WO2014084357A1 - Feuille dotée d'une couche de formation de film de résine durcissable et procédé de fabrication de dispositif à semi-conducteur au moyen de la feuille - Google Patents

Feuille dotée d'une couche de formation de film de résine durcissable et procédé de fabrication de dispositif à semi-conducteur au moyen de la feuille Download PDF

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Publication number
WO2014084357A1
WO2014084357A1 PCT/JP2013/082187 JP2013082187W WO2014084357A1 WO 2014084357 A1 WO2014084357 A1 WO 2014084357A1 JP 2013082187 W JP2013082187 W JP 2013082187W WO 2014084357 A1 WO2014084357 A1 WO 2014084357A1
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WIPO (PCT)
Prior art keywords
resin film
forming layer
curable resin
sheet
silane coupling
Prior art date
Application number
PCT/JP2013/082187
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English (en)
Japanese (ja)
Inventor
雄一 小曾根
正啓 古館
市川　功
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2014549922A priority Critical patent/JP6298409B2/ja
Priority to CN201380062060.XA priority patent/CN104797423B/zh
Priority to KR1020157013915A priority patent/KR102224971B1/ko
Publication of WO2014084357A1 publication Critical patent/WO2014084357A1/fr

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Classifications

    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • 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
    • 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

  • This invention relates to the sheet
  • Semiconductor wafers such as silicon and gallium arsenide are manufactured in a large diameter state. After the semiconductor wafer is cut and separated (diced) into element pieces (semiconductor chips), the semiconductor wafer is transferred to the next bonding process. At this time, the semiconductor wafer is subjected to dicing, cleaning, drying, expanding, and pick-up processes while being attached to an adhesive sheet called a dicing sheet, and then transferred to the next bonding process.
  • various dicing / die bonding sheets having both a wafer fixing function and a die bonding function have been proposed in order to simplify the pick-up process and the bonding process (see, for example, Patent Document 1).
  • the dicing die-bonding sheet enables so-called direct die bonding, and can omit the application process of the die fixing adhesive.
  • a dicing die bond sheet By using a dicing die bond sheet, a semiconductor chip with an adhesive layer can be obtained, and direct die bonding of the chip becomes possible.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-17246.
  • the adhesive strength particularly the shear strength, may not be improved as expected.
  • 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 2 JP 2009-200909A. -138026.
  • the adhesion between the chip and the protective film is improved by using a silane coupling agent, and the peeling at the interface between the protective film and the chip is suppressed. Adhesive strength and shear strength may not be improved.
  • the present invention has been made in view of the prior art as described above, and is a resin film forming layer functioning as a precursor of an adhesive film or a protective film or a cured resin film (hereinafter referred to as “cured film”). Is intended to improve the adhesion between the adherend semiconductor chip and the semiconductor wafer.
  • the present inventors have intensively studied. As a result, when the silane coupling agent is simply added to the resin film forming layer and the silane coupling agent is uniformly present inside the resin film forming layer, the shear strength of the cured film is improved as expected. I found it not. As a result of further investigation, the concentration gradient in the thickness direction of the silane coupling agent was controlled, and the silane coupling agent was unevenly distributed on the surface (that is, the adhesive interface with the adherend), resulting in a small amount of silane coupling agent. Even so, it succeeded in improving the adhesive strength.
  • the present invention for solving the above problems includes the following gist.
  • the curable resin film-forming layer contains a curable binder component and a silane coupling agent (C), and the silane coupling agent on at least one surface of the resin film in the cured resin film of the curable resin film-forming layer
  • the surface silicon element concentration (X) derived from (C) is measured at at least one point each in a depth range of 40 to 60 nm, 60 to 80 nm, and 80 to 100 nm in the depth direction from the surface, for a total of 3 points or more.
  • a semiconductor wafer is attached to the curable resin film-forming layer of the sheet with the curable resin film-forming layer according to [6], and the semiconductor wafer is diced into a semiconductor chip.
  • a method for manufacturing a semiconductor device comprising: a step of fixing and remaining a resin film forming layer and peeling it from a support sheet, and thermocompression bonding the semiconductor chip to an adherend via the resin film forming layer.
  • the silane coupling agent is unevenly distributed at the adhesion interface with the adherend, thereby providing the semiconductor chip as the adherend. This makes it possible to improve adhesion to semiconductor wafers. Moreover, in this invention, the unexpected effect that there existed the said effect was obtained, the one where the compounding quantity of a silane coupling agent is smaller.
  • seat with a curable resin film formation layer which concerns on this invention has a support sheet and the curable resin film formation layer formed in this support sheet so that peeling was possible.
  • curable resin film forming layer At least the functions required for the curable resin film-forming layer (hereinafter sometimes simply referred to as “resin film-forming layer”) are (1) film-forming property (sheet-forming property) and (2) initial adhesiveness. (3) It is curable.
  • the resin film-forming layer can be provided with (1) film-forming property (sheet-forming property) and (3) curability by adding a curable binder component.
  • a curable binder component a polymer component (A ) And the first binder component containing the curable component (B) or the second binder component containing the curable polymer component (AB) having the properties of the component (A) and the component (B). Can do.
  • the initial adhesiveness may be pressure-sensitive adhesiveness, It may have a property of being softened and bonded by heat.
  • the initial adhesiveness is usually controlled by adjusting various properties of the binder component and adjusting the blending amount of the inorganic filler (D) described later.
  • hardenable binder component provides film forming property and curability to a resin film formation layer by containing a polymer component (A) and a sclerosing
  • a 1st curable binder component does not contain a curable polymer component (AB) for convenience which distinguishes from a 2nd curable binder component.
  • the polymer component (A) is added to the resin film-forming layer mainly for the purpose of imparting film-forming properties (sheet-forming property) to the resin film-forming layer.
  • 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).
  • GPC gel permeation chromatography method
  • 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.
  • an acrylic polymer, polyester, phenoxy resin (for the purpose of distinguishing from the curable polymer (AB) described later, limited to those having no epoxy group), polycarbonate, polyether, polyurethane A rubber polymer or the like can be used as the polymer component (A).
  • an acrylic urethane resin obtained by reacting a urethane prepolymer having an isocyanate group at a molecular terminal with an acrylic polyol having an hydroxyl group and an acrylic polyol having a combination of two or more of these Also good.
  • 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.
  • Tg glass transition temperature
  • the weight average molecular weight of the acrylic polymer (A1) is more preferably 100,000 to 1,500,000. By setting the weight average molecular weight of the acrylic polymer (A1) in the above range, the adhesion of the resin film forming layer to the adherend is improved. If the weight average molecular weight of the acrylic polymer (A1) is too low, the adhesion between the resin film forming layer and the support sheet is increased, and transfer failure of the resin film forming layer may occur.
  • the acrylic polymer (A1) contains (meth) acrylic acid ester at least in the constituent monomer.
  • Examples of (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, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate, etc .; having a cyclic skeleton (meth) Acrylate, specifically cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate
  • (meth) acryl may be used in the meaning including both acryl and methacryl.
  • a monomer having a hydroxyl group may be used as the monomer constituting the acrylic polymer (A1).
  • a monomer having a hydroxyl group when used, when a hydroxyl group is introduced into the acrylic polymer (A1) and the resin film forming layer additionally contains an energy ray-curable component (B2), this and the acrylic polymer Compatibility with (A1) is improved.
  • the monomer having a hydroxyl group include (meth) acrylic acid ester having a hydroxyl group such as 2-hydroxylethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-methylolalkyl (meth) acrylamide and the like. .
  • a monomer having a carboxyl group may be used as the monomer constituting the acrylic polymer (A1).
  • a carboxyl group is introduced into the acrylic polymer (A1), and the resin film forming layer additionally contains an energy ray curable component (B2).
  • 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; (meth) acrylic acid, maleic acid , Fumaric acid, itaconic acid and the like.
  • an epoxy-based thermosetting component as the curable component (B) described below, the carboxyl group and the epoxy group in the epoxy-based thermosetting component react with each other. The amount used is preferably small.
  • a monomer having an amino group may be used as a monomer constituting the acrylic polymer (A1).
  • a monomer having an amino group examples include (meth) acrylic acid esters having an amino group such as monoethylamino (meth) acrylate.
  • the monomer constituting the acrylic polymer (A1) vinyl acetate, styrene, ethylene, ⁇ -olefin and the like may be used.
  • the acrylic polymer (A1) may be cross-linked.
  • Crosslinking is performed by adding a crosslinking agent to the composition for forming the resin film-forming layer in which the acrylic polymer (A1) before being crosslinked has a crosslinkable functional group such as a hydroxyl group. This is carried out by the reaction of the functional group with the functional group of the crosslinking agent.
  • 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 resin film forming layer 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.
  • Non-acrylic resin In addition, as the polymer component (A), polyester, phenoxy resin (for the purpose of distinguishing from the curable polymer (AB) described later, limited to those having no epoxy group), polycarbonate, poly One type of non-acrylic resin (A2) selected from ethers, polyurethanes, rubber polymers, or a combination of two or more of these may be used, or a combination of two or more types. Such a resin preferably has a weight average molecular weight of 20,000 to 100,000, more preferably 20,000 to 80,000.
  • the glass transition temperature of the non-acrylic resin (A2) is preferably in the range of ⁇ 30 to 150 ° C., more preferably in the range of ⁇ 20 to 120 ° C.
  • the glass transition temperature of the non-acrylic resin is preferably in the range of ⁇ 30 to 150 ° C., more preferably in the range of ⁇ 20 to 120 ° C.
  • non-acrylic resin (A2) is used in combination with the above-mentioned acrylic polymer (A1), delamination between the support sheet and the resin film-forming layer during transfer of the resin film-forming layer to the adherend is performed. This can be easily carried out, and furthermore, the resin film forming layer follows the transfer surface, and the generation of voids can be suppressed.
  • the content of the non-acrylic resin (A2) is such that the non-acrylic resin (A2) and the acrylic polymer (
  • the mass ratio (A2: A1) to A1) is usually in the range of 1:99 to 60:40, preferably 1:99 to 30:70.
  • the content of the non-acrylic resin (A2) is in this range, the above effect can be obtained.
  • the curable component (B) is added to the resin film forming layer mainly for the purpose of imparting curability to the resin film forming layer.
  • a thermosetting component (B1) or an energy beam curable component (B2) can be used. Moreover, you may use combining these.
  • the thermosetting component (B1) contains at least a compound having a functional group that reacts by heating.
  • the energy ray-curable component (B2) contains a compound (B21) having a functional group that reacts by irradiation with energy rays, and is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams.
  • Curing is realized by the functional groups of these curable components reacting to form a three-dimensional network structure. Since the curable component (B) is used in combination with the polymer component (A), from the viewpoint of suppressing the increase in viscosity of the coating composition for forming the resin film-forming layer and improving the handleability. Usually, its weight average molecular weight (Mw) is 10,000 or less, preferably 100 to 10,000.
  • thermosetting component resin film forming layer When the thermosetting component resin film forming layer is cured, it may be difficult to irradiate the resin film forming layer sandwiched between the chip mounting portion and the chip with energy rays. It is preferable to use the sex component (B1).
  • the thermosetting component for example, an epoxy thermosetting component is preferable.
  • the epoxy thermosetting component preferably contains a compound (B11) having an epoxy group and a combination of a compound (B11) having an epoxy group and a thermosetting agent (B12).
  • epoxy compound (B11) Compound having an epoxy group
  • a conventionally known compound can be used. Specifically, polyfunctional epoxy resin, bisphenol A type diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene (DCPD) type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin And epoxy compounds having two or more functional groups in the molecule, such as 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 resin film forming layer preferably contains 1 to 1500 parts by mass of the epoxy compound (B11), more preferably 100 parts by mass of the polymer component (A). Is contained in an amount of 3 to 1200 parts by mass.
  • content of an epoxy compound (B11) into the said range, the adhesiveness of the resin film formation layer with respect to a to-be-adhered body improves.
  • the amount of the epoxy compound (B11) exceeds 1500 parts by mass, the peeling force between the resin film forming layer and the support sheet increases, and transfer failure of the resin film forming layer may occur.
  • 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. Examples of 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.
  • the curing agent having a phenol hydroxyl group examples include polyfunctional phenol resins, biphenols, novolac phenol resins, dicyclopentadiene phenol resins, zyloc phenol resins, and aralkyl phenol resins.
  • Specific examples of the curing agent having an amino group include DICY (dicyandiamide). These can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the thermosetting agent (B12) 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 epoxy compound (B11).
  • content of a thermosetting agent (B12) into the said range, the adhesiveness of the resin film formation layer with respect to a to-be-adhered body improves. If the content of the thermosetting agent is excessive, the moisture absorption rate of the resin film forming layer increases and the reliability of the semiconductor device may be lowered.
  • Curing accelerator A curing accelerator (B13) may be used to adjust the thermosetting speed of the resin film-forming layer.
  • the curing accelerator (B13) is particularly preferably used when an epoxy thermosetting component is used as the thermosetting component (B1).
  • 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-di (hydroxymethyl) imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; organics such as tributylphosphine, diphenylphosphine, triphenylphosphine Phosphines; 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 preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12). Included in the amount of.
  • the curing accelerator (B13) 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.
  • the content of the curing accelerator (B13) is excessive, the curing accelerator having a high polarity moves to the adhesion interface side in the resin film forming layer under high temperature and high humidity, and is unevenly distributed, thereby reliability of the semiconductor device. It is thought to decrease.
  • the energy ray curable component resin film forming layer contains the energy ray curable component, so that a resin film can be formed by short-time energy ray irradiation without performing a heat curing step requiring a large amount of energy and a long time.
  • the layer can be cured. Thereby, the manufacturing cost can be reduced.
  • the resin film forming layer includes both the thermosetting component (B1) and the energy ray curable component (B2), the resin film forming layer is used before the thermosetting step. Can be pre-cured by irradiation with energy rays. This makes it possible to control the adhesion at the interface between the resin film forming layer and the support sheet, and to improve the process suitability of the adhesive film in processes performed before the thermosetting process such as the wire bonding process. It becomes.
  • a compound (B21) having a functional group that reacts by irradiation with energy rays may be used alone, but photopolymerization with a compound (B21) having a functional group that reacts by irradiation with energy rays. It is preferable to use a combination of initiators (B22).
  • (B21) Compound having a functional group that reacts upon irradiation with energy rays
  • Compound (B21) having a functional group that reacts upon irradiation with energy rays (hereinafter sometimes referred to as “energy ray-reactive compound (B21)”) Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate Examples include acrylate compounds such as acrylate and dicyclopentadiene dimethoxydiacrylate, and oligoester acrylate, urethane acrylate oligomer, and epoxy.
  • the resin film forming layer preferably contains 1 to 1500 parts by mass of the energy ray reactive compound (B21) with respect to 100 parts by mass of the polymer component (A). More preferably, it is contained in an amount of 3 to 1200 parts by mass.
  • photopolymerization initiator (B22) 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 (B22) can be used individually by 1 type or in combination of 2 or more types.
  • the blending ratio of the photopolymerization initiator (B22) 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 ray reactive compound (B21). .
  • the blending ratio of the photopolymerization initiator (B22) is less than 0.1 parts by mass, sufficient curability may not be obtained due to insufficient photopolymerization, and if it exceeds 10 parts by mass, the residue does not contribute to photopolymerization. May cause a malfunction.
  • the second curable binder component imparts film forming properties (sheet forming properties) and curability to the resin film forming layer by containing the curable polymer component (AB).
  • the curable polymer component (AB) 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 examples thereof include a functional group that reacts by heating and a functional group that reacts by energy rays.
  • the functional functional group may be added to the unit of the continuous structure that becomes the skeleton of the curable polymer component (AB) or may be added to the terminal.
  • the functional functional group may be added to the side chain or directly to the main chain. You may do it.
  • the weight average molecular weight (Mw) of the curable polymer component (AB) is usually 20,000 or more from the viewpoint of achieving the purpose of imparting a film forming property (sheet forming property) to the resin film forming layer.
  • the functional group that reacts by heating includes an epoxy group.
  • examples of the curable polymer component (AB) having an epoxy group include a high molecular weight epoxy group-containing compound and a phenoxy resin having an epoxy group.
  • the curable polymer component (AB) is a polymer similar to the above-mentioned acrylic polymer (A1), and is polymerized using a monomer having an epoxy group as the monomer (epoxy) Group-containing acrylic polymer).
  • monomers include (meth) acrylic acid esters having a glycidyl group such as glycidyl (meth) acrylate.
  • the preferred embodiment is the same as that of the acrylic polymer (A1).
  • thermosetting agent (B12) or the curing accelerator (B13) is used as in the case of using an epoxy thermosetting component as the curable component (B). ) May be used in combination.
  • Examples of the functional group that reacts with energy rays include a (meth) acryloyl group.
  • the curable polymer component (AB) having a functional group that reacts with energy rays an acrylate compound having a polymer structure such as polyether acrylate, and the like having a high molecular weight can be used.
  • a raw material polymer having a functional group X such as a hydroxyl group in a side chain, a functional group Y that can react with the functional group X (for example, an isocyanate group when the functional group X is a hydroxyl group) and energy beam irradiation a polymer prepared by reacting a low molecular compound having a functional group that reacts with the above may be used.
  • the preferred mode of the raw material polymer is the same as that of the acrylic polymer (A).
  • the photopolymerization initiator (B22) may be used in the same manner as when the energy ray curable component (B2) is used. .
  • the second binder component may contain the above-described polymer component (A) and curable component (B) in combination with the curable polymer component (AB).
  • the resin film forming layer contains a silane coupling agent (C) in addition to the curable binder component.
  • the silane coupling agent (C) is a silicon compound having a functional group that reacts with an inorganic substance and a functional group that reacts with an organic functional group, and the adhesion of the resin film forming layer to an adherend, Blended to improve adhesion.
  • the silane coupling agent (C) the water resistance can be improved without impairing the heat resistance of the cured film obtained by curing the resin film forming layer.
  • the sheet with a curable resin film-forming layer of the present invention is characterized in that the silane coupling agent (C) is unevenly distributed on the surface of the curable resin film-forming layer.
  • the dispersion state of the silane coupling agent (C) is determined by measuring the concentration of silicon element derived from the silane coupling agent (C) in the surface and thickness direction by X-ray photoelectron spectroscopy (XPS) on the cured resin film. It can be confirmed with. That is, the surface silicon element concentration (X) is measured by XPS analysis. Thereafter, the C 60 ion sputtering cutting in the thickness direction to a predetermined depth, repeatedly carrying out the XPS analysis, measuring the change in the silicon ion concentration in the thickness direction.
  • XPS X-ray photoelectron spectroscopy
  • silane coupling agent (C) Silicon element concentration from can be measured with high accuracy. Further, according to XPS, since a silicon element derived from an organic compound and a silicon element derived from an inorganic compound can be distinguished, even if the resin film contains a silica filler or the like, the silane coupling agent (C) Each of silicon derived from silicon and silicon derived from a silica filler can be quantified.
  • a silicon-containing inorganic compound such as a silica filler is substantially present in a region of 100 nm or less from the upper and lower surfaces of the curable resin film-forming layer.
  • the silicon element derived from the organosilicon compound can be quantified with high accuracy.
  • the silicon element concentration derived from the silane coupling agent (C) on at least one surface of the cured resin film is defined as “surface silicon element concentration (X)”, and the resin film Silane coupling agent measured at least one point each in the depth range of 40 to 60 nm (40 nm or more and less than 60 nm, the same applies hereinafter), 60 to 80 nm, and 80 to 100 nm in total in the depth direction from the surface.
  • X / Y is 3.4 or more, preferably 3.7 to 30, more preferably Is in the range of 4 to 10, and the silane coupling agent (C) is unevenly distributed on the surface of the resin film.
  • the average value of the silicon element concentration measured a plurality of times is used as the silicon element in the region. Concentration.
  • the silane coupling agent (C) is unevenly distributed on at least one surface of the curable resin film-forming layer.
  • the silane coupling agent (C) is the first adhesion surface with the adherend. It is preferable to be unevenly distributed on the surface (that is, the surface opposite to the support sheet).
  • the silane coupling agent (C) is unevenly distributed in both surfaces.
  • the silane coupling agent (C) is preferably unevenly distributed on the adhesion surface with the adherend, but may be unevenly distributed on both surfaces.
  • the functional group that reacts with the organic functional group is a functional group that the polymer (A), the curable component (B), the curable polymer component (AB), and the like have.
  • a silane coupling agent which is a reactive group is preferably used.
  • Examples of such a silane coupling agent (C) include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (Methacryloxypropyl) trimethoxysilane, ⁇ -aminopropyltrimethoxysilane, N-6- (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N-6- (aminoethyl) - ⁇ -aminopropylmethyldiethoxy Silane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, bis (3-
  • the silane coupling agent (C) is unevenly distributed on the surface of the layer (that is, the adhesive interface with the adherend).
  • the silane coupling agent (C) having an epoxy group is particularly suitable. Although this reason is not necessarily clear, compatibility with other resin which forms a curable resin film formation layer is adjusted by selecting an epoxy group as an organic functional group, and as a result, silane coupling agent (C) is more It is thought that it is likely to be unevenly distributed.
  • the number average molecular weight of the silane coupling agent (C) is preferably in the range of 120 to 1000, more preferably 160 to 500.
  • the silane coupling agent (C) is curable resin by being in the range. This is thought to be due to being able to move appropriately to the extent that it is unevenly distributed in the film forming layer.
  • the number average molecular weight of the silane coupling agent (C) is large, the movement of the silane coupling agent (C) is restricted, and it becomes difficult to move to the adhesion interface. As a result, aggregation and reaction of the silane coupling agent (C) are likely to occur inside the layer, which may be a starting point of aggregation fracture inside the layer, and the shear adhesiveness may be reduced.
  • the silane coupling agent equivalent with respect to 1 g of the curable resin film forming layer is preferably more than 0 meq / g and not more than 4.0 ⁇ 10 ⁇ 2 meq / g, and more preferably 1.0 ⁇ 10 ⁇ 7 to 1. It is 0 ⁇ 10 ⁇ 2 meq / g, particularly preferably 1.0 ⁇ 10 ⁇ 6 to 5.0 ⁇ 10 ⁇ 3 meq / g.
  • the silane coupling agent equivalent is calculated based on the alkoxy group of the silane coupling agent (C).
  • the compounding quantity of the silane coupling agent (C) in a curable resin film formation layer is the range which satisfies the said silane coupling agent equivalent, Specifically, all the solids of a curable resin film formation layer
  • the amount of the silane coupling agent (C) is preferably 0.0001 to 30 parts by mass, more preferably 0.01 to 20 parts by mass per 100 parts by mass of the minute. When there are too few compounding quantities of a silane coupling agent (C), required adhesiveness may not be acquired.
  • the silane coupling agent (C) is surprisingly unevenly distributed on the surface of the layer, and the amount of the silane coupling agent (C) is small. In addition, there was an effect that sufficient adhesive strength with the adherend was obtained. The reason for this is not necessarily clear, but the reason why a small amount is preferable is that when the amount of the silane coupling agent (C) increases, the silane coupling agent (C) is dispersed throughout the resin layer. Aggregation and reaction of the silane coupling agent (C) may occur, and the silane coupling agent (C) is dispersed not only on the surface of the layer but also inside the layer.
  • the silane coupling agent (C) dispersed in the layer serves as a starting point for cohesive failure and the shear adhesiveness is lowered.
  • the blending amount of the silane coupling agent (C) is small, aggregation within the layer does not occur, and the silane coupling agent (C) on this surface is coated as a result of being unevenly distributed on the layer surface. Contributes to improved adhesion to the body.
  • the self-aggregation of the silane coupling agent (C) does not occur inside the layer, it is considered that the shear strength is hardly lowered.
  • the surface of the silane coupling agent (C) is obtained by applying and drying the coating liquid.
  • a curable resin film-forming layer that is unevenly distributed is obtained.
  • a silane coupling agent (C ) May be applied and dried.
  • the resin film forming layer may contain the following components.
  • the inorganic filler resin film forming layer may contain an inorganic filler (D).
  • the inorganic filler 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, and glass fibers.
  • silica filler and alumina filler are preferable.
  • the said inorganic filler (D) can be used individually or in mixture of 2 or more types. As a range of the content of the inorganic filler (D) for obtaining the above-mentioned effect more reliably, when used as a protective film, it is preferably based on 100 parts by mass of the total solid content constituting the resin film forming layer.
  • the amount is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and particularly preferably 10 to 50 parts by mass.
  • a coloring agent (E) can be mix
  • a coloring agent resin film formation layer By blending the colorant (E), it is possible to prevent malfunction of the semiconductor device due to infrared rays generated from surrounding devices when the semiconductor device is incorporated into equipment. .
  • the resin film forming layer is engraved by means such as laser marking, there is an effect that marks such as characters and symbols can be easily recognized. These effects are particularly useful when the resin film forming layer is used as a protective film.
  • the colorant (E) organic or inorganic pigments and dyes are used. Among these, black pigments and black dyes are preferred from the viewpoint of electromagnetic wave and infrared shielding properties. Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like, but are not limited thereto. As the black dye, a high-concentration vegetable dye, azo dye or the like is used, but is not limited thereto. Carbon black is particularly preferable from the viewpoint of increasing the reliability of the semiconductor device.
  • the blending amount of the colorant (E) is preferably 0.1 to 35 parts by weight, more preferably 0.5 to 25 parts by weight, particularly preferably 100 parts by weight of the total solid content constituting the resin film forming layer. Is 1 to 15 parts by mass.
  • 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 comprising the above components may be a single composition film or a laminated film of two or more films having different compositions.
  • the film bonded to the semiconductor wafer side contains a large amount of components having relatively adhesive properties, and the film bonded to the chip mounting portion has a curable component.
  • the thickness of the resin film forming layer is usually 3 to 100 ⁇ m, preferably 4 to 95 ⁇ m, particularly preferably about 5 to 85 ⁇ m.
  • the resin film forming layer may be supplied to the attaching step with the semiconductor wafer while being detachably supported on the support sheet.
  • the resin film forming layer is laminated on the support sheet so as to be peelable.
  • the support sheet may be a single-layer or multi-layer resin film, and may further be a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is formed on the resin film.
  • the resin film is not particularly limited.
  • low density polyethylene LDPE
  • linear low density polyethylene LLDPE
  • ethylene / propylene copolymer polypropylene
  • polybutene polybutadiene
  • polymethylpentene ethylene / vinyl acetate copolymer
  • Polymer ethylene / (meth) acrylic acid copolymer, ethylene / (meth) methyl acrylate copolymer, ethylene / (meth) ethyl acrylate copolymer, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer
  • a resin film made of polyurethane film, ionomer or the like is used.
  • the resin films can be used by laminating or combining two or more kinds. Furthermore, the thing which colored these resin films, or what gave printing etc. can be used.
  • the resin film may be a sheet formed by extrusion forming a thermoplastic resin, or may be a stretched film, and a sheet obtained by thinning and curing a curable resin by a predetermined means. May be used.
  • the thickness of the support sheet is not particularly limited, and is preferably 30 to 300 ⁇ m, more preferably 50 to 200 ⁇ m. By setting the thickness of the support sheet within the above range, sufficient flexibility is imparted to the adhesive sheet including the support sheet and the resin film forming layer, and therefore, good adhesiveness to the semiconductor wafer is exhibited.
  • the surface tension of the surface of the support sheet in contact with the resin film forming layer is preferably 40 mN / m or less, more preferably 37 mN / m or less, particularly preferably 35 mN. / M or less.
  • the lower limit is usually about 25 mN / m.
  • Such a support 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 resin film 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 applied as it is without solvent, or diluted or emulsified with a solvent, using a gravure coater, Mayer bar coater, air knife coater, roll coater, etc. Then, the resin film to which the release agent is applied is subjected to room temperature or heating, or cured by electron beam, wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion processing, etc. May be formed.
  • the support sheet may be an adhesive sheet having an adhesive layer on the resin film.
  • the resin film forming layer is detachably laminated on the pressure-sensitive adhesive layer. Therefore, the pressure-sensitive adhesive layer may be weakly adhesive, or may be energy-ray curable, whose adhesive strength is reduced by irradiation with energy rays.
  • the releasable pressure-sensitive adhesive layer is made of various 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 on the surface, energy ray curing) Mold adhesive, thermal expansion component-containing adhesive, etc.).
  • the adhesive strength of the adhesive layer to the SUS plate at 23 ° C. is preferably 30 to 120 mN / 25 mm, and preferably 50 to 100 mN / 25 mm. More preferably, it is 60 to 90 mN / 25 mm.
  • this adhesive force is too low, the adhesiveness between the resin film forming layer and the adhesive layer becomes insufficient, and the resin film forming layer and the adhesive layer may be peeled off.
  • the adhesive force is too high, the resin film forming layer and the pressure-sensitive adhesive layer are excessively adhered to each other, causing a pickup failure.
  • the surface of the resin film on which the pressure-sensitive adhesive layer is provided is optionally roughened by sandblasting or solvent treatment, or corona discharge treatment, electron beam Irradiation, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, oxidation treatment such as hot air treatment, and the like can be performed.
  • primer treatment can also be performed.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 2 to 80 ⁇ m, and particularly preferably 3 to 50 ⁇ m.
  • the resin film-forming layer is obtained by applying and drying a composition for a resin film-forming layer obtained by mixing each of the above components in an appropriate solvent on a support sheet.
  • the composition for a resin film forming layer may be applied on a process film different from the support sheet, dried to form a film, and transferred onto the support sheet.
  • the sheet with a curable resin film-forming layer according to the present invention is formed by detachably forming the resin film-forming layer on a support sheet.
  • the shape of the sheet with the curable resin film forming layer according to the present invention is preliminarily cut into a tape shape or a shape suitable for adhering the resin film forming layer to the adherend (semiconductor wafer or the like) on the support sheet. It can take any shape such as a supported shape.
  • a light-peelable release film is laminated on the upper surface of the resin film-forming layer separately from the support sheet. It may be left.
  • the resin film forming layer of the sheet with the curable resin film forming layer functions as an adhesive film.
  • the adhesive film is usually affixed to the backside of a semiconductor wafer, etc., cut into individual chips through a dicing process, and then placed on a predetermined adherend on a substrate or the like (die-bonded). Used for adhesive fixing. Such an adhesive film is sometimes referred to as a die attachment film.
  • the semiconductor device using the resin film forming layer of the present invention as an adhesive film has a strong adhesive strength, a high durability, and a harsh environment by the action of the silane coupling agent unevenly distributed on the adhesion interface with the adherend. Maintains performance even underneath.
  • the resin film forming layer can be a protective film for the ground surface of the chip.
  • 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 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 resin film forming layer is used as an adhesive film.
  • a semiconductor wafer is bonded to the resin film forming layer of the sheet, and the semiconductor wafer is diced into semiconductor chips.
  • the resin film forming layer is fixedly left on the back surface of the semiconductor chip and peeled off from the support sheet, and the semiconductor chip is attached to a deposition part such as a die pad part or another semiconductor chip via the resin film forming layer. It is preferable to include a step of thermocompression bonding.
  • 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.
  • the back side of the semiconductor wafer is placed on the resin film forming layer of the sheet with a curable resin film forming layer according to the present invention, and lightly pressed to fix the semiconductor wafer. At that time, if 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 film forming layer is spared. May be cured to increase the cohesive force of the resin film forming layer and reduce the adhesive force between the resin film forming layer and the support sheet.
  • 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). For example, the irradiation may be performed after dicing or after the following expanding step. Good. Further, the energy beam irradiation may be performed in a plurality of times.
  • the support sheet of the sheet with the resin film forming layer is expanded, the interval between the semiconductor chips is expanded, and the semiconductor chips can be picked up more easily.
  • 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.
  • the cut resin film forming layer can be adhered to the back surface of the semiconductor chip and peeled off from the support sheet.
  • thermocompression bonding means that the semiconductor chip is placed on the adherend via the resin film forming layer and the resin film forming layer is heated.
  • the adherend may be heated before placing the semiconductor chip or immediately after placing.
  • the pressure for mounting during thermocompression bonding is usually 1 kPa to 200 MPa.
  • the heating temperature during thermocompression bonding is usually 80 to 200 ° C., preferably 100 to 180 ° C., and the heating time is usually 0.1 seconds to 5 minutes, preferably 0.5 seconds to 3 minutes. It is.
  • the semiconductor chip After the semiconductor chip is thermocompression bonded to the adherend, further heating may be performed as necessary. By further heating, the semiconductor chip can be firmly bonded to the adherend.
  • 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.
  • thermocompression bonding step may be performed in a temporarily bonded state, and thermocompression bonding may be performed using heating in resin sealing usually performed in package manufacture.
  • the resin film forming layer is cured, and the semiconductor chip can be bonded to the adherend via the resin film forming layer. Since 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 package is improved.
  • seat with a curable resin film formation layer of this invention is used for formation of the protective film for chips. That is, in the second method for manufacturing a semiconductor device according to the present invention, the back surface of the semiconductor wafer having a circuit formed on the front surface and the back surface ground is pasted on the resin film forming layer of the sheet with the curable resin film forming layer. And a resin film forming layer is cured to obtain a semiconductor chip having a protective film on the back surface.
  • the semiconductor chip manufacturing method 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 protective film that is the curable resin film-forming layer or the cured resin film and the support sheet
  • the resin film forming layer is cured and becomes a protective film in the step (2). Therefore, in the step after the step (2), even though “resin film forming layer” is described, It means “membrane”.
  • the resin film forming layer of the sheet with the curable resin film forming layer 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 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, and a protective film is formed on the entire back surface of the wafer.
  • the thermosetting component (B1) is used as the curable component (B)
  • the resin film forming layer is cured by thermosetting.
  • the energy beam curable component (B2) or the curable polymer component (AB) is blended in the resin film forming layer, the resin film forming layer can be cured by energy beam irradiation.
  • thermosetting component (B1) and the energy ray curable component (B2) or the curable polymer component (AB) are used in combination
  • curing by heating and energy ray irradiation may be performed simultaneously.
  • the energy rays to be irradiated include ultraviolet rays (UV) and electron beams (EB), and preferably ultraviolet rays are used.
  • UV ultraviolet rays
  • EB electron beams
  • 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 solution for forming a protective film is directly applied to the back surface of a 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 semiconductor chip having a protective film on the back surface is obtained.
  • a semiconductor chip having a protective film on the back surface can be obtained by picking up the diced chip by a general-purpose means such as a collet.
  • 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 semiconductor device can be manufactured by mounting the semiconductor chip 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 (attachment part) such as a die pad part or another semiconductor chip.
  • the sheet with a curable resin film-forming layer of the present invention can be used for adhesion or surface protection of a semiconductor compound, glass, ceramics, metal, etc., in addition to the above usage method.
  • ⁇ Surface silicon element concentration (X)> The curable resin film forming layer is heated at 125 ° C. for 60 minutes and further at 175 ° C. for 120 minutes to cure the curable resin film forming layer, and the surface silicon element concentration of the cured film is measured by X-ray photoelectron spectroscopy (XPS). did. XPS uses PHI Quantera SXM (manufactured by ULVAC-PHI), monochromatic Alk ⁇ as X-ray source, output 25 W (15 kV, 100 ⁇ m diameter), photoelectron extraction angle 45 °, pass energy 55.0 eV, step The surface silicon element concentration (X) was measured at a resolution of 0.05 eV.
  • ⁇ Average value of internal silicon element concentration (Y)> The curable resin film forming layer is cured in the same manner as the above surface silicon element concentration (X), the cured film is C60 ion sputtered, shaved to a certain depth from the surface, and the silicon element concentration inside the cured film is reduced in the same manner as described above. It was measured. C 60 ion sputtering conditions were set at an acceleration voltage 10kV, 1 min / cycle. The sputtering rate of the cured film under these conditions was 11.7 mm / min.
  • the silicon element concentration is measured at a total of three or more points, and the average value is calculated.
  • the average value (Y) of the internal silicon element concentration was obtained.
  • the average value of the silicon element concentration measured a plurality of times is used as the silicon element in the region. Concentration.
  • ultraviolet rays were irradiated (350 mW / cm 2 and 190 mJ / cm 2 ) from the support sheet surface of the sheet using an ultraviolet irradiation device (Adwill (registered trademark) RAD2000, manufactured by Lintec Corporation).
  • Adwill registered trademark
  • dicing was performed on a chip having a size of 5 mm ⁇ 5 mm, and the chip was picked up from the support sheet together with the curable resin film forming layer to obtain an upper chip.
  • the amount of cut at the time of dicing was set to cut by 20 ⁇ m with respect to the support sheet.
  • the upper chip obtained in the above (1-1) is placed on the surface of the chip coated with the polyimide resin (polyimide surface) under the conditions of 100 ° C., 300 gf / chip for 1 second via the curable resin film forming layer. And bonded. Thereafter, the curable resin film-forming layer was cured by heating at 125 ° C. for 60 minutes and further at 175 ° C. for 120 minutes to obtain a test piece.
  • the polyimide resin polyimide surface
  • test piece is left to stand in an environment of 85 ° C. and 85% RH for 48 hours to absorb moisture, and the resorbed test piece is subjected to IR reflow (reflow furnace: manufactured by Sagami Riko Co., Ltd.) at a maximum temperature of 260 ° C. and a heating time of 1 minute. , WL-15-20DNX type) three times, and further a pressure cooker test (conditions: 121 ° C., 2.2 atm, 100% RH) for 168 hours, heat-humidized test piece (test piece for measurement) Got.
  • IR reflow reflow furnace: manufactured by Sagami Riko Co., Ltd.
  • WL-15-20DNX type three times
  • pressure cooker test conditions: 121 ° C., 2.2 atm, 100% RH
  • Each component constituting the curable resin film forming layer is as follows.
  • a curable resin film forming layer was prepared by blending each component as the same composition except that the amount of the silane coupling agent was changed as shown in Table 1.
  • (A: Polymer component) (A1) Acrylic polymer: 100 parts by mass of Coponil N-4617 (Mw: about 370,000) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
  • Non-acrylic resin Thermoplastic polyester resin (Byron 220 manufactured by Toyobo Co., Ltd.) 40 54 parts by mass (B: curable component)
  • Epoxy compound (B11a) Liquid epoxy resin: Bisphenol A type epoxy resin 20% by weight acrylic particle-containing product (Nippon Shokubai Eposet BPA328, epoxy equivalent 235 g / eq) 58.01 parts by mass
  • Solid epoxy resin Cresol novolac type epoxy Resin (manufactured by Nippon Kayaku Co., Ltd.
  • thermosetting agent novolak type phenolic resin (PAPS-PN4, manufactured by Asahi Organic Materials Co., Ltd., phenolic hydroxyl group equivalent 104 g / eq, softening point 111 ° C.) 24 parts by mass (B13) curing accelerator: 2-phenyl-4,5-di (hydroxymethyl) imidazole (Curesol 2PHZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.26 parts by mass (B21) Energy ray reactive compound: di 22.3 parts by mass of cyclopentadiene dimethoxydiacrylate (KAYARAD R-684, manufactured by Nippon Kayaku Co., Ltd.) (B22) Photopolymerization initiator: ⁇ -hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co
  • a composition for a curable resin film-forming layer was prepared with the same composition except that the amount of the silane coupling agent was changed as shown in Table 1, and the solid content concentration was 50% by weight with methyl ethyl ketone. And dried on a silicone-treated release film (SP-PET 381031 manufactured by Lintec Corporation) so that the thickness is about 60 ⁇ m after drying (drying conditions: 100 ° C. for 2 minutes in an oven). A curable resin film-forming layer formed on the release film was obtained.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

Le problème décrit par la présente invention est d'améliorer l'adhérence entre une couche de formation de film de résine, qui sert de précurseur d'un film adhésif ou d'un film protecteur, ou un film de résine durci obtenu par ce biais et une puce à semi-conducteur ou une plaquette à semi-conducteur qui est une partie adhérée. La solution selon l'invention porte sur une feuille qui est dotée d'une couche de formation de film de résine durcissable, qui comprend une feuille de support et la couche de formation de film de résine durcissable qui est formée de manière pelable sur la feuille de support, et qui est caractérisée en ce que: la couche de formation de film de résine durcissable comprend un élément liant durcissable et un agent de couplage silane (C); et, sur au moins une surface d'un film de résine qui est obtenu par le durcissement de la couche de formation de film de résine durcissable, la concentration (X) d'un élément de silicium de surface dérivé de l'agent de couplage silane (C) représente au moins 3,4 fois la concentration moyenne (Y) d'un élément de silicium interne dérivé de l'agent de couplage silane (C), ladite concentration moyenne (Y) étant déterminée par la mesure de la concentration de silicium interne dérivée de l'agent de couplage silane (C) au moins au niveau d'un point dans chacune des plages de profondeur de 40-60 nm, 60-80 nm et 80-100 nm dans la direction de la profondeur depuis la surface susmentionnée, à savoir, au moins au niveau de trois points au total.
PCT/JP2013/082187 2012-11-30 2013-11-29 Feuille dotée d'une couche de formation de film de résine durcissable et procédé de fabrication de dispositif à semi-conducteur au moyen de la feuille WO2014084357A1 (fr)

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JP2014549922A JP6298409B2 (ja) 2012-11-30 2013-11-29 硬化性樹脂膜形成層付シートおよび該シートを用いた半導体装置の製造方法
CN201380062060.XA CN104797423B (zh) 2012-11-30 2013-11-29 带固化性树脂膜形成层的片材以及使用了该片材的半导体装置的制造方法
KR1020157013915A KR102224971B1 (ko) 2012-11-30 2013-11-29 경화성 수지막 형성층이 형성된 시트 및 그 시트를 사용한 반도체 장치의 제조 방법

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JP2012263034 2012-11-30
JP2012-263034 2012-11-30

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KR (1) KR102224971B1 (fr)
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KR102293573B1 (ko) 2017-09-15 2021-08-25 린텍 가부시키가이샤 필름상 소성 재료, 및 지지 시트를 가지는 필름상 소성 재료
WO2019098326A1 (fr) * 2017-11-17 2019-05-23 リンテック株式会社 Puce de semi-conducteur avec premier film de protection, procédé de fabrication de puce de semi-conducteur avec un premier film de protection, et procédé d'évaluation de stratifié de puce de semi-conducteur et premier film de protection
WO2020059572A1 (fr) * 2018-09-20 2020-03-26 三井化学東セロ株式会社 Procédé de fabrication de dispositif électronique
JP6497477B1 (ja) * 2018-10-03 2019-04-10 東洋インキＳｃホールディングス株式会社 電磁波シールドシート、および電子部品搭載基板
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JP6298409B2 (ja) 2018-03-20
JPWO2014084357A1 (ja) 2017-01-05
TW201435036A (zh) 2014-09-16
CN104797423B (zh) 2017-06-13
KR102224971B1 (ko) 2021-03-08
CN104797423A (zh) 2015-07-22
KR20150090080A (ko) 2015-08-05

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