JP6298409B2 - Sheet with curable resin film forming layer and method for manufacturing semiconductor device using the sheet - Google Patents

Description

  The present invention relates to a sheet with a curable resin film forming layer capable of forming a resin film functioning as an adhesive film or a protective film in a semiconductor chip with high adhesive strength. Moreover, this invention relates to the manufacturing method of the semiconductor device using the said sheet | seat with a curable resin film formation layer.

  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.

  Among these processes, in order to simplify the processes of the pick-up process and the bonding process, various dicing / die-bonding sheets having both a wafer fixing function and a die bonding function have been proposed (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. 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.

  In recent years, the required physical properties of semiconductor devices have become very strict, and there is a strong demand for reliably suppressing defects such as delamination at the adhesive interface even in harsh environments. Addition of a silane coupling agent to the adhesive layer in order to improve the adhesive strength is also widely performed (Patent Document 1: Japanese Patent Laid-Open No. 2000-17246). However, even if a silane coupling agent is added to the adhesive layer, the adhesive strength, particularly the shear strength, may not be improved as expected.

  In recent years, semiconductor devices have been manufactured using a so-called face down method. In the face-down method, a semiconductor chip (hereinafter simply referred to as “chip”) having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. For this reason, the surface (chip back surface) opposite to the circuit surface of the chip may be exposed.

  The exposed back surface of the chip may be protected by an organic film. Conventionally, 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. However, since the thickness accuracy of the protective film formed in this way is not sufficient, the product yield may be lowered.

  In order to solve the above problems, a protective film forming sheet for a chip having a protective film forming layer composed of a thermosetting component or an energy ray curable component and a binder polymer component has been disclosed (Patent Document 2: JP 2009-200909A). -138026). Even in such a protective film forming layer, 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.

JP 2000-17246 A JP 2009-138026 A

  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.

  In order to solve this problem, 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.

That is, the present invention for solving the above problems includes the following gist.
[1] A support sheet and a curable resin film-forming layer formed on the support sheet so as to be peelable,
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, and a total of 3 or more points. The sheet | seat with a curable resin film formation layer which is 3.4 times or more of the average value (Y) of the internal silicon element density | concentration derived from the made silane coupling agent (C).
[2] Formation of curable resin film according to [1], wherein the surface silicon element concentration (X) on both surfaces of the cured resin film is 3.4 times or more the average value (Y) of the internal silicon element concentration Layered sheet.
[3] The curability according to [1] or [2], wherein the silane coupling agent equivalent to 1 g of the curable resin film-forming layer is greater than 0 meq / g and not greater than 4.0 × 10 ⁻² meq / g. Sheet with resin film forming layer.
[4] The sheet with a curable resin film-forming layer according to any one of [1] to [3], wherein the silane coupling agent (C) has an epoxy group.
[5] The sheet with a curable resin film-forming layer according to any one of [1] to [4], wherein the silane coupling agent (C) has a number average molecular weight of 120 to 1,000.
[6] The curable resin film-forming layer or the cured resin film functions as an adhesive film for fixing the semiconductor chip to the substrate or another semiconductor chip according to any one of [1] to [5]. Sheet with curable resin film forming layer.
[7] The sheet with a curable resin film forming layer according to any one of [1] to [5], wherein the cured resin film of the curable resin film forming layer functions as a protective film for a semiconductor wafer or a chip.
[8] 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.
[9] A semiconductor chip having a protective film by attaching a semiconductor wafer to the curable resin film forming layer of the sheet with a curable resin film forming layer according to [7], curing the curable resin film forming layer, and A method for manufacturing a semiconductor device, comprising the step of:
[10] The method for manufacturing a semiconductor device according to [9], further including 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,
Step (2): A protective film is obtained by curing the curable resin film-forming layer.
Step (3): Dicing the semiconductor wafer and the curable resin film forming layer or the protective film.

  In the present invention, in the resin film forming layer functioning as a precursor of the adhesive film or the protective film or the cured film thereof, 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.

  Hereinafter, the present invention will be described more specifically, including its best mode. The sheet | 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. As the 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.

  Until the resin film forming layer is cured, it is a function for temporarily attaching to an adherend (semiconductor wafer or semiconductor chip). (2) The initial adhesiveness may be pressure-sensitive adhesiveness, It may have a property of being softened and bonded by heat. (2) 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.

(First curable binder component)
A 1st sclerosing | hardenable binder component provides film forming property and curability to a resin film formation layer by containing a polymer component (A) and a sclerosing | hardenable component (B). In addition, a 1st curable binder component does not contain a curable polymer component (AB) for convenience which distinguishes from a 2nd curable binder component.

(A) Polymer 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.

In order to achieve the above object, the polymer component (A) has a weight average molecular weight (Mw) of 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 by, for example, using a high-speed GPC device “HLC-8120GPC” manufactured by Tosoh Corporation, 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.

  In addition, for convenience to distinguish from the curable polymer (AB) described later, the polymer component (A) does not have a curing functional functional group described later.

  As the polymer component (A), 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. In addition, 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. Furthermore, two or more of these may be used in combination, including a polymer in which two or more are bonded.

(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. By setting the glass transition temperature (Tg) of the acrylic polymer (A1) within the above range, the adhesion of the resin film forming layer to the adherend is improved. If the glass transition temperature of the acrylic polymer (A1) is too low, the peeling force between the resin film forming layer and the support sheet may be increased, and transfer failure of the resin film forming layer may occur.

  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 in at least a constituent monomer.

  As the (meth) acrylic acid ester, an alkyl (meth) acrylate 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) Acrylates, specifically cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopenteni Oxyethyl (meth) acrylate, imide (meth) acrylate. Moreover, what is (meth) acrylic acid ester can be illustrated among what is illustrated as a monomer which has a hydroxyl group mentioned later, a monomer which has a carboxyl group, and a monomer which has an amino group.

  In the present specification, (meth) acryl may be used to include both acrylic and methacrylic.

  A monomer having a hydroxyl group may be used as the monomer constituting the acrylic polymer (A1). When such a monomer is 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. Examples of 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. .

  As the monomer constituting the acrylic polymer (A1), a monomer having a carboxyl group may be used. When such a monomer is used, a carboxyl group is introduced into the acrylic polymer (A1), and the resin film forming layer additionally contains an energy ray curable component (B2). Compatibility with the polymer (A1) is improved. Examples of 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. When using 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.

  As a monomer constituting the acrylic polymer (A1), a monomer having an amino group may be used. Examples of such a monomer include (meth) acrylic acid esters having an amino group such as monoethylamino (meth) acrylate.

  In addition, vinyl acetate, styrene, ethylene, α-olefin, or the like may be used as a 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 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. By crosslinking the acrylic polymer (A1), it is possible to adjust the initial adhesive force and cohesive force of the resin film-forming layer.

  Examples of the crosslinking agent include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.

  Examples of 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.

  Specifically, as the organic polyvalent isocyanate compound, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4′- Diisocyanate, diphenylmethane-2,4′-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, and lysine isocyanates thereof Examples thereof include polyhydric alcohol adducts.

  Specific examples of organic polyvalent imine compounds include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylol. Mention may be made of methane-tri-β-aziridinylpropionate and N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine.

  A crosslinking agent is 0.01-20 mass parts normally with respect to 100 mass parts of acrylic polymers (A1) before bridge | crosslinking, Preferably it is 0.1-10 mass parts, More preferably, it is 0.5-5 mass parts. Used in ratio.

  In the present invention, 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.

(A2) 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, and more preferably 20,000 to 80,000.

  The glass transition temperature of the non-acrylic resin (A2) is preferably -30 to 150 ° C, more preferably -20 to 120 ° C. By setting the glass transition temperature of the non-acrylic resin in the above range, the adhesion of the resin film forming layer to the adherend is improved. If the glass transition temperature of the non-acrylic resin is too low, the peeling force between the resin film forming layer and the support sheet is increased, and transfer failure of the resin film forming layer may occur.

  When the 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.

  When the non-acrylic resin (A2) is used in combination with the above-mentioned acrylic polymer (A1), 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. When the content of the non-acrylic resin (A2) is in this range, the above effect can be obtained.

(B) Curable component 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. As the curable component (B), 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, and preferably 100 to 10,000.

(B1) 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). As 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).

(B11) Compound having an epoxy group As the compound (B11) having an epoxy group (hereinafter sometimes referred to as “epoxy compound (B11)”), 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.

  When the epoxy compound (B11) is used, the resin film forming layer preferably contains 1 to 1500 parts by mass of the epoxy compound (B11) with respect to 100 parts by mass of the polymer component (A), more preferably. 3 to 1200 parts by mass are included. By making 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. When 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.

(B12) Thermosetting agent The 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.

  Specific examples of the curing agent having a phenol hydroxyl group 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.

  It is preferable that it is 0.1-500 mass parts with respect to 100 mass parts of epoxy compounds (B11), and, as for content of a thermosetting agent (B12), it is more preferable that it is 1-200 mass parts. By making 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.

(B13) 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. 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. When 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.

(B2) 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. Moreover, when using as an adhesive film for die-bonding, when 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.

  As the energy ray-curable component (B2), 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. Acrylate, and an acrylate compound having a polymerizable structure acrylate compounds such as polyether acrylates and itaconic acid oligomers, include the relatively low molecular weight. Such a compound has at least one polymerizable double bond in the molecule.

  When the energy ray reactive compound (B21) is used, 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 3 to 1200 parts by mass.

(B22) By combining the photopolymerization initiator energy beam reactive compound (B21) with the photopolymerization initiator (B22), the polymerization curing time can be shortened and the amount of light irradiation can be reduced.

  Specific examples of such a photopolymerization initiator (B22) 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. 2,4-diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy- 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and β -Chloranthraquinone and the like. 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, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the energy ray reactive compound (B21). .

  If 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.

(Second curable binder component)
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).

(AB) Curable polymer component 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. When the functional functional group is added in the unit of the continuous structure that becomes the skeleton of the curable polymer component (AB), 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.

  An example of a functional group that reacts by heating is 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). Examples of such monomers include (meth) acrylic acid esters having a glycidyl group such as glycidyl (meth) acrylate.

  When an epoxy group-containing acrylic polymer is used, the preferred embodiment is the same as that of the acrylic polymer (A1).

  When the curable polymer component (AB) having an epoxy group is used, the 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. As 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.

  In addition, for example, 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 Alternatively, a polymer prepared by reacting a low molecular compound having a functional group that reacts with the above may be used.

  In this case, when a raw material polymer corresponds to the above-mentioned acrylic polymer (A), the preferable aspect of the raw material polymer is the same as that of the acrylic polymer (A).

  When the curable polymer component (AB) having a functional group that reacts with energy rays is used, 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.

(C) Silane coupling agent 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. By using 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. According to C ₆₀ ion sputtering, less affected by structural destruction against organic, 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. Furthermore, in the sheet with a curable resin film-forming layer shown in the embodiment of the present invention, 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. In the region of 100 nm or less from the upper and lower surfaces, the silicon element derived from the organosilicon compound can be quantified with high accuracy.

  In the sheet with a curable resin film forming layer of the present invention, 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 a total of 3 or more points, at least one point each in the depth range of 40 to 60 nm (40 nm to less than 60 nm, the same applies hereinafter), 60 to 80 nm, and 80 to 100 nm in the depth direction from the surface ( When the average value of the silicon element concentration derived from C) is “average value of internal silicon element concentration (Y)”, 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. In addition, when a plurality of measurements were possible in respective depth ranges of 40 to 60 nm, 60 to 80 nm, and 80 to 100 nm, the average value of the silicon element concentration measured a plurality of times was used as the silicon element in the region. Concentration.

  In the present invention, it is important that the silane coupling agent (C) is unevenly distributed on at least one surface of the curable resin film-forming layer. Specifically, 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). Moreover, when using a resin film formation layer as an adhesive film, since both surfaces of an adhesive film become an adhesive surface, it is preferable that the silane coupling agent (C) is unevenly distributed in both surfaces. When the resin film forming layer is used as a protective film, the silane coupling agent (C) is preferably unevenly distributed on the adhesion surface with the adherend, but may be unevenly distributed on both surfaces.

  As the silane coupling agent (C), 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 silane coupling agent (C) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (Methacryloxypropyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxy Silane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane , Methyltrimethoxy Examples thereof include silane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, 3-octanoylthio-1-propyltriethoxysilane, and 3-aminopropyltriethoxysilane. These can be used individually by 1 type or in mixture of 2 or more types.

  In the curable resin film forming layer, the silane coupling agent (C) is unevenly distributed on the surface of the layer (that is, the adhesive interface with the adherend). As a result of various studies from the viewpoint of uneven distribution of the silane coupling agent (C) on the surface of the layer, it was found that 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.

  From the same viewpoint, 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. Although the reason why the uneven distribution of the silane coupling agent (C) is promoted by the number average molecular weight being in the above range is not necessarily clear, 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. When 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 equivalent of the silane coupling agent relative 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, Most preferably, it is 1.0 * 10 < ^-6 > -5.0 * 10 < ^-3 > meq / g. Here, the silane coupling agent equivalent is calculated based on the alkoxy group of the silane coupling agent (C).

  Moreover, it is preferable that 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 in the range of 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.

  By using these silane coupling agents (C), 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. As a result of the increase in the internal silicon element concentration (Y), it is considered that the silane coupling agent (C) dispersed in the layer serves as a starting point for cohesive failure and the shear adhesiveness is lowered. However, if 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. Moreover, since 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.

  By blending the silane coupling agent (C) as described above into the coating liquid for forming the resin film forming layer, 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. Moreover, for the purpose of making the silane coupling agent (C) unevenly distributed on the surface of the layer, after obtaining a resin film forming layer not containing the silane coupling agent (C), a silane coupling agent (C ) May be applied and dried.

In addition to the curable binder component and the silane coupling agent (C), the resin film forming layer may contain the following components.
(D) The inorganic filler resin film forming layer may contain an inorganic filler (D). By blending the inorganic filler (D) into the resin film forming layer, it becomes possible to adjust the thermal expansion coefficient in the resin film forming layer after curing, and the resin film after curing with respect to the semiconductor chip as the adherend The reliability of the semiconductor device can be improved by optimizing the thermal expansion coefficient of the formation layer. It is also possible to reduce the moisture absorption rate of the cured resin film forming layer.

  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. Among these, 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. Is 1 to 80 parts by mass, more preferably 20 to 75 parts by mass, and particularly preferably 40 to 70 parts by mass. When used as an adhesive film, the total solid content of 100 parts by mass constituting the resin film forming layer is used. 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.

(E) A coloring agent (E) can be mix | blended with a coloring agent resin film formation layer. In particular, when used as a protective film, 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. . In addition, when 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.

  As 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 mass, more preferably 0.5 to 25 parts by mass, particularly preferably 100 parts by mass of the total solid content constituting the resin film forming layer. Is 1-15 parts by mass.

(F) In addition to the above, various additives may be blended in the general-purpose additive resin film forming layer as necessary. Examples of various 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. When the film is composed of two or more kinds of films, for example, 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. You may increase a compounding quantity. Moreover, when using as a protective film, you may increase the filler amount of a film arrange | positioned at the exposed surface side, and the amount of coloring agents.

  The thickness of the resin film forming layer is usually 3 to 100 μm, preferably 4 to 95 μm, and particularly preferably about 5 to 85 μm.

(Support sheet)
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.

(Resin film)
The resin film is not particularly limited. For example, 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.

  Two or more kinds of these resin films can be laminated or used in combination. Furthermore, the thing which colored these resin films, or what gave printing etc. can be used. In addition, 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 a support sheet is not specifically limited, Preferably it is 30-300 micrometers, More preferably, it is 50-200 micrometers. 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.

  When the resin film forming layer is directly formed on the support sheet, 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. .

  As the release agent used for the release treatment, alkyd, silicone, fluorine, unsaturated polyester, polyolefin, wax, and the like are used. In particular, alkyd, silicone, and fluorine release agents are heat resistant. This is preferable.

  In order to release the surface of the resin film using the release agent described above, 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.

(Adhesive layer)
The support sheet may be an adhesive sheet having an adhesive layer on the resin film. In this case, 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.).

  As the weak adhesive, acrylic and silicone are preferably used. In consideration of the peelability of the resin film forming layer, the adhesive strength of the adhesive layer to the SUS plate at 23 ° C. is preferably 30 to 120 mN / 25 mm, and more preferably 50 to 100 mN / 25 mm. More preferably, it is more preferably 60 to 90 mN / 25 mm. When 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. On the other hand, if 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.

  In addition, in order to strengthen the adhesion between the resin film and the pressure-sensitive adhesive layer, 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. Moreover, primer treatment can also be performed.

  Although the thickness of an adhesive layer is not specifically limited, Preferably it is 1-100 micrometers, More preferably, it is 2-80 micrometers, Most preferably, it is 3-50 micrometers.

(Sheet with curable resin film forming layer)
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. Alternatively, 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 | seat with a curable resin film formation layer which concerns on this invention forms the said resin film formation layer so that peeling is possible 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.

  Before using the sheet with a curable resin film-forming layer, in order to protect the resin film-forming layer, 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 such a sheet with a 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. 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.

(Semiconductor chip manufacturing method)
Next, the method for using the sheet with a curable resin film forming layer according to the present invention will be described taking the case of using the resin film forming layer as an adhesive film and the case of using it as a protective film forming layer.

  First, the case where a resin film formation layer is used as an adhesive film will be described. In a first manufacturing method of a semiconductor device using a sheet with a curable resin film forming layer according to the present invention, 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 protective sheet is attached to the circuit surface to protect the circuit on the surface. In the back surface grinding, 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 μm. Thereafter, if necessary, 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, when 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). Next, when an energy ray reactive compound is blended as the curable component (B) in the resin film forming layer, 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. Next, the semiconductor wafer and the resin film forming layer are cut using a cutting means such as a dicing saw to obtain a semiconductor chip with a resin film forming layer. 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.

  Then, if necessary, if the support sheet of the sheet with a resin film forming layer is expanded, the interval between the semiconductor chips is expanded, and the semiconductor chips can be picked up more easily. At this time, a deviation occurs between the resin film forming layer and the support sheet, the adhesive force between the resin film forming layer and the support sheet is reduced, and the pick-up property of the semiconductor chip is improved. When the semiconductor chip is picked up in this manner, the cut resin film forming layer can be adhered to the back surface of the semiconductor chip and peeled off from the support sheet.

  Next, the semiconductor chip is thermocompression-bonded on a die pad of the lead frame or a surface of another semiconductor chip (lower chip) through the resin film forming layer. Here, the 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 at the time of mounting in 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.

  After thermocompression bonding of the semiconductor chip to the adherend, heating may be further 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.

  Alternatively, the heat treatment after mounting (the above-described thermocompression bonding step) may be performed in a temporarily bonded state, and thermocompression bonding may be performed using heating in resin sealing that is normally performed in package manufacturing.

  By passing through such a process, a resin film formation layer hardens | cures and a semiconductor chip can be adhere | attached on a to-be-adhered part via a resin film formation 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.

Next, the case where the sheet | seat with a curable resin film formation layer of this invention is used for formation of the protective film for chips is demonstrated.
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. In addition, the semiconductor chip manufacturing method according to the present invention preferably further includes the following steps (1) to (3), and 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,
Step (2): A protective film is obtained by curing the curable resin film-forming layer.
Step (3): Dicing the semiconductor wafer and the curable resin film forming layer or the protective film.

  In the above, 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”.

  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.

  First, the resin film formation layer of the said sheet | seat with a curable resin film formation layer is affixed on the back surface of the semiconductor wafer in which the circuit was formed in the surface. Next, 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. Next, the resin film forming layer is cured, and a protective film is formed on the entire back surface of the wafer. When the thermosetting component (B1) is used as the curable component (B), the resin film forming layer is cured by thermosetting. Moreover, when 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. Furthermore, in the case where the 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. You may carry out sequentially. Examples of the energy rays to be irradiated include ultraviolet rays (UV) and electron beams (EB), and preferably ultraviolet rays are used. As a result, 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. In addition, 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.

  Next, 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.

  Finally, the diced chip is picked up by a general-purpose means such as a collet to obtain a semiconductor chip having a protective film on the back surface. 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. Then, 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 | seat with a curable resin film formation layer of this invention can also be used for adhesion | attachment or surface protection of a semiconductor compound, glass, ceramics, a metal other than the above usage methods.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the following examples and comparative examples, <surface silicon element concentration (X)>, <average value of internal silicon element concentration (Y)>, and <shear strength> were measured as follows.

<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 Alkα as X-ray source, output 25 W (15 kV, 100 μm 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. At least one point in each depth range of 40 to 60 nm, 60 to 80 nm, and 80 to 100 nm in the depth direction from the cured film surface, 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. In addition, when a plurality of measurements were possible in respective depth ranges of 40 to 60 nm, 60 to 80 nm, and 80 to 100 nm, the average value of the silicon element concentration measured a plurality of times was used as the silicon element in the region. Concentration.

<Shear strength>
The shear strength was measured using a sheet that had been stored for 7 days in an environment of 23 ° C. and 50% relative humidity.

(1-1) Preparation of upper chip Example or comparison was performed on a dry-polished surface of a silicon wafer (200 mm diameter, 500 μm thick) whose surface was dry-polished by a wafer backside grinding apparatus (DGP8760, manufactured by DISCO). The curable resin film-forming layer of the sheet with the curable resin film-forming layer obtained in the example was attached using a tape mounter (Adwill (registered trademark) RAD2500 m / 8, manufactured by Lintec Corporation), and the outer periphery of the support sheet was attached. Fixed to the ring frame. Then, 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).

  Next, using a dicing apparatus (DFD651, manufactured by DISCO), the chip was diced into 5 mm × 5 mm size, 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 μm with respect to the support sheet.

(1-2) Preparation of test specimen for measurement A silicon wafer (200 mm diameter, 725 μm thickness) coated with a polyimide resin (PLH708 manufactured by Hitachi Chemical DuPont Microsystems Co., Ltd.) was diced with a dicing tape (Adwill D- manufactured by Lintec Corporation). 650) was affixed using a tape mounter as described above. Subsequently, the silicon wafer was diced into a chip size of 12 mm × 12 mm using a dicing apparatus in the same manner as described above, and the chip was picked up. The upper chip obtained in (1-1) above is applied to the surface of the chip coated with the polyimide resin (polyimide surface) under the conditions of 100 ° C. and 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 obtained 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), and a pressure cooker test (conditions: 121 ° C., 2.2 atm, 100% RH) for 168 hours, heat-humidized test piece (measurement test piece) Got.

(1-3) Measurement of shear strength The measurement stage of the bond tester (Dage, Bond Tester Series 4000) was set to 250 ° C., and the measurement specimen was left on the measurement stage for 30 seconds. Force (shear strength) when the adhesive state breaks by applying stress in the horizontal direction (shear direction) to the resin film interface at a speed of 500 μm / s at a height of 100 μm from the bonding interface (resin film interface) (N) Was measured. In addition, about the test piece for a measurement of 6 samples, each shear strength was measured and the average value was made into shear strength (N).

[Components of curable resin film-forming layer]
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: Nippon Synthetic Chemical Industry Co., Ltd. Coponil N-4617 (Mw: about 370,000) 100 parts by mass (A2) Non-acrylic resin: Thermoplastic polyester resin (Toyobo Co., Ltd. Byron 220) 40 54 parts by mass (B: curable component)
(B11) 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 (B11b) Solid epoxy resin: Cresol novolac type epoxy Resin (Nippon Kayaku Co., Ltd. EOCN-104S, epoxy equivalent of 213 to 223 g / eq, softening point of 90 to 94 ° C.) 38.67 parts by mass (B11c) solid epoxy resin: polyfunctional epoxy resin (Nippon Kayaku Co., Ltd.) EPPN-502H, epoxy equivalent 158-178 g / eq, softening point 60-72 ° C.) 48.34 parts by mass (B11d) solid epoxy resin: DCPD type epoxy resin (Dainippon Ink Chemical Co., Ltd. EPICLON HP-7200HH, epoxy Equivalent 265-300 g / eq 19.33 parts by mass (B12) 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 (B22) photopolymerization initiator: α-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0, cyclopentadiene dimethoxydiacrylate (KAYARAD R-684 manufactured by Nippon Kayaku Co., Ltd.) .67 parts by mass (C: silane coupling agent)
γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-403 methoxy equivalent 12.7 mmol / g, number average molecular weight 236.3) (blending amount described in Table 1)
(D: inorganic filler)
Si filler (UF-310 manufactured by Tokuyama Corporation) 127.03 parts by mass

[Examples and Comparative Examples]
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 and coated on a release film (SP-PET 381031 manufactured by Lintec Co., Ltd.) so that the thickness is about 60 μm (drying conditions: 100 ° C. for 2 minutes in an oven). A curable resin film-forming layer formed on the release film was obtained. Thereafter, the curable resin film-forming layer and a polyethylene film (thickness 100 μm, surface tension 33 mN / m) as a support sheet are bonded together, and the curable resin film-forming layer is transferred onto the support sheet, thereby achieving desired curing. A sheet with a conductive resin film-forming layer was obtained. Each evaluation result is shown in Table 1.

Claims (10)

A support sheet, and a curable resin film-forming layer formed on the support sheet so as to be peelable;
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, and a total of 3 or more points. der 3.4 times more silane coupling agent (C) the average value of the internal silicon element concentration from (Y) is,
The curable silane coupling agent equivalents relative to the resin film forming layer 1g ^{is, 1.0 × 10 -7 meq / g~1.0} × 10 -2 meq / g Der Ru curable resin film layer with the sheet. 2. The sheet with a curable resin film-forming layer according to claim 1, wherein the surface silicon element concentration (X) on both surfaces of the cured resin film is at least 3.82 times the average value (Y) of the internal silicon element concentration. . The curable resin according to claim 1 or 2, wherein an equivalent of the silane coupling agent with respect to 1 g of the curable resin film forming layer is 1.0 × 10 ⁻⁶ meq / g to 5.0 × 10 ⁻³ meq / g. Sheet with film-forming layer.   The sheet | seat with a curable resin film formation layer in any one of Claims 1-3 in which the said silane coupling agent (C) has an epoxy group.   The number average molecular weight of the said silane coupling agent (C) is 120-1000, The sheet | seat with a curable resin film formation layer in any one of Claims 1-4.   The curable resin film forming layer according to claim 1, wherein the curable resin film forming layer or the cured resin film functions as an adhesive film for fixing the semiconductor chip to the substrate or another semiconductor chip. Layered sheet.   The sheet | seat with a curable resin film formation layer in any one of Claims 1-5 in which the resin film after hardening of the curable resin film formation layer functions as a protective film of a semiconductor wafer or a chip | tip.   A semiconductor wafer is attached to the curable resin film forming layer of the sheet with the curable resin film forming layer according to claim 6, the semiconductor wafer is diced into a semiconductor chip, and the resin film forming layer is formed on the back surface of the semiconductor chip. A method of manufacturing a semiconductor device comprising the steps of: fixing and remaining on the support sheet, and thermocompression bonding the semiconductor chip to the adherend via the resin film forming layer.   The process of sticking a semiconductor wafer to the curable resin film formation layer of the sheet | seat with a curable resin film formation layer of Claim 7, hardening a curable resin film formation layer, and obtaining the semiconductor chip which has a protective film. A method for manufacturing a semiconductor device. The method for manufacturing a semiconductor device according to claim 9, further comprising 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,
Step (2): A protective film is obtained by curing the curable resin film-forming layer.
Step (3): Dicing the semiconductor wafer and the curable resin film forming layer or the protective film.