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WO2014148642A1 - 保護膜形成用フィルムおよび保護膜形成用複合シート - Google Patents

保護膜形成用フィルムおよび保護膜形成用複合シート Download PDF

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Publication number
WO2014148642A1
WO2014148642A1 PCT/JP2014/058038 JP2014058038W WO2014148642A1 WO 2014148642 A1 WO2014148642 A1 WO 2014148642A1 JP 2014058038 W JP2014058038 W JP 2014058038W WO 2014148642 A1 WO2014148642 A1 WO 2014148642A1
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WIPO (PCT)
Prior art keywords
protective film
film
forming
thermosetting
wafer
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PCT/JP2014/058038
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English (en)
French (fr)
Japanese (ja)
Inventor
尚哉 佐伯
山本　大輔
高野　健
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リンテック株式会社
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Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2014530843A priority Critical patent/JP5615471B1/ja
Priority to KR1020217018040A priority patent/KR102377100B1/ko
Priority to KR1020157026015A priority patent/KR20150135284A/ko
Priority to KR1020217018041A priority patent/KR102541666B1/ko
Priority to SG11201507775XA priority patent/SG11201507775XA/en
Priority to CN201480004970.7A priority patent/CN104937712B/zh
Priority to KR1020227007805A priority patent/KR20220035981A/ko
Publication of WO2014148642A1 publication Critical patent/WO2014148642A1/ja
Priority to PH12015502208A priority patent/PH12015502208B1/en

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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • 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
    • 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
    • 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
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • 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
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/02—Polyglycidyl ethers of bis-phenols
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/04—Epoxynovolacs
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds
    • 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 relates to a protective film-forming film capable of forming a protective film on a semiconductor wafer or a semiconductor chip and improving the manufacturing efficiency of the semiconductor chip.
  • the present invention relates to a protective film forming film used for manufacturing a semiconductor chip to be mounted by a so-called face-down method.
  • 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.
  • Patent Document 1 a protective film forming sheet for chips having a curable protective film forming layer containing a heat or energy ray curable component is disclosed.
  • the wafer itself when the wafer itself is sufficiently thick, the wafer itself has not warped.
  • the shrinkage ratio between the wafer surface on which the circuit is formed and the back surface of the wafer on which the circuit is not formed There is a problem that warpage occurs in the thinned wafer due to the difference in the above.
  • a wafer having a large warp may cause a conveyance failure during the subsequent chip manufacturing process.
  • the wafer may be difficult to dice due to the warpage of the wafer.
  • the protective film-forming film attached to the back surface of the wafer is required to have a capability of correcting the warpage of the wafer.
  • the following flip chip type semiconductor back film is used to suppress or prevent warping of semiconductor elements such as semiconductor wafers and semiconductor chips.
  • patent document 3 using the film for flip chip type semiconductor back surfaces whose shrinkage
  • An object of the present invention is to provide a film for forming a protective film that can suppress warping of a wafer and can form a highly reliable protective film on a chip.
  • the gist of the present invention is as follows. [1] It has thermosetting properties, The glass transition temperature after thermosetting is 150 to 300 ° C., A protective film-forming film having a tensile elastic modulus at 23 ° C. of 0.5 to 10 GPa after thermosetting.
  • thermosetting polymer component is contained, and 135 parts by mass of the thermosetting component with respect to a total of 100 parts by mass of the polymer component and the thermosetting polymer component.
  • the protective film-forming film according to [2] which is contained in a part or less.
  • the protective film-forming film contains an inorganic filler, The protective film-forming film according to any one of [1] to [3], wherein the content of the inorganic filler is 10 to 70 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film-forming film.
  • the protective film-forming film contains a thermosetting polymer component, The film for forming a protective film according to any one of [1] to [5], wherein the thermosetting polymer component is an acrylic polymer containing an epoxy group-containing monomer as a constituent monomer.
  • a composite sheet for forming a protective film wherein a support sheet is detachably formed on one side of the film for forming a protective film according to any one of [1] to [6].
  • the protective film-forming film can be cured and contracted by applying a protective film-forming film to the back surface of the wafer and thermally curing the wafer due to shrinkage caused by circuit formation on the wafer front side.
  • the warpage of the wafer can be corrected by the resulting stress, and a highly reliable chip with a protective film can be obtained.
  • the 1st aspect of the composite sheet for protective film formation formed using the film for protective film formation concerning this invention is shown.
  • the 2nd aspect of the composite sheet for protective film formation formed using the film for protective film formation concerning this invention is shown.
  • 3rd aspect of the composite sheet for protective film formation formed using the film for protective film formation which concerns on this invention is shown.
  • 4th aspect of the composite sheet for protective film formation formed using the film for protective film formation which concerns on this invention is shown. It is drawing explaining the "warpage amount" evaluated in the Example.
  • the protective film-forming film of the present invention has thermosetting properties, and has a glass transition temperature (Tg) after thermosetting of 150 to 300 ° C, preferably 170 to 280 ° C, more preferably 220 to 270 ° C.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) after thermosetting of the protective film-forming film is ⁇ 50 to in the dynamic viscoelasticity measurement of the protective film-forming film (protective film) after thermosetting measured at a frequency of 11 Hz. It indicates the temperature at which the loss tangent tan ⁇ exhibits a maximum value in a low temperature region of 30 ° C.
  • the Tg after thermosetting of the protective film-forming film is less than 150 ° C., the fluidity of the protective film-forming film is increased in the thermosetting process of the protective film-forming film usually performed at about 120 to 150 ° C., Stress due to curing shrinkage of the protective film-forming film is relieved and reduced. As a result, the correction of the warpage of the wafer is insufficient.
  • the Tg of the protective film-forming film after thermosetting exceeds 300 ° C., the protective film-forming film or the protective film obtained by thermosetting the film may be peeled off from the wafer or chip. As a result, the reliability of the chip with protective film decreases.
  • the protective film-forming film has a predetermined rigidity in the thermosetting process of the film, so that stress due to curing shrinkage of the film is relieved. Instead, the warpage of the wafer or chips obtained by dividing the wafer into pieces can be corrected.
  • the protective film-forming film has a tensile elastic modulus at 23 ° C. after thermosetting of 0.5 to 10 GPa, preferably 1 to 10 GPa, more preferably more than 5 GPa and 8 GPa or less. If the tensile elastic modulus at 23 ° C. after thermal curing of the protective film-forming film is less than 0.5 GPa, stress due to curing shrinkage of the protective film-forming film cannot be maintained, and the stress is relieved. The correction of the warpage of the wafer becomes insufficient. On the other hand, if the tensile elastic modulus at 23 ° C.
  • the protective film-forming film or the protective film obtained by thermosetting the film may be peeled off from the wafer or chip. There is.
  • the tensile elastic modulus at 23 ° C. after thermosetting of the protective film-forming film within the above range, it is possible to correct the warpage of the wafer and the chip and improve the reliability of the chip with the protective film.
  • the thermal shrinkage rate of the protective film-forming film when heated at 130 ° C. for 2 hours is preferably 0.1 to 10%, more preferably 0.5 to 5%.
  • the thermal shrinkage rate when the protective film-forming film is heated at 130 ° C. for 2 hours within the above range, the effect of correcting the warpage of the wafer (warpage correction performance) is improved.
  • the thermal contraction rate of the protective film-forming film when heated at 130 ° C. for 2 hours is obtained from the area of the protective film-forming film before and after the protective film-forming film is put in an environment at 130 ° C. by the following formula. .
  • Heat shrinkage rate (%) ⁇ (area of protective film forming film before loading) ⁇ (area of protective film forming film after loading) ⁇ / area of protective film forming film before loading ⁇ 100
  • the functions required for the protective film-forming film are (1) sheet shape maintenance, (2) initial adhesiveness, and (3) curability.
  • the film for protective film formation of this invention has thermosetting as above-mentioned, you may have the property hardened
  • the protective film-forming film can be provided with (1) sheet shape maintainability and (3) curability by adding a binder component.
  • the binder component the polymer component (A) and the thermosetting component ( The first binder component containing B) or the second binder component containing the thermosetting polymer component (AB) having the properties of the component (A) and the component (B) can be used.
  • it is a function for temporarily attaching the protective film-forming film to the adherend until it is cured.
  • the initial adhesiveness may be pressure-sensitive adhesiveness, and is softened and bonded by heat. It may be a property to do.
  • the initial adhesiveness is usually controlled by adjusting various properties of the binder component and adjusting the blending amount of the inorganic filler (C) described later.
  • a 1st binder component provides a sheet
  • a 1st binder component does not contain a thermosetting polymer component (AB) for convenience which distinguishes from a 2nd binder component.
  • the polymer component (A) is added to the protective film-forming film mainly for the purpose of imparting sheet shape maintenance to the protective film-forming film.
  • the weight average molecular weight (Mw) of the polymer component (A) is usually 20,000 or more, preferably 20,000 to 3,000,000.
  • the value of the weight average molecular weight (Mw) is a value when measured by a gel permeation chromatography method (GPC) method (polystyrene standard).
  • the measurement by such a method is carried out, for example, by using a high-speed GPC apparatus “HLC-8120GPC” manufactured by Tosoh Corporation and a high-speed column “TSK gold column H XL- H”, “TSK Gel GMH XL ”, “TSK Gel G2000 H XL ”. (The above, all manufactured by Tosoh Corporation) are connected in this order, and the detector is used as a differential refractometer at a column temperature of 40 ° C. and a liquid feed rate of 1.0 mL / min.
  • the polymer component (A) does not have a curing functional functional group described later.
  • polymer component (A) examples include acrylic polymers, polyesters, phenoxy resins (for the purpose of distinguishing from thermosetting polymer components (AB) described later, those having no epoxy group), polycarbonates, and polyethers.
  • Polyurethane, polysiloxane, rubber polymer, etc. can be used.
  • it is an acrylic urethane resin obtained by reacting a urethane prepolymer having an isocyanate group at a molecular terminal with an acrylic polyol which is an acrylic polymer having a hydroxyl group, which is a combination of two or more of these. May be.
  • two or more of these may be used in combination, including a polymer in which two or more are bonded.
  • acrylic polymer (A1) As the acrylic polymer polymer component (A), acrylic polymer (A1) is preferably used.
  • the glass transition temperature (Tg) of the acrylic polymer (A1) is preferably in the range of ⁇ 60 to 50 ° C., more preferably ⁇ 50 to 40 ° C., and further preferably ⁇ 40 to 30 ° C. If the glass transition temperature of the acrylic polymer (A1) is high, the initial adhesiveness of the protective film-forming film is lowered, and it may not be transferred to the adherend. In addition, when the glass transition temperature of the acrylic polymer (A1) is low, the peeling force between the protective film-forming film and a support sheet described later may increase, and transfer failure of the protective film-forming film may occur.
  • the Tg of the acrylic polymer is a value determined from the FOX equation.
  • the weight average molecular weight (Mw) of the acrylic polymer (A1) is preferably 100,000 to 1,500,000.
  • Mw weight average molecular weight of the acrylic polymer (A1)
  • the initial adhesiveness of the protective film-forming film is lowered, and it may not be transferred to the adherend.
  • the weight average molecular weight of the acrylic polymer (A1) is low, the adhesion between the protective film-forming film and the support sheet is increased, which may cause transfer failure of the protective film-forming film.
  • the acrylic polymer (A1) contains (meth) acrylic acid ester in at least a constituent monomer.
  • (meth) acrylic acid esters include alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms, specifically methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 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 (meth) acrylate, octadecyl (meth) acrylate, etc .; (meth) acrylate
  • a (meth) acrylic acid ester having a hydroxyl group a (meth) acrylic acid ester having a carboxyl group, or a (meth) acrylic acid having an amino group
  • a (meth) acrylic acid ester having a hydroxyl group a (meth) acrylic acid ester having a carboxyl group
  • a (meth) acrylic acid having an amino group By using the ester, it becomes easy to control the tensile elastic modulus at 23 ° C. after the thermosetting of the protective film-forming film within a predetermined range.
  • (meth) acryl may be used to include both acrylic and methacrylic.
  • a monomer having a hydroxyl group may be used as a monomer constituting the acrylic polymer (A1).
  • monomers having a hydroxyl group include hydroxyl groups such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate (meth).
  • a monomer having a carboxyl group may be used as the monomer constituting the acrylic polymer (A1).
  • the monomer having a carboxyl group include (meth) acrylic acid esters having a carboxyl group such as 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxypropyl phthalate; Maleic acid, fumaric acid, itaconic acid and the like can be mentioned.
  • an epoxy thermosetting component as the thermosetting component (B) described later, the carboxyl group and the epoxy group in the epoxy thermosetting component react with each other, so that the monomer having a carboxyl group The amount used is preferably small.
  • a monomer having an amino group may be used as the monomer constituting the acrylic polymer (A1).
  • the monomer monomer having an amino group include (meth) acrylic acid esters having an amino group such as monomethylamino (meth) acrylate, monoethylamino (meth) acrylate, and diethylamino (meth) acrylate.
  • vinyl acetate, styrene, ethylene, ⁇ -olefin and the like may be used as the monomer constituting the acrylic polymer (A1).
  • the acrylic polymer (A1) may be cross-linked.
  • Crosslinking is performed by adding a crosslinking agent to the composition for forming a protective film-forming film, in which the acrylic polymer (A1) before being crosslinked has a crosslinkable functional group such as a hydroxyl group. This is performed by reacting the crosslinkable functional group with the functional group of the crosslinker.
  • the cohesive force of the protective film-forming film can be adjusted.
  • the crosslink density of the acrylic polymer (A1) the glass transition temperature of the protective film-forming film after thermosetting and the tensile elastic modulus at 23 ° C. after thermosetting can be controlled.
  • the crosslinking density can be controlled by the addition amount of a crosslinking agent described later.
  • crosslinking agent examples 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 compound examples 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 is usually 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 acrylic polymer (A1) before crosslinking. Used in ratio.
  • the polymer component (A) when the content of the component constituting the protective film-forming film is determined based on the content of the polymer component (A), the polymer component (A) is a crosslinked acrylic polymer. In some cases, the reference content is the content of the acrylic polymer before being crosslinked.
  • thermosetting component (B) Thermosetting component
  • the thermosetting component (B) is added to the protective film-forming film mainly for the purpose of imparting thermosetting properties to the protective film-forming film.
  • the thermosetting component (B) contains at least a compound having a functional group that reacts by heating. Curing is realized by the functional groups of the thermosetting component (B) reacting to form a three-dimensional network structure. Since the thermosetting component (B) is used in combination with the polymer component (A), the viscosity of the coating composition for forming the protective film-forming film is suppressed, and the handleability is improved. Therefore, the weight average molecular weight (Mw) is usually 10,000 or less, preferably 100 to 10,000.
  • thermosetting component (B) for example, an epoxy thermosetting component is preferable.
  • the epoxy thermosetting component contains a compound (B11) having an epoxy group (hereinafter sometimes referred to as “epoxy compound (B11)”), a compound (B11) having an epoxy group, and a thermosetting agent (B12). ) are preferably used, and more preferably a combination of a curing accelerator (B13).
  • (B11) As a compound epoxy compound (B11) having an epoxy group , conventionally known compounds can be used. Specifically, polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, o-cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenols Examples thereof include epoxy compounds having two or more functional groups in the molecule, such as F-type epoxy resins and phenylene skeleton-type epoxy resins. These can be used individually by 1 type or in combination of 2 or more types.
  • thermosetting agent (B12) functions as a curing agent for the epoxy compound (B11).
  • 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.
  • phenolic hydroxyl groups, amino groups, acid anhydrides and the like are preferable, phenolic hydroxyl groups and amino groups are more preferable, and amine-based curing agents having amino groups are particularly preferable.
  • thermosetting agent other than an amine curing agent, such as a phenol curing agent
  • the glass transition temperature after thermal curing of the protective film-forming film is the range described above unless more thermosetting agent is blended. It is difficult to adjust.
  • thermosetting agent (B12) content of the whole thermosetting component (B) must be increased, and there exists a possibility that content of a thermosetting component (B) may become excessive.
  • phenolic curing agent examples include polyfunctional phenolic resin, biphenol, novolac type phenolic resin, dicyclopentadiene type phenolic resin, zylock type phenolic resin, and aralkylphenolic resin.
  • amine curing agent is DICY (dicyandiamide). These can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the ignition curing agent (B12) is usually about 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy compound (B11).
  • the glass transition temperature after the thermosetting of the film for protective film formation can be controlled by adjusting content of an epoxy compound (B11), a thermosetting agent (B12), and a hardening accelerator (B13).
  • the amount of epoxy groups possessed by the epoxy compound (B11) and the amount of active hydrogen possessed by the amine curing agent are in a molar ratio (active hydrogen / Epoxy group), preferably 0.4 to 1.5, more preferably 0.5 to 1.3, particularly preferably 0.6 to 1.1, when the protective film-forming film is thermally cured. It becomes easy to control the later glass transition temperature within the above range.
  • the amine-based curing agent is a film for forming a protective film.
  • the content is preferably 5 to 20 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the epoxy compound (B11).
  • Curing accelerator A curing accelerator (B13) may be used to adjust the rate of thermal curing of the protective film-forming film.
  • the curing accelerator (B13) is particularly preferably used when an epoxy thermosetting component is used as the thermosetting 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 (B13) is contained in an amount of preferably 1 to 10 parts by mass, more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12). It is. By containing the curing accelerator (B13) in an amount within the above range, it has excellent adhesiveness even when exposed to high temperatures and high humidity, and has high reliability even when exposed to severe reflow conditions. Can be achieved. By adding the curing accelerator (B13), the adhesiveness after curing of the protective film-forming film can be improved. Such an action becomes stronger as the content of the curing accelerator (B13) increases.
  • a 2nd binder component provides sheet shape maintenance property and thermosetting to the film for protective film formation by containing a thermosetting polymer component (AB).
  • thermosetting polymer component is a polymer having a functional functional group.
  • the curing functional group is a functional group that can react with each other to form a three-dimensional network structure, and includes a functional group that reacts by heating.
  • the functional functional group may be added to the unit of the continuous structure that becomes the skeleton of the thermosetting polymer component (AB) or may be added to the terminal.
  • the curing functional group may be added to the side chain or directly to the main chain. It may be added.
  • the weight average molecular weight (Mw) of the thermosetting polymer component (AB) is usually 20,000 or more from the viewpoint of achieving the purpose of imparting sheet shape maintainability to the protective film-forming film.
  • thermosetting polymer component (AB) having an epoxy group examples include a phenoxy resin having an epoxy group.
  • thermosetting polymer component (AB) having an epoxy group examples include a phenoxy resin having an epoxy group.
  • it is a polymer similar to the above-mentioned acrylic polymer (A1), which is polymerized using a monomer having an epoxy group as a monomer (epoxy group-containing acrylic polymer). Also good.
  • monomers include epoxy group-containing (meth) acrylic acid esters and non-acrylic epoxy group-containing monomers.
  • epoxy group-containing (meth) acrylic acid esters examples include glycidyl (meth) Non-acrylic epoxy group-containing monomers such as acrylate, ⁇ -methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 3-epoxycyclo-2-hydroxypropyl (meth) acrylate, etc. Examples thereof include glycidyl crotonate and allyl glycidyl ether.
  • the epoxy group-containing monomer an epoxy group-containing (meth) acrylic acid ester is preferable, and glycidyl (meth) acrylate is particularly preferable.
  • the preferred embodiment is the same as that of the acrylic polymer (A1).
  • the thermosetting agent described later as being contained in the second binder component is an amine-based curing agent
  • the epoxy group reacts with active hydrogen possessed by the amine-based curing agent. By doing so, it contributes to the glass transition temperature after thermosetting of the protective film-forming film, and it becomes easy to control the glass transition temperature within the above range. In addition, it becomes easy to control the tensile elastic modulus at 23 ° C. after the thermosetting of the protective film-forming film.
  • thermosetting polymer component (AB) having an epoxy group when used, the thermosetting agent (B12) or the curing accelerator is used as in the case of using the epoxy thermosetting component as the thermosetting component (B). It is preferable to use (B13) in combination.
  • the second binder component may contain the above-described polymer component (A) and thermosetting component (B) in combination with the thermosetting polymer component (AB).
  • the protective film-forming film contains one or both of the thermosetting component (B) and the thermosetting polymer component (AB), the protective film-forming film has thermosetting properties. .
  • the protective film-forming film contains at least the thermosetting component (B). It is preferable. However, when the protective film-forming film contains only the thermosetting component (B), the sheet shape maintainability of the protective film-forming film may be inferior. Then, it is preferable that the film for protective film formation contains a thermosetting component (B) and any one or both of a polymer component (A) and a thermosetting polymer component (AB).
  • the thermosetting component (B) is preferably 70 with respect to a total of 100 parts by mass of the polymer component (A) and the thermosetting polymer component (AB). More than mass parts are contained, more preferably more than 85 parts by mass.
  • the content of the thermosetting component (B) is in such a range with respect to the lower limit, the glass transition temperature after thermosetting of the protective film-forming film and the tensile elastic modulus at 23 ° C. after thermosetting are described above. Easy to adjust.
  • the reference content is the content of the epoxy group-containing acrylic polymer before being crosslinked.
  • the thermosetting component (B) is preferably contained in an amount of 135 parts by mass or less with respect to 100 parts by mass in total of the polymer component (A) and the thermosetting polymer component (AB). It is.
  • the content of the thermosetting component (B) is in such a range with respect to the upper limit, the sheet shape maintainability and flexibility of the protective film-forming film tend to be kept good.
  • the protective film-forming film contains an inorganic filler (C) described later, if the content of the inorganic filler (C) is large, the sheet shape maintainability and flexibility of the protective film-forming film are reduced. In addition, resistance to bending and handleability may be reduced. Therefore, it is particularly preferable that the content of the thermosetting component (B) is in such a range with respect to the upper limit.
  • the protective film-forming film contains a total of 100 masses of the polymer component (A) and the thermosetting polymer component (AB).
  • the epoxy compound (B11) is preferably contained in an amount of 70 parts by mass or more, more preferably 85 to 130 parts by mass, and still more preferably 85 to 120 parts by mass with respect to parts.
  • the film for forming a protective film may contain the following components.
  • the inorganic filler protective film-forming film preferably contains an inorganic filler (C).
  • blending an inorganic filler (C) with the film for protective film formation it becomes easy to adjust the tensile elasticity modulus in 23 degreeC after thermosetting in the above-mentioned range.
  • the inorganic filler (C) is exposed in the portion scraped off by the laser light, and the reflected light diffuses to exhibit a color close to white.
  • the film for protective film formation contains the coloring agent (D) mentioned later, there is an effect that a contrast difference is obtained between the laser marking portion and other portions, and the printing becomes clear.
  • Preferred inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, and the like, beads formed by spheroidizing these, single crystal fibers, glass fibers, and the like.
  • silica filler and alumina filler are preferable.
  • the said inorganic filler (C) can be used individually or in mixture of 2 or more types.
  • the range of the content of the inorganic filler (C) for obtaining the above-mentioned effect more reliably is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film-forming film, More preferred is 40 to 70 parts by mass, and particularly preferred is 55 to 65 parts by mass.
  • the average particle size of the inorganic filler (C) is preferably 0.02 to 5 ⁇ m, more preferably 0.05 to 4.5 ⁇ m, and particularly preferably 0.1 to 4 ⁇ m. By setting the average particle diameter of the inorganic filler (C) within the above range, the warp correction function is improved.
  • the average particle diameter of the inorganic filler (C) is the number average particle diameter calculated as the arithmetic average value of 20 major axis diameters of 20 inorganic fillers (C) randomly selected with an electron microscope.
  • Colorant (D) can be mix
  • the colorant By blending the colorant, malfunction of the semiconductor device due to infrared rays or the like generated from surrounding devices when the semiconductor device is incorporated into equipment can be prevented.
  • the protective film is engraved by means such as laser marking, there is an effect that marks such as characters and symbols can be easily recognized. That is, in a semiconductor device or semiconductor chip on which a protective film is formed, the product number or the like is usually printed on the surface of the protective film by a laser marking method (a method in which the surface of the protective film is scraped off and printed).
  • a laser marking method a method in which the surface of the protective film is scraped off and printed.
  • colorant organic or inorganic pigments and dyes are used.
  • black pigments are preferable from the viewpoint of electromagnetic wave and infrared shielding properties.
  • the black pigment 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 (D) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the colorant (D) is preferably 0.1 to 35 parts by weight, more preferably 0.5 to 25 parts by weight, particularly 100 parts by weight of the total solid content constituting the protective film-forming film.
  • the amount is preferably 1 to 15 parts by mass.
  • Examples of such coupling agents include titanate coupling agents, aluminate coupling agents, silane coupling agents, and the like. Of these, silane coupling agents are preferred.
  • silane coupling agent a functional group that reacts with the organic functional group reacts with a functional group that the polymer component (A), the thermosetting component (B), the thermosetting polymer component (AB), or the like has.
  • a silane coupling agent which is a group is preferably used.
  • Such silane coupling agents include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (methacryloxy).
  • the silane coupling agent is usually 0.1 to 20 parts by mass, preferably 100 parts by mass with respect to a total of 100 parts by mass of the polymer component (A), the thermosetting component (B) and the thermosetting polymer component (AB). It is contained in a proportion of 0.2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass. If the content of the silane coupling agent is less than 0.1 parts by mass, the above effect may not be obtained, and if it exceeds 20 parts by mass, it may cause outgassing.
  • additives may be blended in the film for forming a general-purpose additive protective film as necessary.
  • additives include leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, release agents, and the like.
  • the protective film-forming film has an initial adhesive property and a thermosetting property, and adheres easily by being pressed against a semiconductor wafer, a chip or the like in an uncured state. Moreover, you may heat the film for protective film formation, when pressing. Finally, a protective film having high impact resistance can be provided through thermosetting, excellent in adhesive strength, and can maintain a sufficient protective function even under severe high temperature and high humidity conditions.
  • the protective film-forming film may have a single layer structure or a multilayer structure.
  • the film for forming a protective film is obtained, for example, using a composition (composition for forming a protective film) obtained by mixing the above components at an appropriate ratio.
  • the composition for forming a protective film may be diluted with a solvent in advance, or may be added to the solvent during mixing. Moreover, you may dilute with a solvent at the time of use of the composition for protective film formation. Examples of such a solvent include ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, methyl ethyl ketone, acetonitrile, hexane, cyclohexane, toluene, heptane and the like.
  • the thickness of the protective film-forming film is not particularly limited, but is preferably 3 to 300 ⁇ m, more preferably 5 to 250 ⁇ m, and particularly preferably 7 to 200 ⁇ m.
  • the maximum transmittance at a wavelength of 300 to 1200 nm which is a measure showing the transmittance of visible light and / or infrared rays and ultraviolet rays in the protective film-forming film, is preferably 20% or less, more preferably 0 to 15%. Preferably, it is more than 0% and not more than 10%, particularly preferably 0.001 to 8%.
  • the maximum transmittance of the protective film-forming film at a wavelength of 300 to 1200 nm can be adjusted by the colorant (D).
  • the maximum transmittance of the protective film-forming film was determined by using a UV-vis spectrum inspection apparatus (manufactured by Shimadzu Corporation), and the entire thickness of the protective film-forming film (thickness 25 ⁇ m) after curing at 300 to 1200 nm. The light transmittance was measured and set to the highest value (maximum transmittance).
  • the film for forming a protective film of the present invention is used as a protective film for a semiconductor wafer or chip made of silicon, gallium arsenide, or the like as an adherend.
  • a protective film-forming film can be formed on the process film.
  • Film formation is performed by applying a composition for forming a protective film-forming film on the process film according to a generally known method such as a roll knife coater, gravure coater, die coater, reverse coater, and drying.
  • the process film can be used as it is as a support sheet or cover film which will be described later.
  • the process film may be either the support sheet or the cover film, and the material to be transferred may be the other one of the support sheet or the cover film.
  • the composite sheet for forming a protective film is obtained by forming the support sheet so as to be peelable on one side of the film for forming a protective film.
  • the shape of the composite sheet for forming a protective film is not limited to a single sheet, and may be a long strip or roll it up. Examples of the support sheet include a release sheet, and an adhesive sheet described later can be used.
  • the composite sheet for forming a protective film is affixed to various adherends, and in some cases, the adherend is subjected to necessary processing such as dicing on the composite sheet for forming a protective film. Thereafter, the support film is peeled off by allowing the protective film-forming film to remain adhered to the adherend. That is, it is used in a process including a step of transferring a protective film-forming film from a support sheet to an adherend.
  • the protective film-forming film can have the same shape as the support sheet.
  • the protective film-forming composite sheet is prepared by making the protective film-forming film substantially the same shape as the wafer or including the shape of the wafer, and having a larger size than the protective film-forming film. A pre-molded configuration may be taken that is laminated on the support sheet.
  • release sheets include 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, fluororesin film Etc. are used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient.
  • the surface tension of the surface of the release sheet in contact with the protective film-forming film is preferably 40 mN / m or less, more preferably 37 mN / m or less, and particularly preferably 35 mN / m or less.
  • the lower limit is usually about 25 mN / m.
  • Such a release sheet having a relatively low surface tension can be obtained by appropriately selecting the material, and can also be obtained by applying a release agent to the surface of the release sheet and performing 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 can be used without any solvent, or can be diluted or emulsified in a solvent to obtain a gravure coater, Mayer bar coater, air knife coater.
  • the release sheet coated with a release coater may be applied at room temperature or under heating, or may be cured with an electron beam to form a release agent layer.
  • the surface tension of the release sheet may be adjusted by laminating films by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion processing, or the like. That is, a film in which the surface tension of at least one surface is within a preferable range as the surface in contact with the protective film-forming film of the release sheet described above is such that the surface is in contact with the protective film-forming film.
  • a laminate laminated with another film may be manufactured and used as a release sheet.
  • an adhesive sheet having an adhesive layer formed on a substrate is preferably used as the support sheet.
  • the protective film-forming film is laminated on the pressure-sensitive adhesive layer provided on the support sheet.
  • the pressure-sensitive adhesive layer may be a weakly-adhesive layer having an adhesive strength that can peel off the protective film-forming film, or an energy-ray-curing layer that decreases in adhesive strength when irradiated with energy rays. May be.
  • the pressure-sensitive adhesive layer includes various conventionally known pressure-sensitive adhesives (for example, rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based general-purpose pressure-sensitive adhesives, pressure-sensitive adhesives, energy ray-curable pressure-sensitive adhesives, A thermal expansion component-containing pressure-sensitive adhesive or the like).
  • various conventionally known pressure-sensitive adhesives for example, rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based general-purpose pressure-sensitive adhesives, pressure-sensitive adhesives, energy ray-curable pressure-sensitive adhesives, A thermal expansion component-containing pressure-sensitive adhesive or the like.
  • the protective film-forming composite sheet functions as a dicing sheet for supporting the adherend in the dicing process, there is no need to dice by dicing a separate dicing sheet to the wafer with the protective film-forming film in the dicing process.
  • the manufacturing process of the semiconductor device can be simplified.
  • the protective film-forming composite sheet When the protective film-forming composite sheet has a pre-formed configuration, the protective film-forming composite sheet may have the following first, second, or third configuration.
  • first, second, or third configuration Hereinafter, each configuration of the protective film-forming composite sheet 100 will be described with reference to FIGS.
  • the 1st structure is the structure by which the adhesive sheet 3 in which the adhesive layer 2 was formed on the base material 1 was formed so that peeling was possible on the single side
  • the pressure-sensitive adhesive layer is composed of an energy ray-curable pressure-sensitive adhesive, and the region where the protective film-forming film is laminated is irradiated with energy rays in advance to reduce the adhesiveness. On the other hand, other regions may be maintained with high adhesive strength without being irradiated with energy rays.
  • 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.
  • the second configuration is a configuration in which a jig adhesive layer 4 is separately provided on the pressure-sensitive adhesive layer 2 of the protective film-forming composite sheet 100 in a region that does not overlap with the protective film-forming film 10. is there.
  • tool adhesion layer the layer which consists of a double-sided adhesive sheet which has a core material, and the single layer of an adhesive can be employ
  • the third configuration includes an interfacial adhesion adjusting layer 5 having a shape that can completely include the shape of the protective film-forming film between the protective film-forming film 10 and the pressure-sensitive adhesive layer 2.
  • the interface adhesion adjusting layer may be a predetermined film or an interface adhesion adjusting pressure-sensitive adhesive layer.
  • the interfacial adhesion-adjusting pressure-sensitive adhesive layer is preferably a layer obtained by previously irradiating an energy ray-curable pressure-sensitive adhesive and curing it.
  • the protective film-forming composite sheet By forming the protective film-forming composite sheet in these first to third configurations, the protective film is formed in the region surrounding the protective film-forming film due to sufficient adhesiveness of the pressure-sensitive adhesive layer or the jig adhesive layer.
  • the forming composite sheet can be adhered to a jig.
  • the adhesiveness at the interface between the protective film-forming film and the pressure-sensitive adhesive layer or the interfacial adhesion adjusting layer can be controlled to facilitate the pickup of the protective film-forming film or the chip to which the protective film is fixed.
  • the protective film-forming composite sheet does not have a pre-molded configuration, that is, as shown in FIG. 4, the protective film-forming film 10 and the support sheet (in FIG. 4, the pressure-sensitive adhesive layer 2 is formed on the substrate 1).
  • a jig adhesive layer 4 may be provided on the outer peripheral portion of the surface of the protective film-forming film 10. As the jig adhesive layer, the same one as described above can be used.
  • the thickness of the heel support sheet is usually 10 to 500 ⁇ m, preferably 15 to 300 ⁇ m, particularly preferably 20 to 250 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is 3 to 50 ⁇ m in the support sheet.
  • a cover film may be temporarily attached to the surface opposite to the surface to be attached to the support sheet of the protective film-forming film.
  • the cover film may cover the pressure-sensitive adhesive layer when the support sheet is a pressure-sensitive adhesive sheet or the jig adhesive layer.
  • the same cover film as the above-described release sheet can be used.
  • the film thickness of the cover film is usually about 5 to 300 ⁇ m, preferably about 10 to 200 ⁇ m, particularly preferably about 20 to 150 ⁇ m.
  • Such a protective film-forming film of the protective film-forming composite sheet can be used as a protective film of an adherend.
  • the protective film-forming film is affixed to the back surface of the face-down chip semiconductor wafer or semiconductor chip, and is cured by an appropriate means to have a function of protecting the semiconductor wafer or semiconductor chip as an alternative to the sealing resin.
  • the protective film When pasted on a semiconductor wafer, the protective film has a function of reinforcing the wafer, so that damage to the wafer can be prevented.
  • the method for manufacturing a semiconductor device preferably includes a step of attaching a protective film-forming film of the protective film-forming composite sheet to a semiconductor wafer to obtain a semiconductor chip having the protective film.
  • a protective film-forming film of the protective film-forming composite sheet is attached to the back surface of a semiconductor wafer having a circuit formed on the front surface, and then a semiconductor chip having a protective film on the back surface is obtained.
  • the protective film is preferably a protective film for a semiconductor wafer or a semiconductor chip.
  • the method for manufacturing a semiconductor device preferably further includes the following steps (1) to (3), and in order to exert the function of correcting the warpage of the wafer included in the protective film-forming film, Step (2) is performed prior to 3).
  • the process (3) is performed from the viewpoint of simplifying the manufacturing process of the semiconductor device.
  • Step (1) peeling off the protective film-forming film or protective film and the support sheet
  • Step (2) The protective film-forming film is cured to obtain a protective film.
  • the method for manufacturing a semiconductor device in the present invention may further include the following step (4) in addition to the above steps (1) to (3).
  • 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 50 to 500 ⁇ m.
  • the crushed layer is removed by chemical etching, plasma etching, or the like.
  • a protective film-forming film of the protective film-forming composite sheet is attached to the back surface of the semiconductor wafer.
  • the steps (1) to (3) are performed in the order of the steps (1), (2), (3), the steps (2), (1), (3) or the steps (2), (3), It is performed in any order of the order of (1). 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 protective film-forming film of the protective film-forming composite sheet is attached to the back surface of the semiconductor wafer having a circuit formed on the front surface.
  • the support sheet is peeled from the protective film-forming film to obtain a laminate of the semiconductor wafer and the protective film-forming film.
  • the protective film-forming film is cured, and a protective film is formed on the entire surface of the wafer.
  • the protective film-forming film is cured by thermosetting.
  • a protective film made of a cured resin is formed on the back surface of the wafer, and the strength is improved as compared with the case of the wafer alone, so that damage during handling of the thinned wafer can be reduced.
  • the thickness of the protective film is excellent compared to a coating method in which a coating liquid for the protective film is directly applied to the back surface of the wafer or chip.
  • the laminated body of the semiconductor wafer and the protective film is diced for each circuit formed on the wafer surface. Dicing is performed so as to cut both the wafer and the protective film.
  • the wafer is diced by a conventional method using a dicing sheet. As a result, a group of semiconductor chips that are separated on the dicing sheet and have a protective film on the back surface is obtained.
  • Laser printing is performed by a laser marking method, and the surface of the protective film is scraped off by laser light irradiation to mark a product number or the like on the protective film.
  • a semiconductor chip having a protective film on the back surface is picked up by a general-purpose means such as a collet to obtain a chip with a protective film. Then, the semiconductor device can be manufactured by mounting the chip with protective film on a predetermined base by the face-down method. Further, a semiconductor device can be manufactured by adhering a semiconductor chip having a protective film on the back surface to another member (on the chip mounting portion) such as a die pad portion or another semiconductor chip. According to the present invention as described above, a protective film having high thickness uniformity can be easily formed on the back surface of the chip, and cracks after the dicing process and packaging are less likely to occur.
  • the step (3) is performed before the step (1) (steps (2), (3),
  • the composite sheet for forming a protective film can serve as a dicing sheet. That is, it can be used as a sheet for supporting the semiconductor wafer during the dicing process.
  • the semiconductor wafer is bonded to the inner peripheral portion of the protective film forming composite sheet via the protective film forming film, and the outer peripheral portion of the protective film forming composite sheet is joined to another jig such as a ring frame.
  • the composite sheet for forming a protective film attached to the semiconductor wafer is fixed to the apparatus, and dicing is performed.
  • the protective film-forming film of the present invention and the protective film-forming composite sheet using the film can be used for the protection of semiconductor compounds, glass, ceramics, metals, etc., in addition to the above usage methods.
  • ⁇ Glass transition temperature after thermosetting> Four protective film-forming films with a thickness of 45 ⁇ m are laminated and thermally cured (at 130 ° C. for 2 hours) in an oven to form a strip with a width of 4.5 mm, a length of 20.0 mm, and a thickness of 0.18 mm.
  • the test piece was produced by cutting. Using a viscoelasticity measuring apparatus (DMA instruments made by TA instruments, DMA Q800), in a tensile mode, the tan ⁇ (ratio of loss elastic modulus to storage elastic modulus) of the test piece was set to a frequency of 11 Hz, a heating rate of 3 ° C./min, The measurement was performed at 0 to 300 ° C. in an air atmosphere. The temperature at which tan ⁇ exhibited the maximum value in this temperature range was read and used as the glass transition temperature (Tg) after thermosetting of the protective film-forming film.
  • Tg glass transition temperature
  • thermosetting> The storage elastic modulus at 23 ° C. of the measurement data obtained by the above measurement of ⁇ glass transition temperature after thermosetting> was read, and the tensile elastic modulus at 23 ° C. after thermosetting of the protective film-forming film was obtained.
  • a test piece (size: 100 mm ⁇ 100 mm) in which a film for forming a protective film having a thickness of 45 ⁇ m was attached to a copper foil having a thickness of 30 ⁇ m was thermally cured (at 130 ° C. for 2 hours) in an atmosphere in an oven. Then, due to the shrinkage accompanying thermal curing of the protective film-forming film, the distance between the points is the maximum value in the rounded shape of the copper foil that is rounded with the surface on which the protective film-forming film is attached inside. The following two points were taken and the distance was measured. It means that the copper foil is greatly warped as the distance is smaller, and the stress due to thermal shrinkage of the protective film-forming film is larger, so that it can be judged that the warp correction ability is high.
  • ⁇ Reliability evaluation> 1 Production of chip with protective film # 2000 Polished protective film-forming film of composite sheet for protective film formation on a polished silicon wafer (200 mm diameter, 350 ⁇ m thickness) tape mounter (Adwill RAD-3600 F / 12) was applied while heating to 70 ° C., and then the support sheet was peeled off. Thereafter, the protective film-forming film was cured by heating at 130 ° C. for 2 hours to obtain a laminate of a silicon wafer and a protective film.
  • the protective film side of the laminate obtained above is affixed to a dicing tape (Adwill D-686H manufactured by Lintec Corporation), and is diced to a size of 3 mm ⁇ 3 mm using a dicing apparatus (DFD651 manufactured by Disco Corporation). A chip with a protective film for property evaluation was obtained.
  • ⁇ Wafer warpage evaluation> An 8-inch wafer with a circuit having a thickness of 200 ⁇ m and having a concave warpage (warpage amount: 10 mm) on the circuit surface side (surface side) was prepared (see FIG. 5). Next, a protective film-forming film was attached to the back surface of the wafer, and heat cured at 130 ° C. for 2 hours. Then, the case where the amount of warpage of the obtained wafer was 2 mm or less was evaluated as “good”, and the case where the amount of warpage of the wafer exceeded 2 mm was evaluated as “bad”. If the amount of warpage of the wafer is 2 mm or less, it can be transferred by a general wafer mounter.
  • composition for forming protective film Each component which comprises the composition for protective film formation is shown below.
  • A1-1) Polymer component: acrylic polymer obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 15 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate, and 10 parts by mass of 2-hydroxyethyl acrylate (weight) (Average molecular weight: 900,000, glass transition temperature: -28 ° C)
  • A1-2 Polymer component: acrylic polymer obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 35 parts by mass of methyl acrylate, and 10 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 900,000, Glass transition temperature: -31 ° C)
  • B11-1) Bisphenol A type epoxy resin (Mitsubishi Chemical jER828, epoxy equivalent of 184 to 194 g / eq)
  • B11-2) Bis
  • Examples and Comparative Examples The said component was mix
  • the compounding quantity of each component in Table 1 shows the mass part of solid content conversion, and solid content means all components other than a solvent in this invention.
  • the protective film-forming composition having the composition shown in Table 1 was diluted with methyl ethyl ketone so that the solid content concentration was 61% by mass, and the release-treated surface of the support sheet (SP-PET3811 manufactured by Lintec, thickness 38 ⁇ m) Coating and drying (drying conditions: 120 ° C.
  • Base material 2 Adhesive layer 3: Adhesive sheet (support sheet) 4: Jig adhesion layer 5: Interfacial adhesion adjustment layer 10: Film for protective film formation 100: Composite sheet for protective film formation

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Dicing (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
PCT/JP2014/058038 2013-03-22 2014-03-24 保護膜形成用フィルムおよび保護膜形成用複合シート WO2014148642A1 (ja)

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JP2014530843A JP5615471B1 (ja) 2013-03-22 2014-03-24 保護膜形成用フィルムおよび保護膜形成用複合シート
KR1020217018040A KR102377100B1 (ko) 2013-03-22 2014-03-24 보호막 형성용 필름 및 보호막 형성용 복합 시트
KR1020157026015A KR20150135284A (ko) 2013-03-22 2014-03-24 보호막 형성용 필름 및 보호막 형성용 복합 시트
KR1020217018041A KR102541666B1 (ko) 2013-03-22 2014-03-24 보호막 형성용 필름 및 보호막 형성용 복합 시트
SG11201507775XA SG11201507775XA (en) 2013-03-22 2014-03-24 Protective film-forming film and protective film-forming composite sheet
CN201480004970.7A CN104937712B (zh) 2013-03-22 2014-03-24 保护膜形成用膜及保护膜形成用复合片
KR1020227007805A KR20220035981A (ko) 2013-03-22 2014-03-24 보호막 형성용 필름 및 보호막 형성용 복합 시트
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KR20210074413A (ko) 2021-06-21
KR102377100B1 (ko) 2022-03-21
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CN104937712A (zh) 2015-09-23
KR20220035981A (ko) 2022-03-22
TWI516530B (zh) 2016-01-11
CN104937712B (zh) 2018-03-27
TW201510008A (zh) 2015-03-16
KR20150135284A (ko) 2015-12-02
SG11201507775XA (en) 2015-10-29
PH12015502208B1 (en) 2016-02-01
KR102541666B1 (ko) 2023-06-13
KR20210074414A (ko) 2021-06-21
JP5615471B1 (ja) 2014-10-29

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