Measurement of minimum complex viscosity η * min up to solder melting point About the obtained adhesive film for joining semiconductor chips, using a rheometer (STRESSTECH, manufactured by REOLOGICA), sample thickness 600 μm, strain control (1 rad), frequency 10 Hz, temperature increase rate 20 ° C./min, measurement temperature range 60 ° C. to 300 ° C. The value of the lowest complex viscosity during the measurement is the lowest complex viscosity η * min (Pa · s) up to the solder melting point. did.
（３）｛複素粘度η＊（１Ｈｚ）｝／｛複素粘度η＊（１０Ｈｚ）｝の測定
得られた半導体チップ接合用接着フィルムについて、ＳＴＲＥＳＳＴＥＣＨ（ＲＥＯＬＯＧＩＣＡ社製）を用いて、サンプル厚み６００μｍ、歪制御（１ｒａｄ）、周波数１Ｈｚ又は１０Ｈｚ、温度１４０℃で測定を行うことにより、｛複素粘度η＊（１Ｈｚ）｝／｛複素粘度η＊（１０Ｈｚ）｝の値を求めた。 (3) Measurement of {complex viscosity η * (1 Hz)} / {complex viscosity η * (10 Hz)} With respect to the obtained adhesive film for joining semiconductor chips, a sample thickness of 600 μm, strain was measured using STRESSTECH (manufactured by REOLOGICA). The value of {complex viscosity η * (1 Hz)} / {complex viscosity η * (10 Hz)} was determined by measurement at control (1 rad), frequency 1 Hz or 10 Hz, and temperature 140 ° C.
（４）フィレットの断面形状
得られた半導体チップ接合用接着フィルムを、ハンダボール（高さ８５μｍ）が１５０μｍ間隔でチップ全面に３１３６個形成されたフルアレイのＴＥＧチップ（１０ｍｍ×１０ｍｍ×厚み７２５μｍ）にラミネートした後、チップサイズに合わせて半導体チップ接合用接着フィルムを裁断し、樹脂付ＴＥＧチップを得た。次いで、得られた樹脂付ＴＥＧチップのハンダとデイジーチェーンとなるように配線されたハンダプリコート付ガラスエポキシＴＥＧ基板に、ステージ温度１２０℃、ヘッド温度１４０℃２０秒、２８０℃５秒、ヘッド圧１００Ｎで樹脂付ＴＥＧチップをフリップチップボンディングした。その後、１９０℃３０分でポストキュア（後硬化）を行い、積層体を得た。
得られた積層体を冷間樹脂で埋め込んだ後、チップ辺の中央付近の部分まで断面研磨を行い、ＴＥＧチップの側壁とフィレットとが成す角度（フィレット角度）を測定した。 (4) Fillet cross-sectional shape The obtained adhesive film for bonding a semiconductor chip to a full-array TEG chip (10 mm × 10 mm × thickness 725 μm) in which 3136 solder balls (height 85 μm) are formed on the entire surface of the chip at intervals of 150 μm. After laminating, the semiconductor chip bonding adhesive film was cut according to the chip size to obtain a TEG chip with resin. Next, a solder pre-coated glass epoxy TEG substrate wired so as to form a daisy chain with solder of the obtained resin-attached TEG chip, a stage temperature of 120 ° C., a head temperature of 140 ° C. for 20 seconds, 280 ° C. for 5 seconds, a head pressure of 100 N The TEG chip with resin was flip chip bonded. Thereafter, post-curing (post-curing) was performed at 190 ° C. for 30 minutes to obtain a laminate.
After embedding the obtained laminate with a cold resin, cross-section polishing was performed up to a portion near the center of the chip side, and an angle (fillet angle) formed between the side wall of the TEG chip and the fillet was measured.
（５）リフロー試験
上記（４）にて得られた積層体について、あらかじめ導通抵抗値（以下、初期抵抗とする）を測定しておき、６０℃、６０％ＲＨで４０時間吸湿させ、ピーク温度２６０℃のリフローオーブンに３回通してリフロー試験を行った後、再び導通抵抗値を測定した。リフロー試験後の導通抵抗値が初期抵抗値から１０％以上変化した場合を不良とし、８つの積層体を作製して不良個数を評価した。 (5) Reflow test For the laminate obtained in the above (4), the conduction resistance value (hereinafter referred to as initial resistance) is measured in advance, and moisture absorption is performed at 60 ° C. and 60% RH for 40 hours. After conducting a reflow test by passing through a reflow oven at 260 ° C. three times, the conduction resistance value was measured again. A case where the conduction resistance value after the reflow test was changed by 10% or more from the initial resistance value was regarded as defective, and eight laminates were produced and the number of defects was evaluated.
（６）冷熱サイクル試験１
上記（５）にてリフロー試験を行った積層体について、－５５～１２５℃（３０分／１サイクル）、１０００サイクルの冷熱サイクル試験を行った後、導通抵抗値を測定した。冷熱サイクル試験後の導通抵抗値が初期抵抗値から１０％以上変化した場合を不良とし、８つの積層体を作製して不良個数を評価した。
不良個数が０個であった場合を○、１個であった場合を△、２個以上であった場合を×とした。 (6) Thermal cycle test 1
The laminate subjected to the reflow test in (5) above was subjected to 1000 cycles of a thermal cycle test at −55 to 125 ° C. (30 minutes / 1 cycle), and then the conduction resistance value was measured. The case where the conduction resistance value after the thermal cycle test was changed by 10% or more from the initial resistance value was regarded as defective, and eight laminates were produced and the number of defects was evaluated.
The case where the number of defects was 0 was marked as ◯, the case where it was 1 as Δ, and the case where it was 2 or more as x.
（７）冷熱サイクル試験２
上記（５）にてリフロー試験を行った積層体について、－５５～１２５℃（３０分／１サイクル）、３０００サイクルの冷熱サイクル試験を行った後、導通抵抗値を測定した。冷熱サイクル試験後の導通抵抗値が初期抵抗値から１０％以上変化した場合を不良とし、８つの積層体を作製して不良個数を評価した。
不良個数が２個以下であった場合を◎、３～４個であった場合を○、５～６個であった場合を△、７個以上であった場合を×とした。 (7) Thermal cycle test 2
The laminate subjected to the reflow test in (5) above was subjected to a thermal cycle test of −55 to 125 ° C. (30 minutes / 1 cycle) and 3000 cycles, and then the conduction resistance value was measured. The case where the conduction resistance value after the thermal cycle test was changed by 10% or more from the initial resistance value was regarded as defective, and eight laminates were produced and the number of defects was evaluated.
When the number of defects was 2 or less, ◎, when 3-4, ◯, when 5-6, Δ, when 7 or more, x.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
本発明によれば、フィレット形状を、凸形状にならないように制御し、信頼性の高い半導体装置を製造することのできる半導体チップ接合用接着材料を提供することができる。また、本発明によれば、該半導体チップ接合用接着材料からなる半導体チップ接合用接着フィルム、該半導体チップ接合用接着材料又は該半導体チップ接合用接着フィルムを用いた半導体装置の製造方法、及び、該半導体装置の製造方法により得られる半導体装置を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the adhesive material for semiconductor chip joining which can control a fillet shape so that it may not become convex shape, and can manufacture a highly reliable semiconductor device can be provided. Further, according to the present invention, a semiconductor chip bonding adhesive film made of the semiconductor chip bonding adhesive material, a method of manufacturing a semiconductor device using the semiconductor chip bonding adhesive material or the semiconductor chip bonding adhesive film, and A semiconductor device obtained by the method for manufacturing the semiconductor device can be provided.
１　基板
２　半導体チップ
３　半導体チップ接合用接着材料
４　バンプ 1 Substrate 2 Semiconductor chip 3 Adhesive material for bonding semiconductor chip 4 Bump

Claims (9)

  1. 粘弾性測定装置で測定した２５℃せん断弾性率Ｇｒが１×１０６Ｐａ以上、レオメーターで測定したハンダ融点までの最低複素粘度η＊ｍｉｎが５×１０１Ｐａ・ｓ以下であり、温度１４０℃、歪量１ｒａｄ、周波数１Ｈｚで測定した複素粘度η＊（１Ｈｚ）が温度１４０℃、歪量１ｒａｄ、周波数１０Ｈｚで測定した複素粘度η＊（１０Ｈｚ）の０．５～４．５倍であることを特徴とする半導体チップ接合用接着材料。 The 25 ° C. shear modulus Gr measured with a viscoelasticity measuring device is 1 × 10 6 Pa or more, the lowest complex viscosity η * min to the solder melting point measured with a rheometer is 5 × 10 1 Pa · s or less, and the temperature is 140 The complex viscosity η * (1 Hz) measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 1 Hz is 0.5 to 4.5 times the complex viscosity η * (10 Hz) measured at a temperature of 140 ° C., a strain amount of 1 rad, and a frequency of 10 Hz. An adhesive material for bonding a semiconductor chip.
  2. エポキシ化合物、及び、前記エポキシ化合物と反応可能な官能基を有する高分子化合物を含有し、前記エポキシ化合物と反応可能な官能基を有する高分子化合物の重量平均分子量が５万以下であることを特徴とする請求項１記載の半導体チップ接合用接着材料。 An epoxy compound and a polymer compound having a functional group capable of reacting with the epoxy compound are contained, and the polymer compound having a functional group capable of reacting with the epoxy compound has a weight average molecular weight of 50,000 or less. The adhesive material for bonding a semiconductor chip according to claim 1.
  3. ウエハ、半導体チップ又は基板に接着剤層を予め搭載するフリップチップ実装に用いられることを特徴とする請求項１又は２記載の半導体チップ接合用接着材料。 3. The adhesive material for bonding a semiconductor chip according to claim 1, wherein the adhesive material is used for flip chip mounting in which an adhesive layer is previously mounted on a wafer, a semiconductor chip or a substrate.
  4. 請求項１、２又は３記載の半導体チップ接合用接着材料を用いた半導体装置の製造方法であって、
    請求項１、２又は３記載の半導体チップ接合用接着材料に溶剤を添加して調製した接着剤溶液をウエハに塗布し、前記溶剤を乾燥してフィルム化する
    ことを特徴とする半導体装置の製造方法。     A method of manufacturing a semiconductor device using the adhesive material for bonding a semiconductor chip according to claim 1, 2, or 3,
    An adhesive solution prepared by adding a solvent to the semiconductor chip bonding adhesive material according to claim 1, 2 or 3 is applied to a wafer, and the solvent is dried to form a film. Method.
  5. 請求項１、２又は３記載の半導体チップ接合用接着材料に溶剤を添加して調製した接着剤溶液をスピンコート又はスクリーン印刷によってウエハに塗布することを特徴とする請求項４記載の半導体装置の製造方法。 5. The semiconductor device according to claim 4, wherein an adhesive solution prepared by adding a solvent to the adhesive material for bonding semiconductor chips according to claim 1, is applied to a wafer by spin coating or screen printing. Production method.
  6. 請求項１、２又は３記載の半導体チップ接合用接着材料からなることを特徴とする半導体チップ接合用接着フィルム。 An adhesive film for bonding a semiconductor chip, comprising the adhesive material for bonding a semiconductor chip according to claim 1, 2 or 3.
  7. 請求項６記載の半導体チップ接合用接着フィルムを用いた半導体装置の製造方法であって、
    請求項６記載の半導体チップ接合用接着フィルムをラミネートによってウエハ又は半導体チップに供給する
    ことを特徴とする半導体装置の製造方法。     A method of manufacturing a semiconductor device using the adhesive film for bonding a semiconductor chip according to claim 6,
    A method of manufacturing a semiconductor device, comprising supplying the adhesive film for bonding a semiconductor chip according to claim 6 to a wafer or a semiconductor chip by laminating.
  8. 請求項６記載の半導体チップ接合用接着フィルムを用いた半導体装置の製造方法であって、
    請求項６記載の半導体チップ接合用接着フィルムを半導体チップのチップサイズに合わせて裁断し、他の半導体チップ又は基板に供給する
    ことを特徴とする半導体装置の製造方法。     A method of manufacturing a semiconductor device using the adhesive film for bonding a semiconductor chip according to claim 6,
    A method for manufacturing a semiconductor device, comprising cutting the semiconductor chip bonding adhesive film according to claim 6 in accordance with a chip size of the semiconductor chip and supplying the cut film to another semiconductor chip or a substrate.
  9. 請求項４、５、７又は８記載の半導体装置の製造方法により得られる半導体装置であって、
    半導体チップと、他の半導体チップ又は基板とが接着剤層を介してボンディングされており、
    前記半導体チップの側壁に這い上がるフィレットが形成されており、
    前記半導体チップの側壁と前記フィレットとが成す角度が７０°未満である
    ことを特徴とする半導体装置。     A semiconductor device obtained by the method for manufacturing a semiconductor device according to claim 4,
    The semiconductor chip and another semiconductor chip or substrate are bonded via an adhesive layer,
    A fillet that rises on the side wall of the semiconductor chip is formed,
    An angle formed between a side wall of the semiconductor chip and the fillet is less than 70 °.
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WO2014046128A1 (en) * 2012-09-24 2014-03-27 積水化学工業株式会社 Adhesive for electronic components and method for producing semiconductor chip mounter
JPWO2013133240A1 (en) * 2012-03-07 2015-07-30 住友電気工業株式会社 PRINTING ADHESIVE AND METHOD FOR PRODUCING CONNECTED BODY USING THE SAME
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CN102834907B (en) 2016-03-16
JP2012089877A (en) 2012-05-10
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JP4922474B2 (en) 2012-04-25
KR20130064043A (en) 2013-06-17

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