WO2014083872A1 - チップ用樹脂膜形成用シート及び半導体装置の製造方法 - Google Patents
チップ用樹脂膜形成用シート及び半導体装置の製造方法 Download PDFInfo
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- WO2014083872A1 WO2014083872A1 PCT/JP2013/066471 JP2013066471W WO2014083872A1 WO 2014083872 A1 WO2014083872 A1 WO 2014083872A1 JP 2013066471 W JP2013066471 W JP 2013066471W WO 2014083872 A1 WO2014083872 A1 WO 2014083872A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- 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
- H01L23/295—Organic, e.g. plastic containing a filler
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- 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
- H01L23/296—Organo-silicon compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention provides a resin film forming sheet for a chip that can efficiently form a resin film having high adhesive strength and thermal conductivity on any surface of a semiconductor chip and can manufacture a highly reliable semiconductor device. About.
- chip a semiconductor chip having electrodes such as bumps on a circuit surface
- the electrodes are bonded to a substrate.
- the surface (chip back surface) opposite to the circuit surface of the chip may be exposed.
- the exposed chip back surface may be protected by an organic film.
- a chip having a protective film made of an organic film is obtained by applying a liquid resin to the back surface of a wafer by spin coating, drying and curing, and cutting the protective film together with the wafer.
- the thickness accuracy of the protective film formed in this way is not sufficient, the product yield may be lowered.
- a protective film-forming sheet for chips having a support sheet and a protective film-forming layer formed on the support sheet and comprising a heat or energy ray-curable component and a binder polymer component is disclosed.
- Patent Document 1 a protective film-forming sheet for chips having a support sheet and a protective film-forming layer formed on the support sheet and comprising a heat or energy ray-curable component and a binder polymer component is disclosed.
- a semiconductor wafer manufactured in a large diameter state may be cut and separated (diced) into element pieces (semiconductor chips) and then transferred to the next bonding process.
- the semiconductor wafer is subjected to dicing, cleaning, drying, expanding, and pick-up processes in a state of being adhered to the adhesive sheet in advance, and then transferred to the next bonding process.
- Patent Document 2 various dicing / die bonding adhesive sheets having both a wafer fixing function and a die bonding function have been proposed in order to simplify the pickup process and the bonding process (for example, Patent Document 2). reference).
- the adhesive sheet disclosed in Patent Document 2 enables so-called direct die bonding, and the application process of the die bonding adhesive can be omitted.
- the adhesive sheet it is possible to obtain a semiconductor chip having an adhesive layer attached to the back surface, and direct die bonding such as between an organic substrate and a chip, between a lead frame and a chip, and between a chip and a chip is possible. It becomes.
- Such an adhesive sheet achieves a wafer fixing function and a die bonding function by imparting fluidity to the adhesive layer, and heat or energy ray curing formed on the support sheet and the support sheet. It has an adhesive layer composed of an adhesive component and a binder polymer component.
- an adhesive layer is applied to the bump formation surface, that is, the surface of the chip, Die bonding will be performed.
- Patent Document 3 discloses a heat conductive adhesive film in which a magnetic field is applied to a film composition containing boron nitride powder and the boron nitride powder in the composition is oriented and solidified in a certain direction.
- the heat conductive adhesive film formed using the film composition of patent document 3 has the process of applying a magnetic field in a manufacturing process as mentioned above, and the manufacturing process is complicated.
- the resin film forming composition is thickened due to the small particle diameter.
- the coating suitability of the resin film-forming composition is lowered, and it may be difficult to form a smooth resin film.
- the addition amount of boron nitride powder is reduced in order to avoid thickening of the resin film forming composition, the high thermal conductivity of the resin film cannot be obtained.
- Patent Document 4 describes that a compound obtained by adding and condensing a silane coupling agent to a polysiloxane oligomer is added to a resin composition in order to improve adhesiveness.
- An object of the present invention is to provide a sheet capable of imparting heat dissipation characteristics to the obtained semiconductor device and having excellent adhesion.
- the present inventors have added a specific inorganic filler and a silane coupling agent to a resin film forming layer formed on any surface of a semiconductor chip.
- the inventors have conceived that adhesiveness to an adherend (semiconductor wafer, semiconductor chip, etc.) and heat dissipation characteristics of a semiconductor device can be improved, and the present invention has been completed.
- the present invention includes the following gist. [1] having a support sheet and a resin film forming layer formed on the support sheet;
- the resin film-forming layer contains a binder polymer component (A), a curable component (B), an inorganic filler (C), and a silane coupling agent (D),
- the inorganic filler (C) contains nitride particles (C1), A resin film-forming sheet for chips, wherein the silane coupling agent (D) has a molecular weight of 300 or more.
- the peeling strength and heat conduction can be achieved without applying any special treatment to the semiconductor wafer or chip by using the resin film forming sheet for chip according to the present invention.
- a resin film having an excellent rate can be formed, and the reliability of the obtained semiconductor device can be improved.
- the resin film forming sheet for chips according to the present invention includes a support sheet and a resin film forming layer formed on the support sheet.
- the resin film forming layer includes a binder polymer component (A), a curable component (B), an inorganic filler (C), and a silane coupling agent (D).
- Binder polymer component The binder polymer component (A) is used to impart sufficient adhesiveness (adhesiveness or transferability to a semiconductor wafer or the like) and film-forming property (sheet-forming property) to the resin film-forming layer.
- the binder polymer component (A) conventionally known acrylic polymers, polyester resins, urethane resins, acrylic urethane resins, phenoxy resins, silicone resins, rubber-based polymers, polystyrene, and the like can be used. The presence or absence of such a functional group does not matter.
- the weight average molecular weight (Mw) of the binder polymer component (A) is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. If the weight average molecular weight of the binder polymer component (A) is too low, the peeling force between the resin film-forming layer and the support sheet is increased, and a defect that the resin film-forming layer cannot be transferred may occur. On the other hand, if the weight average molecular weight of the binder polymer component (A) is too high, the adhesiveness of the resin film forming layer is lowered, and transfer to a chip or the like may not be possible, or the resin film may be peeled off from the chip or the like after transfer. Moreover, when the weight average molecular weight of a binder polymer component (A) is too low, the sheet
- the glass transition temperature (Tg) of the acrylic polymer is preferably in the range of ⁇ 60 to 50 ° C., more preferably ⁇ 50 to 40 ° C., and particularly preferably ⁇ 40 to 30 ° C. If the glass transition temperature of the acrylic polymer is too low, the peeling force between the resin film forming layer and the support sheet becomes large, and a defect that the resin film forming layer cannot be transferred may occur. In addition, if the glass transition temperature of the acrylic polymer is too high, the adhesiveness of the resin film forming layer is lowered, and transfer to a chip or the like may not be possible, or the resin film may be peeled off from the chip or the like after transfer. Further, when the glass transition temperature of the acrylic polymer is too low or too high, an appropriate film forming property cannot be obtained when the resin forming layer is produced, and sheet formation may not be possible.
- a (meth) acrylic acid ester monomer or its derivative (s) As a monomer which comprises the said acrylic polymer, a (meth) acrylic acid ester monomer or its derivative (s) is mentioned. Examples thereof include alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms, (meth) acrylates having a cyclic skeleton, (meth) acrylates having a hydroxyl group, and (meth) acrylates having an epoxy group.
- alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) ) Acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl ( Examples include meth) acrylate and octadecyl (meth) acrylate.
- the (meth) acrylate having a cyclic skeleton include cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. , Dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, and the like.
- the (meth) acrylate having a hydroxyl group examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. It is done.
- Specific examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate. In these, the acrylic polymer obtained by superposing
- an acrylic polymer when used, an acrylic polymer can be easily bridge
- the acrylic polymer may be copolymerized with acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, or the like.
- the mass ratio of the monomer having an epoxy group in the total mass of the monomers constituting the acrylic polymer is limited to be low. Is preferred. This tends to increase the adhesive strength between the resin film and the chip. The reason is presumed as follows. When the mass ratio of the monomer having an epoxy group is low in the total mass of monomers constituting the acrylic polymer, the compatibility between the epoxy resin and the acrylic polymer is lowered, and each of them is the main component in the resin film forming layer. A phase separation structure is formed.
- the compounding amount of the monomer having an epoxy group in the total mass of the monomer constituting the acrylic polymer is such that the monomer constituting the acrylic polymer does not include the monomer having an epoxy group or is in the total mass of the monomer constituting the acrylic polymer.
- the mass ratio of the monomer having an epoxy group is preferably more than 0% by mass and 10% by mass or less, and the monomer constituting the acrylic polymer does not include the monomer having the epoxy group, or the monomer constituting the acrylic polymer.
- the mass ratio of the monomer having an epoxy group exceeds 0 mass% and is 7 mass% or less in the total mass.
- a monomer which has an epoxy group the norbornene etc. which have an epoxy group other than (meth) acrylate which has epoxy groups, such as the above-mentioned glycidyl (meth) acrylate, are mentioned, for example.
- An acrylic polymer containing a monomer having an epoxy group as a monomer constituting the polymer is included in the concept of the epoxy resin described later in terms of words, but in the present invention, such an acrylic polymer is not included in the epoxy resin.
- thermosetting component in the curable component (B) when an epoxy compound that is a molecule other than the acrylic polymer and has two or more functions in the molecule is blended in the resin film forming layer, the acrylic polymer is used. The above-mentioned effect by using it will be acquired.
- the binder polymer component (A) may be a mixture of two or more polymers. At this time, the polymers having the same weight average molecular weight may be used, or a difference may be given. By mixing polymers having different weight average molecular weights, it is possible to facilitate delamination between the support sheet and the resin film-forming layer, and to suppress generation of voids during transfer. Furthermore, by selecting the glass transition temperature of the polymer to be mixed with the acrylic polymer, the transfer failure of the resin film forming layer due to the increase in the peeling force with the support sheet and the decrease in the adhesive force between the resin film forming layer and the chip are reduced. It can also be suppressed.
- binder polymer component (A) a polymer having an energy ray polymerizable group in the side chain (energy ray curable polymer) may be used.
- energy ray curable polymer has a function as a binder polymer component (A) and a function as a curable component (B) described later.
- an energy beam polymeric group what is necessary is just to have the same thing as the energy beam polymeric group which the energy beam polymeric compound mentioned later contains.
- a polymer having an energy ray polymerizable group in the side chain for example, a polymer having a reactive functional group X in the side chain, a low molecular weight having a functional group Y capable of reacting with the reactive functional group X and an energy ray polymerizable group
- Examples include polymers prepared by reacting compounds.
- the curable component (B) may be a thermosetting component and a thermosetting agent or an energy beam polymerizable compound. Moreover, you may use combining these.
- the thermosetting component for example, an epoxy resin is preferable.
- epoxy resin a conventionally known epoxy resin can be used.
- epoxy resins include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, and bisphenols.
- epoxy compounds having two or more functional groups in the molecule such as A-type epoxy resin, bisphenol F-type epoxy resin, and phenylene skeleton-type epoxy resin. These can be used individually by 1 type or in combination of 2 or more types.
- the thermosetting component in the resin film forming layer is preferably 1 with respect to 100 parts by mass of the binder polymer component (A). ⁇ 1500 parts by mass, more preferably 3 ⁇ 1200 parts by mass.
- the content of the thermosetting component is less than 1 part by mass, sufficient adhesiveness may not be obtained.
- the content exceeds 1500 parts by mass, the peeling force between the resin film-forming layer and the support sheet increases, and the resin film A transfer defect of the formation layer may occur.
- thermosetting agent functions as a curing agent for thermosetting components, particularly epoxy resins.
- a preferable thermosetting agent includes a compound having two or more functional groups capable of reacting with an epoxy group in one molecule.
- the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. Of these, phenolic hydroxyl groups, amino groups, acid anhydrides and the like are preferable, and phenolic hydroxyl groups and amino groups are more preferable.
- phenolic curing agent having a phenolic hydroxyl group examples include polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins, zyloc type phenolic resins, and aralkylphenolic resins.
- amine curing agent having an amino group is DICY (dicyandiamide). These can be used individually by 1 type or in mixture of 2 or more types.
- the content of the thermosetting agent is preferably 0.1 to 500 parts by mass and more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the thermosetting component.
- the content of the thermosetting agent is small, the adhesiveness may not be obtained due to insufficient curing, and when it is excessive, the moisture absorption rate of the resin film forming layer is increased and the reliability of the semiconductor device may be lowered.
- the energy beam polymerizable compound contains an energy beam polymerizable group and is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams.
- energy beam polymerizable compounds include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, or 1,4-butylene glycol.
- Examples include acrylate compounds such as diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, and itaconic acid oligomer.
- acrylate compounds such as diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, and itaconic acid oligomer.
- Such a compound has at least one polymerizable double bond in the molecule, and usually has a weight average molecular weight of about 100 to 30,000, preferably about 300 to 10,000.
- the energy ray polymerizable compound is preferably used in an amount of 1 to 1500 in the resin film forming layer with respect to 100 parts by mass of the binder polymer component (A).
- the inorganic filler (C) contains nitride particles (C1).
- nitride particles (C1) By blending the inorganic filler (C) containing the nitride particles (C1) into the resin film forming layer, the thermal conductivity of the resin film forming layer is improved, and the semiconductor chip to which the resin film forming layer is attached is mounted. It becomes possible to efficiently diffuse the heat generated by the semiconductor device.
- the coefficient of thermal expansion of the cured resin film can be adjusted, and the reliability of the semiconductor device can be improved using a semiconductor wafer, a semiconductor chip, a lead frame, an organic substrate, or the like as an adherend.
- the moisture absorption rate of the cured resin film can be reduced, the adhesiveness as the resin film can be maintained during heating, and the reliability of the semiconductor device can be improved. Furthermore, by applying laser marking to the resin film, the inorganic filler (C) is exposed at the portion scraped off by the laser beam, and the reflected light diffuses to exhibit a color close to white. Thereby, when the resin film forming layer contains a colorant (E) described later, there is an effect that a contrast difference is obtained between the laser marking portion and other portions, and the printing becomes clear.
- a colorant (E) described later there is an effect that a contrast difference is obtained between the laser marking portion and other portions, and the printing becomes clear.
- the inorganic filler (C) preferably contains particles other than the nitride particles (C1) (hereinafter sometimes referred to as “other particles (C2)”).
- the nitride particles (C1) improve the thermal conductivity of the resin film forming layer, but if the content ratio of the nitride particles (C1) in the resin film forming layer is too large, the adhesion of the resin film forming layer to the adherend May be reduced. Therefore, by using nitride particles (C1) and other particles (C2) in combination, sufficient thermal conductivity is imparted to the resin film forming layer while maintaining the adhesion of the resin film forming layer to the adherend. it can.
- nitride particles (C1) Nitride particles
- the nitride particles (C1) include particles of boron nitride, aluminum nitride, silicon nitride, and the like. Among these, boron nitride particles that can easily obtain a resin film-forming layer having high thermal conductivity are preferable.
- the nitride particles (C1) are preferably anisotropic shaped particles.
- the anisotropically shaped particles have anisotropy, and the specific shape thereof preferably has at least one shape selected from the group consisting of a plate shape, a needle shape and a scale shape.
- the anisotropically shaped particles exhibit high thermal conductivity in the major axis direction. Therefore, in the resin film forming layer, the ratio of the anisotropically shaped particles in which the major axis direction and the thickness direction of the resin film forming layer are substantially the same increases, so that the heat generated in the semiconductor chip causes the resin film forming layer to It becomes easy to diverge through.
- the major axis direction of the nitride particles (C1) and the thickness direction of the resin film forming layer are substantially the same” specifically means that the major axis direction of the nitride particles (C1) is resin.
- the angle formed by the thickness direction of the resin film forming layer and the major axis direction of the nitride particles (C1) is in the range of ⁇ 45 to 45 °.
- the average particle diameter of the nitride particles (C1) is preferably 20 ⁇ m or less, more preferably 5 to 20 ⁇ m, still more preferably 8 to 20 ⁇ m, and particularly preferably 10 to 15 ⁇ m. Moreover, it is preferable that the average particle diameter of nitride particle
- the average particle diameter of the nitride particles (C1) is the number average particle diameter calculated as an arithmetic average value by measuring the major axis diameter of 20 nitride particles (C1) randomly selected with an electron microscope. .
- the particle size distribution (CV value) of the nitride particles (C1) is preferably 5 to 40%, more preferably 10 to 30%. By setting the particle size distribution of the nitride particles (C1) within the above range, efficient and uniform thermal conductivity can be achieved.
- the CV value is an index of particle size variation, and the larger the CV value, the larger the particle size variation.
- the CV value is small, since the particle diameter is uniform, the amount of small-sized particles entering the gap between the particles is reduced, and it becomes difficult to pack the inorganic filler (C) more densely. A resin film forming layer having high thermal conductivity may be difficult to obtain.
- the particle diameter of the inorganic filler (C) may be larger than the thickness of the formed resin film forming layer, resulting in unevenness on the surface of the resin film forming layer.
- the adhesion of the film forming layer may be reduced.
- CV value is too large, it may become difficult to obtain the heat conductive composition which has uniform performance.
- the particle size distribution (CV value) of the nitride particles (C1) is observed with an electron microscope, the major axis diameter is measured for 200 particles, the standard deviation of the major axis diameter is obtained, and the above average particle diameter is determined. Can be obtained by calculating (standard deviation of major axis diameter) / (average particle diameter).
- the aspect ratio of the nitride particles (C1) is preferably 5 or more, more preferably 5 to 30, further preferably 8 to 20, and particularly preferably 10 to 15.
- the aspect ratio is expressed by (major axis number average diameter) / (minor axis number average diameter) of the nitride particles (C1).
- the short axis number average diameter and long axis number average diameter are calculated as the arithmetic average value of the short axis diameter and long axis diameter of 20 nitride particles (C1) randomly selected in a transmission electron micrograph.
- the major axis direction of the nitride particles (C1) and the direction parallel to the resin film forming layer are substantially the same due to the other particles (C2). This prevents the nitride particles (C1) from forming an efficient heat conduction path in the thickness direction of the resin film forming layer, thereby improving the heat conductivity.
- the density of the nitride particles (C1) is preferably 2 to 4 g / cm 3 , more preferably 2.2 to 3 g / cm 3 .
- the thermal conductivity in the major axis direction of the nitride particles (C1) is preferably 60 to 400 W / (m ⁇ K), and more preferably 100 to 300 W / (m ⁇ K).
- the formed heat conduction path has high heat conductivity, and as a result, a resin film forming layer having high heat conductivity can be obtained.
- the thermal conductivity in the major axis direction of the nitride particles (C1) can be measured by a periodic heating method.
- the other particles (C2) include silica particles and alumina particles, and alumina particles are particularly preferable. By using alumina particles, the thermal conductivity is not impaired even in portions other than the thermal conduction path formed by the nitride particles, and as a result, a resin film forming layer having a high thermal conductivity is obtained.
- the shape of the other particles (C2) is not particularly limited as long as the long axis direction of the nitride particles (C1) and the direction parallel to the resin film forming layer are prevented from being substantially the same.
- the typical shape is preferably spherical.
- the major axis direction of the nitride particles (C1) becomes substantially the same as the direction parallel to the resin film forming layer in the manufacturing process of the resin film forming layer.
- the ratio of the nitride particles (C1) in which the major axis direction and the thickness direction of the resin film forming layer are substantially the same can be increased.
- a resin film forming layer having excellent thermal conductivity in the thickness direction of the resin film forming layer is obtained. This is because the presence of other particles (C2) in the resin film forming layer causes the nitride particles (C1) to stand against the other particles (C2), resulting in the nitride particles (C1).
- the major axis direction and the thickness direction of the resin film forming layer are substantially the same.
- the major axis direction of the resin film is caused by stress or gravity applied to the nitride particles (C1) during the manufacturing process (for example, coating process) of the resin film forming layer.
- the ratio of the nitride particles (C1) that are substantially the same as the direction parallel to the formation layer is increased, and it may be difficult to obtain a resin film formation layer having excellent thermal conductivity.
- the average particle diameter of the other particles (C2) is preferably 20 ⁇ m or more, more preferably 20 to 50 ⁇ m, still more preferably 20 to 30 ⁇ m.
- the average particle diameter of the other particles (C2) is preferably 20 ⁇ m or more, more preferably 20 to 50 ⁇ m, still more preferably 20 to 30 ⁇ m.
- the thermal conductivity and film-forming property of the resin film forming layer are improved, and the filling rate of the other particles (C2) in the resin film forming layer is increased. Will improve.
- the nitride particles (C1) have a large specific surface area per unit volume and are likely to increase the viscosity of the resin film-forming composition.
- the average particle size of the other particles (C2) is the number average particle size calculated as the arithmetic average value of 20 major axis diameters of 20 other particles (C2) randomly selected with an electron microscope.
- the average particle diameter of the other particles (C2) is preferably 0.01 to 0.65 times the thickness of the resin film forming layer described later.
- the average particle diameter of the other particles (C2) is less than 0.01 times the thickness of the resin film-forming layer, nitride particles whose major axis direction is substantially the same as the direction parallel to the resin film-forming layer ( The ratio of C1) increases, it becomes difficult to form an efficient heat conduction path, and the heat conductivity of the resin film forming layer may be lowered.
- the average particle diameter of the other particles (C2) exceeds 0.65 times the thickness of the resin film forming layer, the surface of the resin film forming layer is uneven, and the adhesion of the resin film forming layer to the adherend is caused. May decrease. Moreover, it may be difficult to obtain a thermally conductive resin film forming composition having uniform performance.
- the particle size distribution (CV value) of the other particles (C2) is preferably 5 to 40%, more preferably 10 to 30%.
- the particle size distribution of the other particles (C2) is preferably 5 to 40%, more preferably 10 to 30%.
- the adhesion of the resin film forming layer to the adherend may be inferior. Moreover, when CV value is too large, it may become difficult to obtain the heat conductive composition which has uniform performance.
- the particle size distribution (CV value) of other particles (C2) was observed with an electron microscope, the major axis diameter was measured for 200 particles, the standard deviation of the major axis diameter was determined, and the average particle diameter described above was obtained. Can be obtained by calculating (standard deviation of major axis diameter) / (average particle diameter).
- the mass ratio of the inorganic filler (C) in the total mass of the resin film-forming layer is preferably 30 to 60% by mass, more preferably 40 to 60% by mass, based on the total solid content constituting the resin film-forming layer. Particularly preferred is 50 to 60% by mass.
- the mass ratio of the nitride particles (C1) in the total mass of the resin film forming layer is preferably 40% by mass or less, more preferably 20 to 40% by mass, and particularly preferably 20 to 30% by mass.
- the weight ratio (C1: C2) of the nitride particles (C1) and other particles (C2) is preferably 1: 5 to 5: 1, more preferably 1: 4 to 4: 1.
- the weight ratio of the nitride particles (C1) and the other particles (C2) within the above range, the nitride particles (C1) whose major axis direction and the thickness direction of the resin film forming layer are substantially the same. The ratio of can be increased. As a result, the thermal conductivity of the resin film forming layer can be improved. Moreover, the thickening of the composition for resin film formation can be suppressed, and a smooth resin film can be formed.
- the concentration of the inorganic filler (C) in the resin film forming layer is preferably 30 to 50% by volume, more preferably 35 to 45% by volume.
- a silane coupling agent (D) having a molecular weight of 300 or more is blended in the resin film forming layer.
- the adhesiveness of the resin film forming layer to the adherend can be improved.
- the water resistance can be improved by using a silane coupling agent (D), without impairing the heat resistance of the resin film obtained by hardening
- the “functional group that reacts with the inorganic substance” may be referred to as “reactive functional group A”
- the “functional group that reacts with the organic functional group” may be referred to as “reactive functional group B”.
- silane coupling agent (D) used in the present invention examples include oligomer type silane coupling agents having a molecular weight of 300 or more.
- the molecular weight of the silane coupling agent (D) is preferably 300 to 5000, more preferably 1000 to 3000.
- the alkoxy equivalent of the silane coupling agent (D) is preferably 10 to 40 mmol / g, more preferably 13 to 30 mmol / g.
- the reactive functional group A an alkoxy group is preferable.
- the reactive functional group B is preferably one that reacts with the functional group of the binder polymer component (A), the curable component (B), and the like, such as an epoxy group, an amino group, (meth) Examples thereof include an acryloyl group, a vinyl group excluding a vinyl group in the (meth) acryloyl group, and a mercapto group. Among these, an epoxy group is preferable.
- alkoxy equivalent shows the absolute number of the alkoxy group contained per unit weight of a compound.
- silane coupling agent (D) examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - ( Low molecular silane coupling agent having two or three alkoxy groups such as methacrylopropyl) trimethoxysilane; low molecular silane coupling agent having four alkoxy groups such as tetramethoxysilane, tetraethoxysilane; etc.
- the oligomer type thing which is the product condensed by hydrolysis and dehydration condensation of group is mentioned.
- a low molecular silane coupling agent having two or three alkoxy groups and a low molecular silane coupling agent having four alkoxy groups are condensed by dehydration condensation.
- the oligomer which is a thing has the functional group which is rich in the reactivity of an alkoxy group, and reacts with a sufficient number of organic functional groups, it is preferable.
- examples of such an oligomer include an oligomer which is a copolymer of 3- (2,3-epoxypropoxy) propylmethoxysiloxane and dimethoxysiloxane.
- the mass ratio of the silane coupling agent (D) in the total mass of the resin film forming layer is preferably 0.3 to 2 mass%, more preferably 0.5 to 2 mass%, particularly preferably 1 to 2 mass%. It is.
- the reactive functional group A of the silane coupling agent (D) is reactive with the inorganic filler (C) (particularly other particles (C2)).
- Adhesion of the resin film forming layer by the nitride particles (C1) by causing a chemical reaction between the functional group B and the functional group of the binder polymer component (A) or the curable component (B) efficiently and forming a network. The decline in sex can be suppressed.
- the resin film forming layer in the present invention has a silane compound (D ′) (hereinafter simply referred to as “silane compound”) having a molecular weight of 300 or more and an alkoxy equivalent of 10 mmol / g or more and having no reactive functional group B. D ′) ”) may be included. Since the silane compound (D ′) does not have the reactive functional group B, it does not react with the functional group of the binder polymer component (A) or the curable component (B), but has the reactive functional group A.
- silane compound (hereinafter simply referred to as “silane compound”) having a molecular weight of 300 or more and an alkoxy equivalent of 10 mmol / g or more and having no reactive functional group B. D ′) ”). Since the silane compound (D ′) does not have the reactive functional group B, it does not react with the functional group of the binder polymer component (A) or the curable component (B), but has the reactive functional group A.
- silane compound (D ′) examples include polymethoxysiloxane, polyethoxysiloxane, a copolymer of methoxysiloxane and dimethylsiloxane, and the like.
- the other component resin film-forming layer can contain the following components in addition to the binder polymer component (A), the curable component (B), the inorganic filler (C), and the silane coupling agent (D).
- a coloring agent (E) can be mix
- the colorant organic or inorganic pigments or dyes are used.
- the dye any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, and a cationic dye can be used.
- the pigment is not particularly limited, and can be appropriately selected from known pigments. Among these, black pigments are preferable from the viewpoint of electromagnetic wave and infrared shielding properties.
- black pigment examples include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like, but are not limited thereto. Carbon black is particularly preferable from the viewpoint of increasing the reliability of the semiconductor device.
- a coloring agent (E) may be used individually by 1 type, and may be used in combination of 2 or more types.
- the blending amount of the colorant (E) is preferably 0.1 to 35 parts by weight, more preferably 0.5 to 100 parts by weight of the total solid content constituting the resin film forming layer excluding the colorant (E). -25 parts by mass, particularly preferably 1-15 parts by mass.
- the curing accelerator (F) is used to adjust the curing speed of the resin film forming layer.
- the curing accelerator (F) is preferably used when an epoxy resin and a thermosetting agent are used in combination, particularly when at least a thermosetting component and a thermosetting agent are used as the curable component (B).
- Preferred curing accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; Organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine; And tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphinetetraphenylborate. These can be used individually by 1 type or in mixture of 2 or more types.
- the curing accelerator (F) is preferably contained in an amount of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the thermosetting component and the thermosetting agent. It is. By containing the curing accelerator (F) in an amount within the above range, it has excellent adhesion even when exposed to high temperatures and high humidity, and high reliability even when exposed to severe reflow conditions. Can be achieved. If the content of the curing accelerator (F) is small, sufficient adhesion cannot be obtained due to insufficient curing, and if it is excessive, the curing accelerator having a high polarity will adhere to the resin film forming layer at high temperature and high humidity. The reliability of the semiconductor device is lowered by moving to the side and segregating.
- the photopolymerization initiator resin film-forming layer contains an energy beam polymerizable compound as the curable component (B)
- energy beam polymerization is performed by irradiating energy rays such as ultraviolet rays when using the compound.
- the active compound is cured.
- the photopolymerization initiator (G) in the composition constituting the resin film forming layer, the polymerization curing time and the amount of light irradiation can be reduced.
- photopolymerization initiator (G) examples include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal.
- a photoinitiator (G) can be used individually by 1 type or in combination of 2 or more types.
- the blending ratio of the photopolymerization initiator (G) is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the energy beam polymerizable compound. If the amount is less than 0.1 parts by mass, satisfactory transferability may not be obtained due to insufficient photopolymerization. If the amount exceeds 10 parts by mass, a residue that does not contribute to photopolymerization is generated, and the curability of the resin film forming layer is not obtained. May be insufficient.
- a crosslinking agent may be added to adjust the initial adhesive force and cohesive strength of the crosslinking agent resin film-forming layer.
- examples of the crosslinking agent (H) include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.
- organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these organic polyvalent isocyanate compounds, and these organic polyvalent isocyanate compounds.
- examples thereof include terminal isocyanate urethane prepolymers obtained by reacting with a polyol compound.
- organic polyvalent isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4′-.
- organic polyvalent imine compounds include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, tetramethylol. Mention may be made of methane-tri- ⁇ -aziridinylpropionate and N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine.
- the crosslinking agent (H) is usually in a ratio of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the binder polymer component (A). Used.
- additives may be blended in the general-purpose additive resin film forming layer as necessary.
- additives include leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, and the like.
- the resin film-forming layer composed of the above components has adhesiveness and curability, and adheres to the semiconductor chip or the like by pressing against a semiconductor chip or the like in an uncured state or by pressing while heating. Then, after curing, a resin film having high impact resistance can be provided, the peel strength is excellent, and a sufficient protective function can be maintained even under severe high temperature and high humidity conditions.
- the resin film forming layer is preferably used as a film adhesive for fixing the semiconductor chip to the substrate or another semiconductor chip or as a protective film for the semiconductor chip.
- the resin film forming layer may have a single layer structure, or may have a multilayer structure as long as one or more layers containing the above components are included.
- the peel strength of the resin film forming layer is preferably 3.5 to 10 N / 10 mm, more preferably 5 to 10 N / 10 mm, and particularly preferably 7 to 10 N / 10 mm.
- the peel strength of the resin film forming layer is within the above range, a semiconductor device having excellent reliability can be manufactured.
- the measuring method of the peeling strength of a resin film formation layer is performed by the same method as an Example.
- the thermal conductivity of the resin film forming layer is preferably 2 W / (m ⁇ K) or more, more preferably 3 W / (m ⁇ K) or more. Further, the thermal conductivity of the cured resin film forming layer (resin film) is preferably 2 W / (m ⁇ K) or more, more preferably 3 W / (m ⁇ K) or more. If the thermal conductivity of the resin film forming layer or the resin film is less than 2 W / (m ⁇ K), the semiconductor device may be deformed due to heat generation of the semiconductor device, causing failure or breakage, and calculation of the semiconductor device. This may cause a reduction in speed or malfunction, and may reduce the reliability of the semiconductor device.
- the thermal conductivity of the resin film forming layer or the resin film By setting the thermal conductivity of the resin film forming layer or the resin film within the above range, the heat dissipation characteristics of the semiconductor device can be improved, and a semiconductor device having excellent reliability can be manufactured.
- the measuring method of the heat conductivity of the resin film formation layer is performed by the same method as an Example.
- thermal diffusivity can be used as an index of the heat dissipation characteristics of the resin film forming layer.
- the thermal diffusivity of the cured resin film forming layer (resin film) is 9.7 ⁇ 10 ⁇ It is preferably 7 m 2 / s or more, and more preferably 1.5 ⁇ 10 ⁇ 6 m 2 / s or more.
- the thermal diffusivity is a value obtained by dividing the thermal conductivity of the resin film forming layer or the resin film by the product of the specific heat and density of the resin film, and the greater the thermal diffusivity, the better the heat dissipation characteristics. .
- the resin film forming layer is obtained by applying and drying a resin film forming composition obtained by mixing the above-described components at an appropriate ratio on a support sheet.
- the composition for forming a resin film may be applied on a process film different from the support sheet and dried to form a film, which may be transferred onto the support sheet.
- each component may be diluted with a dispersion medium or a solvent in advance, or a dispersion medium or a solvent may be added during mixing. It is preferable to use a solvent from the viewpoint of uniformly mixing the above components.
- solvent examples include toluene, xylene, methanol, ethanol, isobutanol, n-butanol, ethyl acetate, methyl ethyl ketone, acetone, tetrahydrofuran, isopropanol, dimethylformamide, N-methylpyrrolidone and the like. These may be used alone or in combination of two or more.
- the resin film forming sheet for chips according to the present invention is formed by releasably forming the resin film forming layer on a support sheet.
- the shape of the resin film forming sheet for chips according to the present invention can take any shape such as a tape shape and a label shape.
- the support sheet for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, Polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A film such as a resin film is used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient. Moreover, the film which colored these can also be used.
- the support sheet is peeled off when used, and the resin film forming layer is transferred to a semiconductor wafer or chip.
- the support sheet needs to withstand the heating during the heat curing of the resin film forming layer, and therefore, an annealed polyethylene terephthalate film having excellent heat resistance, polyethylene Naphthalate film, polymethylpentene film, and polyimide film are preferably used.
- a release agent can be applied to the surface of the support sheet to perform a release treatment.
- alkyd, silicone, fluorine, unsaturated polyester, polyolefin, wax, and the like are used as the release agent used for the release treatment.
- alkyd, silicone, and fluorine release agents are heat resistant. This is preferable.
- the release agent In order to release the surface of a film or the like as a substrate of a support sheet using the above release agent, the release agent is used without any solvent, or diluted or emulsified with a solvent, and then a gravure coater, Mayer bar coater, air knife coater.
- the release agent layer may be formed by coating with a roll coater or the like, and subjecting the support sheet coated with the release agent to room temperature or heating, or curing with an electron beam.
- a support sheet may be obtained by laminating films by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion processing, or the like.
- the resin film forming layer may be laminated on a releasable pressure-sensitive adhesive layer provided on the support sheet.
- the re-peelable pressure-sensitive adhesive layer may be a weak-adhesive layer having an adhesive strength that can peel off the resin film-forming layer, or an energy-ray-curable layer whose adhesive strength is reduced by energy beam irradiation. May be used.
- energy beam irradiation is performed in advance on a region where the resin film forming layer is laminated (for example, the inner periphery of the support sheet) to reduce the adhesiveness.
- regions may not be irradiated with energy rays, and may be maintained with a high adhesive force for the purpose of bonding to a jig, for example.
- an energy beam shielding layer may be provided by printing or the like in a region corresponding to the other region of the support sheet, and the energy beam irradiation may be performed from the support sheet side. .
- Re-peelable pressure-sensitive adhesive layer is a variety of conventionally known pressure-sensitive adhesives (for example, general-purpose pressure-sensitive adhesives such as rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based, energy ray-curable pressure-sensitive adhesives, thermal expansion components) It may be an adhesive or the like, and the surface of the adhesive may be uneven.
- the thickness of the releasable pressure-sensitive adhesive layer is not particularly limited, but is usually 1 to 50 ⁇ m, preferably 5 to 30 ⁇ m.
- the support sheet in the chip-forming resin film forming sheet having such a configuration supports an adherend (semiconductor wafer or chip) in a dicing process, which is a semiconductor device manufacturing process described later, particularly when the resin film is used as a protective film. Therefore, the adhesiveness between the support sheet and the resin film forming layer can be maintained, so that the chip with the resin film forming layer can be prevented from being peeled off from the support sheet in the dicing process.
- the thickness of the support sheet is usually 10 to 500 ⁇ m, preferably 15 to 300 ⁇ m, particularly preferably 20 to 250 ⁇ m.
- the thickness of the resin film forming layer is preferably 25 to 50 ⁇ m, particularly preferably 30 to 45 ⁇ m. Moreover, it is preferable that the thickness of the resin film forming layer is larger than the average particle diameter of the other particles (C2).
- a light peelable release film is laminated on the upper surface of the resin film forming layer separately from the support sheet. May be.
- an adhesive layer or an adhesive tape may be separately provided on the outer peripheral portion of the surface of the resin film forming layer (the surface in contact with the adherend) in order to fix it to another jig such as a ring frame.
- the resin film forming layer of such a resin film forming sheet for chips can function as a film adhesive.
- a film adhesive is usually applied to any surface of a semiconductor wafer, cut into individual chips through a dicing process, and then placed on a substrate (die bond), and a semiconductor chip is bonded and fixed through a curing process. Used for Such a film adhesive is sometimes referred to as a die attachment film. Since the semiconductor device using the resin film forming layer in the present invention as a film adhesive is excellent in heat dissipation characteristics, it is possible to suppress a decrease in reliability.
- the resin film forming layer of the chip resin film forming sheet can be a protective film.
- the resin film forming layer is affixed to the back surface of the face-down chip semiconductor wafer or semiconductor chip, and has a function of protecting the semiconductor chip as an alternative to the sealing resin by being cured by an appropriate means.
- the protective film has a function of reinforcing the wafer, so that damage to the wafer can be prevented.
- the semiconductor device which used the resin film formation layer in this invention as the protective film is excellent in the thermal radiation characteristic, it can suppress the fall of the reliability.
- a method of manufacturing a semiconductor device is a semiconductor device in which a resin film forming layer of the resin film forming sheet for a chip is pasted on the back surface of a semiconductor wafer having a circuit formed on the surface, and then the resin film is formed on the back surface. It is preferable to obtain a chip.
- the resin film is preferably a protective film for a semiconductor chip.
- the method for manufacturing a semiconductor device according to the present invention preferably further includes the following steps (1) to (3), wherein the steps (1) to (3) are performed in an arbitrary order. Step (1): peeling the resin film forming layer or resin film and the support sheet, Step (2): The resin film forming layer is cured to obtain a resin film. Step (3): dicing the semiconductor wafer and the resin film forming layer or resin film.
- the semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium / arsenic. Formation of a circuit on the wafer surface can be performed by various methods including conventionally used methods such as an etching method and a lift-off method. Next, the opposite surface (back surface) of the circuit surface of the semiconductor wafer is ground.
- the grinding method is not particularly limited, and grinding may be performed by a known means using a grinder or the like. At the time of back surface grinding, an adhesive sheet called a surface protection sheet is attached to the circuit surface in order to protect the circuit on the surface.
- the circuit surface side (that is, the surface protection sheet side) of the wafer is fixed by a chuck table or the like, and the back surface side on which no circuit is formed is ground by a grinder.
- the thickness of the wafer after grinding is not particularly limited, but is usually about 20 to 500 ⁇ m.
- the crushed layer generated during back grinding is removed.
- the crushed layer is removed by chemical etching, plasma etching, or the like.
- steps (1) to (3) are performed in an arbitrary order. Details of this process are described in detail in JP-A-2002-280329. As an example, the case where it performs in order of process (1), (2), (3) is demonstrated.
- the resin film forming layer of the above-mentioned resin film forming sheet for chips is attached to the back surface of a semiconductor wafer having a circuit formed on the front surface.
- the support sheet is peeled from the resin film forming layer to obtain a laminate of the semiconductor wafer and the resin film forming layer.
- the resin film forming layer is cured to form a resin film on the entire surface of the wafer.
- a thermosetting component and a thermosetting agent are used as the curable component (B) in the resin film forming layer
- the resin film forming layer is cured by thermosetting.
- the resin film forming layer can be cured by irradiation with energy rays, and the thermosetting component, the thermosetting agent, energy
- the linear polymerizable compound is used in combination, curing by heating and energy beam irradiation may be performed simultaneously or sequentially.
- the energy rays to be irradiated include ultraviolet rays (UV) and electron beams (EB), and preferably ultraviolet rays are used.
- the outstanding heat dissipation characteristic is provided by forming the resin film with high heat conductivity. Further, compared with a coating method in which a coating solution for a resin film is directly applied to the back surface of a wafer or chip, the thickness of the resin film is excellent.
- the laminated body of the semiconductor wafer and the resin film is diced for each circuit formed on the wafer surface. Dicing is performed so as to cut both the wafer and the resin film.
- the wafer is diced by a conventional method using a dicing sheet. As a result, a semiconductor chip having a resin film on the back surface is obtained.
- a semiconductor chip having a resin film on the back surface can be obtained.
- the semiconductor device can be manufactured by mounting the semiconductor chip on a predetermined base by the face-down method.
- a semiconductor device can be manufactured by bonding a semiconductor chip having a resin film on the back surface to another member (on a chip mounting portion) such as a die pad portion or another semiconductor chip.
- a highly uniform resin film can be easily formed on the back surface of the chip, and cracks after the dicing process and packaging are less likely to occur.
- excellent heat dissipation characteristics are imparted to the obtained semiconductor device, it is possible to suppress a decrease in reliability.
- seat for resin film formation for chips is dicing.
- the semiconductor wafer is attached to the inner periphery of the chip resin film forming sheet via the resin film forming layer, and the outer periphery of the chip resin film forming sheet is joined to another jig such as a ring frame.
- the chip resin film forming sheet attached to the semiconductor wafer is fixed to the apparatus, and dicing is performed.
- the resin film forming layer of the sheet is bonded to a semiconductor wafer, and the semiconductor wafer is diced into a semiconductor chip.
- the resin film forming layer is fixedly left on either side of the semiconductor chip and peeled off from the support sheet, and the semiconductor chip is mounted on the die pad portion or another semiconductor chip via the resin film forming layer. It is preferable to include a step of placing. As an example, a manufacturing method for attaching a resin film forming layer to the back surface of a chip will be described below.
- the ring frame and the back side of the semiconductor wafer are placed on the resin film forming layer of the chip resin film forming sheet according to the present invention, and lightly pressed to fix the semiconductor wafer.
- the resin film forming sheet for chips according to the present invention has a resin film forming layer formed on the inner peripheral portion of the support sheet via the re-peeling adhesive layer, and the re-peeling adhesive layer on the outer peripheral portion of the support sheet.
- the semiconductor wafer is fixed on the resin film forming layer, and the ring frame is fixed via the re-peeling adhesive layer on the outer peripheral portion of the support sheet.
- the resin film forming layer does not have tackiness at room temperature, it may be appropriately heated (although it is not limited, 40 to 80 ° C. is preferable).
- the resin film forming layer is irradiated with energy rays from the support sheet side, and the resin layer forming layer is preliminarily formed. It may be hardened to increase the cohesive force of the resin film forming layer and decrease the adhesive force between the resin film forming layer and the support sheet.
- the semiconductor wafer is cut using a cutting means such as a dicing saw to obtain a semiconductor chip.
- the cutting depth at this time is a depth that takes into account the sum of the thickness of the semiconductor wafer and the thickness of the resin film forming layer and the amount of wear of the dicing saw.
- the energy beam irradiation may be performed at any stage after the semiconductor wafer is pasted and before the semiconductor chip is peeled off (pickup).
- the irradiation may be performed after dicing or after the following expanding step. Although it is good, it is preferably performed after the semiconductor wafer is attached and before dicing. Further, the energy beam irradiation may be performed in a plurality of times.
- the resin film forming sheet for chips is expanded, the interval between the semiconductor chips is expanded, and the semiconductor chips can be picked up more easily. At this time, a deviation occurs between the resin film forming layer and the support sheet, the adhesive force between the resin film forming layer and the support sheet is reduced, and the pick-up property of the semiconductor chip is improved. When the semiconductor chip is picked up in this manner, the cut resin film forming layer can be adhered to the back surface of the semiconductor chip and peeled off from the support sheet.
- the semiconductor chip is placed on the die pad of the lead frame or on the surface of another semiconductor chip (lower chip) through the resin film forming layer (hereinafter, the die pad or lower chip surface on which the chip is mounted is referred to as “chip mounting portion”. ).
- the chip mounting part may be heated before mounting the semiconductor chip or immediately after mounting.
- the heating temperature is usually 80 to 200 ° C., preferably 100 to 180 ° C.
- the heating time is usually 0.1 seconds to 5 minutes, preferably 0.5 seconds to 3 minutes.
- the pressure is usually 1 kPa to 200 MPa.
- the heating conditions at this time are in the above heating temperature range, and the heating time is usually 1 to 180 minutes, preferably 10 to 120 minutes.
- the resin film forming layer may be cured by using a heat in resin sealing that is normally performed in package manufacturing, without temporarily performing the heat treatment after placement.
- the resin film formation layer hardens
- the resin film forming layer is fluidized under die bonding conditions, the resin film forming layer is sufficiently embedded in the unevenness of the chip mounting portion, and generation of voids can be prevented and the reliability of the semiconductor device is improved.
- the thermal conductivity of the resin film forming layer is high, the semiconductor device has excellent heat dissipation characteristics, and it is possible to suppress a decrease in reliability.
- the resin film-forming sheet for chips of the present invention can be used for bonding semiconductor compounds, glass, ceramics, metals, etc., in addition to the above-described usage methods.
- the sample was heated and cured (130 ° C., 2 hours), and then the thermal conductivity of the sample was measured using a thermal conductivity measuring device (eye phase mobile 1u manufactured by ai-phase). .
- the case where the thermal conductivity was 2 W / (m ⁇ K) or more was evaluated as “good”, and the other cases were evaluated as “bad”.
- Binder polymer component copolymer of 85 parts by weight of methyl methacrylate and 15 parts by weight of 2-hydroxyethyl acrylate (weight average molecular weight: 400,000, glass transition temperature: 6 ° C.)
- Curing component (B1) Bisphenol A type epoxy resin (epoxy equivalent 180 to 200 g / eq)
- B2) Dicyclopentadiene type epoxy resin (Epiclon HP-7200HH manufactured by DIC Corporation)
- B3) Dicyandiamide Adeka Hardener 3636AS manufactured by Asahi Denka
- Inorganic filler (C1) Boron nitride particles (UHP-2 manufactured by Showa Denko KK, shape: plate, average particle diameter 11.8 ⁇ m, aspect ratio 11.2, major axis direction thermal conductivity 200 W / (m ⁇ K), Density 2.3 g / cm 3 ) (C2)
- Examples and Comparative Examples The above components were blended in the amounts shown in Table 1 to obtain a resin film forming composition.
- a methyl ethyl ketone solution (solid concentration: 61% by weight) of the obtained composition was dried on a release-treated surface of a support sheet (SP-PET 381031, thickness 38 ⁇ m manufactured by Lintec Co., Ltd.) that had been release-treated with silicone, to a thickness of 40 ⁇ m It was coated and dried (drying conditions: 110 ° C. for 1 minute in an oven) to form a resin film-forming layer on the support sheet to obtain a resin film-forming sheet for chips.
- the resin film forming layer of the resin film forming sheet for a chip of the example exhibited excellent peel strength and thermal conductivity. Therefore, a highly reliable semiconductor device can be obtained by using the resin film forming sheet for chips according to the present invention.
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Abstract
Description
また、窒化ホウ素などの無機フィラーは、該シートを製造する際に用いる樹脂膜形成用組成物中において分散性が低く、濡れ性や接着性を向上させることが困難であった。その結果、半導体装置の信頼性が低下することがあった。
なお、特許文献4には、接着性を改善するために樹脂組成物中に、ポリシロキサンオリゴマーにシランカップリング剤を付与、縮合させた化合物を添加することが記載されている。
〔1〕支持シートと、該支持シート上に形成された樹脂膜形成層とを有し、
該樹脂膜形成層が、バインダーポリマー成分(A)、硬化性成分(B)、無機フィラー(C)及びシランカップリング剤(D)を含み、
該無機フィラー(C)が窒化物粒子(C1)を含有し、
該シランカップリング剤(D)の分子量が300以上であるチップ用樹脂膜形成用シート。
樹脂膜形成層は、バインダーポリマー成分(A)、硬化性成分(B)、無機フィラー(C)及びシランカップリング剤(D)を含む。
樹脂膜形成層に十分な接着性(半導体ウエハ等への貼付性や転写性)および造膜性(シート形成性)を付与するためにバインダーポリマー成分(A)が用いられる。バインダーポリマー成分(A)としては、従来公知のアクリルポリマー、ポリエステル樹脂、ウレタン樹脂、アクリルウレタン樹脂、フェノキシ樹脂、シリコーン樹脂、ゴム系ポリマー、ポリスチレン等を用いることができ、熱硬化性の官能基のような官能基の有無は問わない。
アルキル基の炭素数が1~18であるアルキル(メタ)アクリレートとしては、具体的にはメチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、へプチル(メタ)アクリレート、オクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ラウリル(メタ)アクリレート、テトラデシル(メタ)アクリレート、オクタデシル(メタ)アクリレートなどが挙げられる。
環状骨格を有する(メタ)アクリレートとしては、具体的にはシクロアルキル(メタ)アクリレート、ベンジル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、イミド(メタ)アクリレートなどが挙げられる。
水酸基を有する(メタ)アクリレートとしては、具体的にはヒドロキシメチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートなどが挙げられる。
エポキシ基を有する(メタ)アクリレートとしては、具体的にはグリシジル(メタ)アクリレートなどが挙げられる。
これらの中では、水酸基を有しているモノマーを重合して得られるアクリルポリマーが、後述する硬化性成分(B)との相溶性が良いため好ましい。また、水酸基を有しているモノマーを含有しているアクリルポリマーを用いた場合には、後述する架橋剤(H)として有機多価イソシアネート化合物等を用いることによりアクリルポリマーを容易に架橋することができ、硬化前の樹脂膜形成層の凝集性を制御することができる。
また、上記アクリルポリマーは、アクリル酸、メタクリル酸、イタコン酸、酢酸ビニル、アクリロニトリル、スチレンなどが共重合されていてもよい。
エポキシ基を有するモノマーとしては、たとえば上述のグリシジル(メタ)アクリレート等のエポキシ基を有する(メタ)アクリレートの他に、エポキシ基を有するノルボルネン等が挙げられる。
ポリマーを構成するモノマーとしてエポキシ基を有するモノマーを含むアクリルポリマーは、文言上後述するエポキシ樹脂の概念に含まれることになるが、本発明ではかかるアクリルポリマーはエポキシ樹脂に含まれないものとする。すなわち、硬化性成分(B)における熱硬化性成分として、かかるアクリルポリマー以外の分子であって、かかる分子中に2官能以上有するエポキシ化合物を樹脂膜形成層に配合する場合に、かかるアクリルポリマーを用いることによる上述の効果が得られることになる。
さらに、アクリルポリマーと混合するポリマーのガラス転移温度を選択することにより、支持シートとの剥離力増大に起因する樹脂膜形成層の転写不良や、樹脂膜形成層とチップとの接着力の低下を抑制することも可能となる。
硬化性成分(B)は、熱硬化性成分および熱硬化剤、またはエネルギー線重合性化合物を用いることができる。また、これらを組み合わせて用いてもよい。熱硬化性成分としては、たとえば、エポキシ樹脂が好ましい。
無機フィラー(C)は窒化物粒子(C1)を含有する。窒化物粒子(C1)を含有する無機フィラー(C)を樹脂膜形成層に配合することにより、樹脂膜形成層の熱伝導率を向上させ、樹脂膜形成層が貼付された半導体チップを実装した半導体装置の発した熱を効率的に拡散することが可能となる。また、硬化後の樹脂膜における熱膨張係数を調整することが可能となり、半導体ウエハ、半導体チップ、リードフレームや有機基板等を被着体として半導体装置の信頼性を向上させることができる。さらにまた、硬化後の樹脂膜の吸湿率を低減させることが可能となり、加熱時に樹脂膜としての接着性を維持し、半導体装置の信頼性を向上させることができる。さらに、樹脂膜にレーザーマーキングを施すことにより、レーザー光により削り取られた部分に無機フィラー(C)が露出して、反射光が拡散するために白色に近い色を呈する。これにより、樹脂膜形成層が後述する着色剤(E)を含有する場合、レーザーマーキング部分と他の部分にコントラスト差が得られ、印字が明瞭になるという効果がある。
窒化物粒子(C1)としては、窒化ホウ素、窒化アルミニウム、窒化珪素等の粒子が挙げられる。これらのうちでも高い熱伝導率を有する樹脂膜形成層が得られやすい窒化ホウ素粒子が好ましい。
なお、本発明において「窒化物粒子(C1)の長軸方向と樹脂膜形成層の厚み方向とが略同一」とは、具体的には、窒化物粒子(C1)の長軸方向が、樹脂膜形成層の厚み方向に平行な状態を0°としたとき、樹脂膜形成層の厚み方向と窒化物粒子(C1)の長軸方向とがなす角度が-45~45°の範囲にあることをいう。
他の粒子(C2)としては、シリカ粒子、アルミナ粒子などが挙げられ、アルミナ粒子が特に好ましい。アルミナ粒子を用いることで、窒化物粒子が形成する熱伝導パス以外の部分でも熱伝導性が損なわれず、結果として熱伝導率の高い樹脂膜形成層が得られる。
他の粒子(C2)の形状は、窒化物粒子(C1)の長軸方向と、樹脂膜形成層と平行な方向とが略同一となることを妨げる形状であれば特に限定されず、その具体的な形状は、好ましくは球状である。このような形状の他の粒子(C2)を用いることで、樹脂膜形成層の製造工程において、窒化物粒子(C1)の長軸方向が樹脂膜形成層と平行な方向と略同一となることを抑制し、その長軸方向と樹脂膜形成層の厚み方向とが略同一となった窒化物粒子(C1)の割合を高めることができる。その結果、樹脂膜形成層の厚み方向に優れた熱伝導率を有する樹脂膜形成層が得られる。これは、樹脂膜形成層中に、他の粒子(C2)が存在することにより、窒化物粒子(C1)が他の粒子(C2)に立て掛かるように存在する結果、窒化物粒子(C1)の長軸方向と樹脂膜形成層の厚み方向とが略同一となることに起因する。異方形状の窒化物粒子(C1)のみを用いた場合、樹脂膜形成層の製造工程(例えば塗布工程)中に窒化物粒子(C1)にかかる応力や重力により、その長軸方向が樹脂膜形成層に平行な方向と略同一となる窒化物粒子(C1)の割合が高まり、優れた熱伝導率を有する樹脂膜形成層を得ることが困難になることがある。
また、樹脂膜形成層の全質量中における窒化物粒子(C1)の質量割合は、好ましくは40質量%以下、より好ましくは20~40質量%、特に好ましくは20~30質量%である。窒化物粒子(C1)の質量割合を上記範囲とすることで、効率的な熱伝導パスが形成され、樹脂膜形成層の熱伝導率を向上させることができる。
無機物と反応する官能基および有機官能基と反応する官能基を有し、分子量が300以上であるシランカップリング剤(D)を樹脂膜形成層に配合することで、樹脂膜形成層の被着体に対する接着性を向上させることができる。また、シランカップリング剤(D)を使用することで、樹脂膜形成層を硬化して得られる樹脂膜の耐熱性を損なうことなく、その耐水性を向上することができる。なお、以下において、上記「無機物と反応する官能基」を「反応性官能基A」と、上記「有機官能基と反応する官能基」を「反応性官能基B」と記載することがある。
反応性官能基Aとしては、アルコキシ基が好ましい。また、反応性官能基Bとしては、バインダーポリマー成分(A)や硬化性成分(B)などが有する官能基と反応するものが好ましく、このようなものとして、エポキシ基、アミノ基、(メタ)アクリロイル基、(メタ)アクリロイル基中のビニル基を除くビニル基、メルカプト基が挙げられ、これらの中でも、エポキシ基が好ましい。なお、アルコキシ当量は化合物の単位重量当たりに含まれるアルコキシ基の絶対数を示す。
このようなシランカップリング剤(D)を用いることにより、樹脂膜形成層の熱伝導率を維持しつつ、所定の剥離強度を有する樹脂膜形成層を得ることが容易になる。
樹脂膜形成層は、上記バインダーポリマー成分(A)、硬化性成分(B)、無機フィラー(C)及びシランカップリング剤(D)に加えて下記成分を含むことができる。
樹脂膜形成層には、着色剤(E)を配合することができる。着色剤を配合することで、半導体装置を機器に組み込んだ際に、周囲の装置から発生する赤外線等による半導体装置の誤作動を防止することができる。このような効果は、特に樹脂膜を保護膜として用いた場合に有用である。着色剤としては、有機または無機の顔料または染料が用いられる。
染料としては、酸性染料、反応染料、直接染料、分散染料、カチオン染料等のいずれの染料であっても用いることが可能である。また、顔料も、特に制限されず、公知の顔料から適宜選択して用いることができる。
これらの中でも電磁波や赤外線遮蔽性の点から黒色顔料が好ましい。黒色顔料としては、カーボンブラック、酸化鉄、二酸化マンガン、アニリンブラック、活性炭等が用いられるが、これらに限定されることはない。半導体装置の信頼性を高める観点からは、カーボンブラックが特に好ましい。着色剤(E)は1種を単独で用いてもよいし、2種以上を併せて用いてもよい。
着色剤(E)の配合量は、着色剤(E)を除く樹脂膜形成層を構成する全固形分100質量部に対して、好ましくは0.1~35質量部、さらに好ましくは0.5~25質量部、特に好ましくは1~15質量部である。
硬化促進剤(F)は、樹脂膜形成層の硬化速度を調整するために用いられる。硬化促進剤(F)は、特に、硬化性成分(B)として、少なくとも熱硬化性成分および熱硬化剤を用いる場合において、エポキシ樹脂と熱硬化剤とを併用するときに好ましく用いられる。
樹脂膜形成層が、硬化性成分(B)として、エネルギー線重合性化合物を含有する場合には、その使用に際して、紫外線等のエネルギー線を照射して、エネルギー線重合性化合物を硬化させる。この際、樹脂膜形成層を構成する組成物中に光重合開始剤(G)を含有させることで、重合硬化時間ならびに光線照射量を少なくすることができる。
樹脂膜形成層の初期接着力および凝集力を調節するために、架橋剤を添加することもできる。架橋剤(H)としては有機多価イソシアネート化合物、有機多価イミン化合物などが挙げられる。
樹脂膜形成層には、上記の他に、必要に応じて各種添加剤が配合されてもよい。各種添加剤としては、レベリング剤、可塑剤、帯電防止剤、酸化防止剤、イオン捕捉剤、ゲッタリング剤、連鎖移動剤などが挙げられる。
樹脂膜形成層は、上記各成分を適宜の割合で混合してなる樹脂膜形成用組成物を、支持シート上に塗布乾燥して得られる。また、支持シートとは別の工程フィルム上に樹脂膜形成用組成物を塗布、乾燥して成膜し、これを支持シート上に転写してもよい。混合に際しては、各成分を予め分散媒や溶媒を用いて希釈しておいてもよく、また混合時に分散媒や溶媒を加えてもよい。上記各成分を均一に混合できる観点から溶媒を用いることが好ましい。溶媒としては、例えば、トルエン、キシレン、メタノール、エタノール、イソブタノール、n-ブタノール、酢酸エチル、メチルエチルケトン、アセトン、テトラヒドロフラン、イソプロパノール、ジメチルホルムアミド、N-メチルピロリドンなどが挙げられる。これらは、1種単独で用いても、2種以上を組み合わせて用いてもよい。
次に本発明に係るチップ用樹脂膜形成用シートの利用方法について、該シートを半導体装置の製造方法に適用した場合を例にとって説明する。
工程(1):樹脂膜形成層または樹脂膜と、支持シートとを剥離、
工程(2):樹脂膜形成層を硬化し樹脂膜を得る、
工程(3):半導体ウエハと、樹脂膜形成層または樹脂膜とをダイシング。
その際、樹脂膜形成層が室温ではタック性を有しない場合は適宜加温しても良い(限定するものではないが、40~80℃が好ましい)。
次いで、樹脂膜形成層に硬化性成分(B)としてエネルギー線重合性化合物が配合されている場合には、樹脂膜形成層に支持シート側からエネルギー線を照射し、樹脂層形成層を予備的に硬化し、樹脂膜形成層の凝集力を上げ、樹脂膜形成層と支持シートとの間の接着力を低下させておいてもよい。
その後、ダイシングソーなどの切断手段を用いて、上記の半導体ウエハを切断し半導体チップを得る。この際の切断深さは、半導体ウエハの厚みと、樹脂膜形成層の厚みとの合計およびダイシングソーの磨耗分を加味した深さにする。
なお、エネルギー線照射は、半導体ウエハの貼付後、半導体チップの剥離(ピックアップ)前のいずれの段階で行ってもよく、たとえばダイシングの後に行ってもよく、また下記のエキスパンド工程の後に行ってもよいが、半導体ウエハの貼付後であってダイシング前に行うことが好ましい。さらにエネルギー線照射を複数回に分けて行ってもよい。
チップ用樹脂膜形成用シートの樹脂膜形成層上に、厚み350μmのシリコンウエハを載置し、70℃で熱ラミネートした。次いで、チップ用樹脂膜形成用シートの支持シートを剥離した。その後、10mm幅の銅箔(厚み150μm)を樹脂膜形成層上に70℃で熱ラミネートし、加熱オーブン内で熱硬化(130℃、2時間)した後、汎用の引張試験機(SHIMADZU製 AG-IS MS)を用いて90°ピール試験を行い、銅箔の剥離強度を測定した。剥離強度が3.5~10N/10mmであった場合を「良好」、それ以外の場合を「不良」と評価した。
(硬化前)
樹脂膜形成層(厚さ:40μm)を、裁断して各片が1cmの正方形の試料を得た。次いで、熱伝導率測定装置(ai-phase社製 アイフェイズ・モバイル1u)を用いて、温度熱分析法で該試料の厚み方向における熱伝導率を測定した。熱伝導率が2W/(m・K)以上の場合を「良好」、それ以外の場合を「不良」と評価した。
(硬化後)
樹脂膜形成層(厚さ:40μm)を、裁断して各片が1cmの正方形の試料を得た。次いで、該試料を加熱(130℃、2時間)して硬化させた後、熱伝導率測定装置(ai-phase社製 アイフェイズ・モバイル1u)を用いて、該試料の熱伝導率を測定した。熱伝導率が2W/(m・K)以上の場合を「良好」、それ以外の場合を「不良」と評価した。
樹脂膜形成層を構成する各成分を下記に示す。
(A)バインダーポリマー成分:メタクリル酸メチル85質量部とアクリル酸2-ヒドロキシエチル15質量部との共重合体(重量平均分子量:40万、ガラス転移温度:6℃)
(B)硬化性成分:
(B1)ビスフェノールA型エポキシ樹脂(エポキシ当量180~200g/eq)
(B2)ジシクロペンタジエン型エポキシ樹脂(DIC株式会社製 エピクロンHP-7200HH)
(B3)ジシアンジアミド(旭電化製 アデカハードナー3636AS)
(C)無機フィラー:
(C1)窒化ホウ素粒子(昭和電工(株)製 UHP-2、形状:板状、平均粒子径11.8μm、アスペクト比11.2、長軸方向の熱伝導率200W/(m・K)、密度2.3g/cm3)
(C2)アルミナフィラー(昭和電工(株)製 CB-A20S、形状:球状、平均粒子径20μm、密度4.0g/cm3)
(C3)シリカフィラー(溶融石英フィラー、平均粒子径3μm)
(D)シランカップリング剤:
(D1)オリゴマータイプシランカップリング剤(信越化学工業株式会社製 X-41-1056 アルコキシ当量17.1mmol/g、分子量500~1500)
(D2)モノマータイプシランカップリング剤(γ-グリシドキシプロピルメチルジエトキシシラン、信越化学工業株式会社製 KBE-402 アルコキシ当量10.8mmol/g、分子量248.4)
(E)着色剤:黒色顔料(カーボンブラック、三菱化学社製 #MA650、平均粒子径28nm)
(F)硬化促進剤:2-フェニル-4,5-ジヒドロキシメチルイミダゾール(四国化成工業社製 キュアゾール2PHZ-PW)
上記各成分を表1に記載の量で配合し、樹脂膜形成用組成物を得た。得られた組成物のメチルエチルケトン溶液(固形濃度61重量%)を、シリコーンで剥離処理された支持シート(リンテック株式会社製 SP-PET381031、厚さ38μm)の剥離処理面上に乾燥後40μmの厚みになるように塗布、乾燥(乾燥条件:オーブンにて110℃、1分間)して、支持シート上に樹脂膜形成層を形成し、チップ用樹脂膜形成用シートを得た。
Claims (13)
- 支持シートと、該支持シート上に形成された樹脂膜形成層とを有し、
該樹脂膜形成層が、バインダーポリマー成分(A)、硬化性成分(B)、無機フィラー(C)及びシランカップリング剤(D)を含み、
該無機フィラー(C)が窒化物粒子(C1)を含有し、
該シランカップリング剤(D)の分子量が300以上であるチップ用樹脂膜形成用シート。 - 該樹脂膜形成層の全質量中におけるシランカップリング剤(D)の質量割合が0.3~2質量%である請求項1に記載のチップ用樹脂膜形成用シート。
- シランカップリング剤(D)のアルコキシ当量が10~40mmol/gである請求項1または2に記載のチップ用樹脂膜形成用シート。
- 該樹脂膜形成層の全質量中における窒化物粒子(C1)の質量割合が40質量%以下である請求項1~3のいずれかに記載のチップ用樹脂膜形成用シート。
- 該樹脂膜形成層の全質量中における無機フィラー(C)の質量割合が30~60質量%である請求項1~4のいずれかに記載のチップ用樹脂膜形成用シート。
- 無機フィラー(C)が窒化物粒子(C1)以外の他の粒子(C2)を含有する請求項1~5のいずれかに記載のチップ用樹脂膜形成用シート。
- 窒化物粒子(C1)が窒化ホウ素粒子である請求項1~6のいずれかに記載のチップ用樹脂膜形成用シート。
- 他の粒子(C2)の平均粒子径が20μm以上である請求項6に記載のチップ用樹脂膜形成用シート。
- 無機フィラー(C)における窒化物粒子(C1)と他の粒子(C2)との重量比率(C1:C2)が1:5~5:1である請求項6または8に記載のチップ用樹脂膜形成用シート。
- 他の粒子(C2)の平均粒子径が、樹脂膜形成層の厚みの0.01~0.65倍である請求項6、8または9のいずれかに記載のチップ用樹脂膜形成用シート。
- 樹脂膜形成層の剥離強度が3.5~10N/10mmである請求項1~10のいずれかに記載のチップ用樹脂膜形成用シート。
- 樹脂膜形成層の熱伝導率が2W/(m・K)以上である請求項1~11のいずれかに記載のチップ用樹脂膜形成用シート。
- 請求項1~12のいずれかに記載のチップ用樹脂膜形成用シートを用いる半導体装置の製造方法。
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TWI577775B (zh) | 2017-04-11 |
JP6427791B2 (ja) | 2018-11-28 |
EP2927952A4 (en) | 2016-08-03 |
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JPWO2014083872A1 (ja) | 2017-01-05 |
CN104871310B (zh) | 2018-03-09 |
KR102140470B1 (ko) | 2020-08-03 |
KR20150092101A (ko) | 2015-08-12 |
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