KR20090104714A - Adhesive composition, adhesive sheet and production method of semiconductor device - Google Patents

Abstract

PURPOSE: An adhesive composition and an adhesive sheet are provided to prevent a chip from being crushed and split by reducing power for a pick-up process. CONSTITUTION: An adhesive composition includes an acrylic polymer, an epoxy resin, a thermosetting agent, and a silicone compound. The silicone compound is organopolysiloxane having an aromatic ring-containing group as a side chain. The silicone compound has 50~100,000 mm^2/s dynamic viscosity at 25°C. The aromatic ring-containing group excludes a reactive organic functional group.

Description

Adhesive composition, adhesive sheet and production method of semiconductor device

INDUSTRIAL APPLICATION This invention is an adhesive agent sheet which has an adhesive agent composition especially suitable for use in the dicing process of obtaining a chip from a semiconductor wafer, and the die bonding process of a chip to an organic substrate, a lead frame, etc., and the adhesive agent layer which consists of this adhesive agent composition. And a method for manufacturing a semiconductor device using the same.

Semiconductor wafers such as silicon and gallium arsenide are manufactured in a large diameter state, and the wafers are cut and diced into small pieces (chips) and then transferred to a die bonding step, which is the next step. At this time, the semiconductor wafer is subjected to dicing, cleaning, drying, expanding, and picking up in a state where the semiconductor wafer is previously attached to the adhesive sheet, and then transferred to the next bonding step.

In order to simplify the process of a pick-up process and a die bonding process among these processes, the various adhesive sheets for dicing and die bonding which combine the wafer holding function and the die bonding function simultaneously are proposed (for example, patent documents 1-4). ).

In patent documents 1-4, the adhesive sheet in which the adhesive agent layer which consists of specific compositions is formed on a base material is disclosed. This adhesive layer has the function of fixing a wafer at the time of wafer dicing, and when picking up a chip | tip after completion | finish of dicing, an adhesive agent layer peels from a base material with a chip | tip. When the chip with an adhesive agent layer is put on the die pad part of a board | substrate, and it heats, the thermosetting resin in an adhesive agent layer expresses adhesive force, and adhesion | attachment of a chip | tip and a board | substrate is completed.

Thereafter, in order to obtain electrical conduction between the chip and the wire pad portion of the substrate or the lead portion of the metal frame, metal wires such as gold wires are connected (wire bonding) to the wire pad portions of the chip and the substrate. Thereafter, for the purpose of electrical and mechanical protection from external environments, sealing or pottering is carried out by transfer molding, and solder balls are mounted on the back of the substrate, or the metal lead frame is unsealed. By soldering a part, it becomes possible to complete it as a semiconductor device and to make electrical connection with an external system.

The adhesive sheet disclosed by the said patent document enables what is called direct die bonding, and can apply the coating process of the adhesive agent for die bonding. A low molecular weight energy ray curable compound is compounded in the adhesive agent disclosed in the said patent document as an energy ray curable component. By irradiating an energy ray before picking up a chip after dicing, the said energy-beam curable compound polymerizes and hardens, the adhesive force of an adhesive agent layer falls, and peeling of an adhesive agent layer from a base material becomes easy. Moreover, in the adhesive agent layer of the said adhesive sheet, all the components harden | cure after die-bonding which passed through energy ray hardening and thermosetting, and adhere | attachs a chip | tip and a board | substrate firmly.

In addition, Patent Document 4 discloses an adhesive agent composition comprising (A) an adhesive component, (B) a thermosetting adhesive component, and (C) a compound in which a silane coupling agent is added and condensed to a polysiloxane oligomer, As said compound (C), the compound represented by a following formula is disclosed.

In the above formula, R is a methyl group or an ethyl group, S is a group introduced by R or a silane coupling agent, and in one molecule of the compound (C), two or more groups introduced by the silane coupling agent are preferably included. .

In recent years, however, further high integration has been desired for semiconductor devices. In order to highly integrate a semiconductor device, a plurality of chips may be stacked vertically within a limited fixed height range, and therefore, it is required to further thin a chip constituting the semiconductor device.

And with thinning of a chip | tip, the peeling force at the time of picking up a chip | tip (the force required to peel an adhesive agent layer with a chip | tip from the base material of this adhesive sheet) becomes a big factor which determines a yield. If this value is large, the chip breaks or breaks off at the time of pickup, resulting in a decrease in the yield of the chip. In addition, the strength of wafers and chips during transport is a big factor in determining product yield.

In other words, recently required high integration of semiconductor devices has caused a decrease in yield of semiconductor devices.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-32181

[Patent Document 2] Japanese Patent Application Laid-Open No. 8-239636

[Patent Document 3] Japanese Patent Application Laid-Open No. 10-8001

[Patent Document 4] Japanese Patent Application Laid-Open No. 2000-17246

For this reason, in a semiconductor device in which a thin chip is mounted, it is required to obtain a good product with a high yield as a semiconductor device without cracking or breaking the chip at the time of its manufacture.

This invention is made | formed in view of the prior art as mentioned above, and aims at responding to the said request further by examining the adhesive agent used at the time of dicing and die bonding of a chip | tip.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining for the purpose of solving such a subject, the present inventors discovered that the said subject can be solved by the adhesive sheet which has the adhesive agent layer which consists of an adhesive composition containing a specific silicone compound component, The present invention has been completed.

When the adhesive sheet is used, even when the chip is thin, the peeling force at the time of picking up the chip is small, so that a good product can be obtained in a high yield as a semiconductor device without breaking or chipping the chip in the pick-up step.

That is, the summary of this invention is as follows.

[1] An adhesive agent composition comprising an acrylic polymer (A), an epoxy resin (B), a thermosetting agent (C), and a silicone compound (D), wherein the silicone compound (D) is an aromatic ring-containing group as a side chain An organopolysiloxane which has a reactive organic functional group (except reactive organic functional group), Furthermore, the kinematic viscosity in 25 degreeC is 50-100,000 mm <2> / s, The adhesive agent composition characterized by the above-mentioned.

[2] The adhesive agent composition according to the above [1], wherein the aromatic ring-containing group is an aralkyl group.

[3] The adhesive agent composition according to the above [1] or [2], wherein the thermosetting agent (C) is a thermosetting agent having a phenolic hydroxyl group and / or an amino group.

[4] The adhesive sheet, wherein the adhesive layer made of the adhesive composition of the above-mentioned [1] or [2] is formed on the substrate.

[5] The adhesive sheet, wherein the adhesive layer made of the adhesive composition according to the above [3] is formed on the substrate.

[6] a step of bonding the semiconductor wafer to the adhesive layer of the adhesive sheet as described in [4] above, a step of dicing the semiconductor wafer into a chip, and the chip on the back surface of the adhesive agent Manufacture of a semiconductor device comprising a step of transferring a layer and peeling it from the base material of the adhesive sheet, and a step of thermocompression bonding the peeled chip onto the die pad portion via an adhesive layer transferred to the back side of the chip. Way.

[7] A step of bonding the semiconductor wafer to the adhesive layer of the adhesive sheet as described in [5] above, a step of dicing the semiconductor wafer into a chip, and the chip on the back side of the adhesive agent. Manufacture of a semiconductor device comprising a step of transferring a layer and peeling it from the base material of the adhesive sheet, and a step of thermocompression bonding the peeled chip onto the die pad portion via an adhesive layer transferred to the back side of the chip. Way.

According to the adhesive sheet of the present invention, in the manufacture of a semiconductor device on which a thin chip is mounted, the force required for pick-up in the pick-up step is reduced, and the chip is hardly split or broken. For this reason, a good product can be obtained with a high yield as a semiconductor device.

Moreover, according to this invention, the manufacturing method of the semiconductor device using this adhesive sheet is provided.

Hereinafter, the present invention will be described in further detail.

[Adhesive Adhesive Composition of the Present Invention]

The adhesive agent composition of this invention contains an acrylic polymer (A), an epoxy resin (B), a thermosetting agent (C), and a specific silicone compound (D) as an essential component, and in order to improve various physical properties, Other components may be included as needed. Hereinafter, each of these components is demonstrated concretely.

<(A) Acrylic Polymer>

As the acrylic polymer (A), a conventionally known acrylic polymer can be used. It is preferable that it is 10,000 or more and 2 million or less, and, as for the weight average molecular weight of an acrylic polymer (A), it is more preferable that it is 100,000 or more and 1.5 million or less. When the weight average molecular weight of an acrylic polymer is too low, the adhesive force with a base material may become high, and the pick-up defect of a chip may generate | occur | produce, and when it exceeds 2 million, when the adhesive agent layer to a board | substrate unevenness cannot be followed There is a cause of occurrence of voids and the like. In addition, in this specification, a weight average molecular weight points out the weight average molecular weight by standard polystyrene molecular weight conversion measured by GPC.

Glass transition temperature of an acrylic polymer (A) becomes like this. Preferably it is -60 degreeC or more and 20 degrees C or less, More preferably, it is -50 degreeC or more and 10 degrees C or less, Especially preferably, it is in the range of -40 degreeC or more and 5 degrees C or less. If the glass transition temperature is too low, the peeling force of the adhesive agent layer and the substrate may increase, so that pick-up failure of the chip may not be improved. If the glass transition temperature is too high, the adhesive force for fixing the wafer may become insufficient.

As a monomer which forms the structural unit of an acrylic polymer (A), the (meth) acrylic acid ester monomer or its derivative (s) is mentioned.

Examples of the (meth) acrylic acid ester monomer include alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group, and examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are mentioned.

Moreover, as a derivative of a (meth) acrylic acid ester monomer, the (meth) acrylate which has a cyclic skeleton is mentioned, for example, As such a compound, for example, cycloalkyl (meth) acrylate and benzyl ( Meta) acrylate, isobonyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, imide acrylate, glycidyl methacrylate, glycidyl acrylate Can be mentioned.

As another example of this derivative, (meth) acrylate containing a hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy Propyl methacrylate.

In addition, acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, etc. may be copolymerized with the acrylic polymer (A).

Among the monomers exemplified above, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate having a hydroxyl group are epoxy resins (B). It is preferable because compatibility with is good.

An acrylic polymer (A) can be used individually by 1 type or in combination of 2 or more type.

<(B) Epoxy Resin>

As an epoxy resin (B), conventionally well-known various epoxy resins can be used individually by 1 type or in combination of 2 or more types. Conventionally known various epoxy resins include bisphenol A diglycidyl ether and hydrogenated substances thereof, ortho cresol novolac type epoxy resins (see formula 1 below), dicyclopentadiene type epoxy resins (see formula 2 below), biphenyl type Epoxy compounds which have two or more functional groups in a molecule | numerator, such as an epoxy resin (refer Formulas 3 and 4 below) and a polyfunctional epoxy resin (see Formula 5 below), are mentioned. As an epoxy resin (B), it is preferable that an aromatic ring is contained in the main skeleton.

(Wherein n represents an integer of 0 or more)

(Wherein n represents an integer of 0 or more)

(Wherein n represents an integer of 0 or more)

(Wherein R is a hydrogen atom or a methyl group)

(Wherein n represents an integer of 0 or more)

<(C) thermosetting agent>

A thermosetting agent (C) functions as a hardening | curing agent of an epoxy resin (B), and by using this, physical properties, such as adjustment of the thermosetting reaction rate of the adhesive agent layer which becomes an adhesive agent composition, and the elasticity modulus of the hardened | cured material of this adhesive agent layer are preferable. You can adjust the area.

As a preferable thermosetting agent, the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, A phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acid anhydride, etc. are mentioned as this functional group. Among these, from a hardenable viewpoint, Preferably they are a phenolic hydroxyl group, an amino group, and an acid anhydride, More preferably, they are a phenolic hydroxyl group and an amino group.

Specific examples of these thermosetting agents include phenolic thermosetting agents such as novolak-type phenol resins (see formula 6), dicyclopentadiene-type phenol resins (see formula 7 below), and polyfunctional phenol resins (see formula 8 below); Amine type hardening | curing agents, such as DICY (dicyandiamide), are mentioned. These thermosetting agents can be used individually or in mixture of 2 or more types.

(Wherein n represents an integer of 0 or more)

(Wherein n represents an integer of 0 or more)

(Wherein n represents an integer of 0 or more)

As a thermosetting agent (C), it is preferable that an aromatic ring is contained in the main skeleton.

The content of the epoxy resin (B) and the thermosetting agent (C) is preferably an amount of 1 to 1500 parts by weight, more preferably 3 to 1000 parts by weight based on 100 parts by weight of the acrylic polymer (A). Do. If it is less than 1 weight part, sufficient adhesiveness may not be obtained and the effect of this invention may not fully be acquired. On the other hand, when it exceeds 1500 weight part, it may become difficult to process an adhesive agent composition into a sheet form.

In addition, the usage-amount of a thermosetting agent (C) becomes like this. Preferably it is 0.1-500 weight part with respect to 100 weight part of epoxy resins (B), More preferably, it is 1-200 weight part. When the usage-amount of the thermosetting agent (C) with respect to an epoxy resin (B) is too small, adhesiveness may not be obtained due to lack of hardening, and when too much, a moisture absorption may become high and the reliability of a semiconductor device may fall.

<(D) Silicone Compound>

The adhesive agent composition of this invention is characterized by including a specific silicone compound (D), and picking up a chip | tip in the pick-up process of the chip | tip divided into (dicing) by this, The required force (pickup force) can be lowered so that chips can be picked up one by one without breaking or breaking.

Here, a silicone compound (D) is organopolysiloxane which has an aromatic ring containing group (except reactive organic functional group) as a side chain, and says that kinematic viscosity in 25 degreeC is 50-100,000 mm <2> / s.

The polysiloxane is a compound in which a plurality of unit structures (X represents a side chain) represented by -Si (X) ₂ -O- is connected, and the number of the unit structures is not particularly limited as long as the range of the kinematic viscosity is satisfied. 3 or more.

The silicone compound (D) lowers the pick-up force by the siloxane moiety of the organopolysiloxane, and has the above-mentioned aromatic ring-containing group in the side chain, thereby having high fat solubility and high compatibility with other components in the adhesive composition. In addition, the epoxy resin (B) and the thermosetting agent (C) in an adhesive agent composition often have an aromatic ring as a component, and in such a case, mutual compatibility is carried out by the said aromatic ring containing group of a silicone compound (D). Even higher. By adding a silicone compound (D) having high compatibility with other components in the adhesive composition, it is possible to effectively prevent the chip from breaking or breaking during the pick-up process. (D) is hard to leak out in an adhesive agent layer at the time of a heating process, such as a die bonding process, or to generate | occur | produce as outgas.

The aromatic ring-containing group is an aromatic ring-containing group excluding a reactive organic functional group, and examples thereof include a phenyl group and an aralkyl group. The aralkyl group herein refers to an alkyl moiety being linear or branched, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and preferably 6 to 10 carbon atoms, more preferably an aryl moiety. Aralkyl group of six. Preferred examples of the aralkyl group include benzyl group, phenylethyl group, phenylpropoxy and phenylisopropyl group.

As said aromatic ring containing group, an aralkyl group is preferable. When the aromatic ring is bonded directly to the silicon of the polysiloxane skeleton via an alkyl moiety as in the aralkyl group, rather than the aromatic ring directly bonded to silicon, the degree of freedom of the aromatic ring is high, and the epoxy resin (B), the thermosetting agent (C), This is because compatibility is further enhanced by taking an optimum arrangement therewith.

The reactive organic functional group refers to a functional group having an electron donating group or an electron withdrawing group. Specific examples thereof include a hydroxyalkyl group, a carboxyalkyl group, an aminoalkyl group, an epoxy group-containing alkyl group, an alicyclic epoxy group-containing alkyl group, a methacryl group-containing alkyl group, a phenol group-containing alkyl group and a mercaptoalkyl group.

Moreover, the ratio which the said aromatic ring containing group in a side chain occupies is 5-100 mol% normally, Preferably it is 10-90 mol%, More preferably, it is 15-80 mol%. When the ratio of the aromatic ring-containing group to the side chain is less than 5 mol%, compatibility with the adhesive layer is insufficient, and outgas or the like may occur in the die bonding step or the like. Incidentally, the side chain portions other than those occupied by the aromatic ring-containing group are occupied by alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group.

On the other hand, the dynamic viscosity at 25 degrees C of a silicone compound (D) is 50-100,000 mm <2> / s, Preferably it is 200-10,000 mm <2> / s, More preferably, it is 500-3,000 mm <2> / s.

If the kinematic viscosity at 25 ° C. is less than 50 mm 2 / s, the silicon compound (D) will bleed out from the adhesive layer at the time of die bonding, and if it exceeds 100,000 mm 2 / s, it will be different from the silicone compound (D) in the adhesive layer. The components are phase separated and a uniform pick-up force is not obtained.

In addition, in this specification, a kinematic viscosity points out the value measured with the Uberode viscometer based on JISK2283.

Although the effect which reduces pick-up force is acquired with the adhesive agent composition which mix | blended PDMS (polydimethylsiloxane) which is the most common silicone compound, a problem arises in the wire bonding process after a die bonding process. This is because PDMS has poor compatibility with epoxy resins through a process that requires heating such as a thermosetting process or a wire bonding process at the time of die bonding, so that low-molecular siloxanes are oozed out of the adhesive layer or released as outgas. It is considered that this is because the wire pad portion connecting the wire such as gold or aluminum is contaminated, and as a result, stable connection strength is not obtained.

On the other hand, since the silicone compound (D) used by this invention has an aromatic ring containing group in a side chain, it has high compatibility with the phenol resin used as an epoxy resin (B) or a thermosetting agent (C), It is thought that it is difficult to exude to the outside. For this reason, a silicone compound (D) hardly leaks out of an adhesive agent layer, and is hard to generate | occur | produce as an outgas. Therefore, when the adhesive agent composition of this invention is used, stable wire bonding property is realized without the wire pad part being contaminated in the die bonding process of a chip | tip.

A silicone compound (D) can be manufactured by a conventionally well-known method, and can also be obtained as a commercial item, For example, as an organopolysiloxane which has an aralkyl group in a side chain, "XF42-334 (Momentive Papmans. "Material Rouge Japan Advanced Chemical Co., Ltd." and "X-22-1877 (Shin-Etsu Chemical Co., Ltd.)" are mentioned as organopolysiloxane which has a phenyl isopropyl group in a side chain.

The silicone compound which has an aromatic ring containing group in these side chains can be used individually or in combination of 2 or more types, respectively.

Content of a silicone compound (D), Preferably it is 0.001-5 weight part with respect to the weight of an adhesive agent layer, More preferably, it is 0.05-1 weight part. Although an adhesive agent layer is described in detail later, it is obtained by apply | coating and drying an adhesive agent composition on a base material. In order to make it easier to apply an adhesive composition on a base material, it is common to contain a solvent in an adhesive agent composition. Therefore, the weight of an adhesive agent layer removes the weight of volatile components, such as a solvent, from the weight of the whole adhesive agent composition.

If it is 0.001 weight part or less, the effect of lowering pick-up force may not fully be acquired, and if it is 5 weight part or more, the adhesive force with the chip of an adhesive agent layer may fall, and reliability as a semiconductor device may fall.

As explained above, the adhesive agent composition of this invention contains an acrylic polymer (A), an epoxy resin (B), a thermosetting agent (C), and the silicone compound (D) which has a specific side chain. Since the silicone compound (D) can lower the pick-up force and hardly bleed out of the adhesive layer or occur as outgas, the adhesive sheet having the adhesive layer of the adhesive composition of the present invention can be used. In the wire bonding step performed after die bonding of the chip, the wire can be stably connected to the chip without contaminating the wire pad portion existing around the adhesive surface. As a result, a good product can be obtained with a high yield as a semiconductor device. The adhesive agent composition of this invention may contain the following components as needed in order to improve various physical properties.

<(E) Curing accelerator>

A hardening accelerator (E) is used to adjust the hardening rate of an adhesive agent composition. As a preferable hardening accelerator, the compound which can accelerate | stimulate reaction with an epoxy group, a phenolic hydroxyl group, an amino group, etc. are mentioned. Specifically,

Tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol;

Imidazoles such as 2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole;

Organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine;

Tetraphenyl boron salts, such as tetraphenyl phosphonium tetraphenyl borate and a triphenyl phosphine tetraphenyl borate, etc. are mentioned.

These can be used individually or in mixture of 2 or more types.

It is preferable to contain 0.01-100 weight part with respect to 100 weight part of epoxy resins (B) from a hardening point (E) from a sclerosis | hardenability viewpoint, 0.1-50 weight part is more preferable, 1-30 weight part is more preferable.

<(F) Coupling agent>

Coupling agent (F) is used in order to improve the adhesiveness and adhesiveness to the to-be-adhered body of an adhesive agent composition. Moreover, by using a coupling agent, the water resistance can be improved, without impairing the heat resistance of the hardened | cured material obtained by hardening | curing an adhesive agent composition. As a coupling agent, the compound which has group which reacts with the functional group which the said (A) component, (B) component, (C) component, etc. have is used preferably.

As a coupling agent (F), a silane coupling agent is preferable. Such coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ- (methacrylo) Propyl) 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-tri Ethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, and the like.

Since these coupling agents have at least 2 or more types of functional groups in a molecule | numerator, they improve adhesiveness of an adhesive agent layer, a chip | tip, or an organic substrate after hardening.

These can be used individually or in mixture of 2 or more types. When using these coupling agents (F), it is 0.1-20 weight part normally with respect to 100 weight part of epoxy resins (B), Preferably it is used in the ratio of 0.5-15 weight part, More preferably, it is 1-10 weight part. When it is less than 0.1 weight part, the effect as a coupling agent may not be acquired, and when it exceeds 20 weight part, there exists a possibility that a coupling agent may be discharge | released as outgas.

<(G) crosslinking agent>

In order to adjust the initial adhesive force and cohesion force of the adhesive agent composition of this invention, it is also possible to contain a crosslinking agent (G). Examples of the crosslinking agent (G) include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.

As said organic polyvalent isocyanate compound, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, an alicyclic polyvalent isocyanate compound, etc. are mentioned.

More specific examples of the organic polyvalent isocyanate compound include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane- 4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-di Isocyanate, dicyclohexyl methane-2,4'- diisocyanate, and lysine isocyanate. Moreover, the trimer of these polyvalent isocyanate compounds, the terminal isocyanate urethane prepolymer obtained by making these polyvalent isocyanate compounds, and a polyol compound react etc. are contained in the said organic polyvalent isocyanate compound.

Specific examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-b-aziridinylpropionate, tetramethyl Olmethane-tri-b-aziridinylpropionate and N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylenemelamine.

These can be used individually or in mixture of 2 or more types.

The crosslinking agent (G) is usually used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the acrylic polymer (A).

<(H) inorganic filler>

By mixing the inorganic filler (H) with the adhesive agent composition of the present invention, the thermal expansion coefficient thereof can be adjusted, and the heat resistance of the semiconductor device can be improved by optimizing the thermal expansion coefficient of the adhesive agent layer after curing with respect to the chip or the organic substrate. Can be. Moreover, it becomes possible to reduce the moisture absorption after hardening of an adhesive agent layer.

Preferred inorganic fillers include silica, alumina, talc, calcium carbonate, titanium white, bengal, silicon carbide, boron nitride, powders such as beads, spherical beads, single crystal fibers, glass fibers and the like.

In this invention, use of a silica powder and an alumina powder is preferable among these.

These can be used individually or in mixture of 2 or more types.

An inorganic filler (H) can be adjusted in the range of 0 to 80 weight% normally with respect to the whole adhesive agent composition.

<(I) energy ray polymerizable compound>

An energy ray polymeric compound (I) may be mix | blended with the adhesive agent composition of this invention. Since the adhesive force of an adhesive agent layer can be reduced by hardening the adhesive agent layer which the energy-beam polymerizable compound (I) was mix | blended by energy ray irradiation, the interlayer peeling of the base material and adhesive agent layer in a pick-up process is carried out. It can be performed easily.

The energy ray polymerizable compound (I) is a compound which is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams.

Specific examples of the energy ray-polymerizable compound (I) include dicyclopentadienedimethoxydiacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol monohydroxypenta. Acrylate, dipentaerythritol hexaacrylate or 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy modified Acrylate type compounds, such as an acrylate, a polyether acrylate, and an itaconic acid oligomer, are mentioned.

Such a compound has one or more polymerizable double bonds in a molecule | numerator, and a weight average molecular weight is 100-30,000 normally, Preferably it is about 300-10,000.

These can be used individually by 1 type or in combination of 2 or more types.

In the case of using the energy ray polymerizable compound (I), the content of the energy ray polymerizable compound (I) in the adhesive composition is usually 1 to 400 parts by weight, preferably 3 to 100 parts by weight of the acrylic polymer (A). 300 parts by weight, more preferably 10 to 200 parts by weight. When it exceeds 400 weight part, the adhesiveness of the adhesive agent layer with respect to an organic substrate or a lead frame may fall.

<(J) Photoinitiator>

The adhesive agent composition which the energy-beam polymerizable compound (I) was mix | blended may irradiate an ultraviolet-ray as an energy ray at the time of its use. At this time, by adding a photoinitiator (J) in this composition, polymerization hardening time and a light irradiation amount can be reduced.

As such a photoinitiator (J), specifically, benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin Methyl benzoate, benzoin dimethyl ketal, 2,4-diethyl thioxanthone, α-hydroxycyclohexylphenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, diacetyl, β -Chloro anthraquinone, etc. are mentioned.

A photoinitiator (J) can be used individually by 1 type or in combination of 2 or more types.

Although the compounding ratio of a photoinitiator (J) should theoretically be determined based on the amount of unsaturated bonds in the adhesive agent, its reactivity, and the reactivity of the photoinitiator used, it is not necessarily easy in a complicated mixture system.

When using a photoinitiator (J), as a general guideline, the content of the photoinitiator (J) in an adhesive agent composition is 0.1-10 weight part is preferable with respect to 100 weight part of energy ray polymeric compounds (I), 1 5 weight part is more preferable. If it is less than 0.1 weight part, satisfactory pick-up property may not be obtained by lack of photopolymerization, and when it exceeds 10 weight part, the residue which does not contribute to photopolymerization may produce | generate, and the hardenability of an adhesive agent layer may become inadequate.

<Other Ingredients>

Various additives may be mix | blended with the adhesive agent composition of this invention as needed other than said component. For example, a flexible component can be added in order to maintain the flexibility of the hardened | cured material after an adhesive agent layer hardens. The flexible component is a component having flexibility at room temperature and under heating, and one that is not substantially cured by heating or energy ray irradiation is selected. The flexible component may be a polymer made of a thermoplastic resin or an elastomer, or may be a graft component of a polymer or a block component of a polymer. In addition, the modified resin may be a modified component previously modified with an epoxy resin.

Moreover, as various additives of the adhesive agent composition of this invention, a plasticizer, an antistatic agent, antioxidant, a pigment, dye, etc. are mentioned.

The adhesive agent composition which consists of each above-mentioned component has pressure-sensitive adhesiveness and heat hardenability, and has a function to temporarily hold various adherends in an uncured state. Finally, the cured product having high impact resistance can be provided through thermal curing, and the balance between shear strength and peeling strength is excellent, and sufficient adhesive physical properties can be maintained even under strict wet heat conditions.

And the adhesive agent composition of this invention reduces pick-up force, makes it possible to obtain a good product with a high yield as a chip, and also the wire pad part which exists around an adhesive surface in the wire bonding process performed after die bonding of a chip | tip. It is also possible to stably connect the wire to the chip without contaminating it. As a result, a good product can be obtained with a high yield as a semiconductor device.

The adhesive agent composition of this invention is obtained by mixing each said component in an appropriate ratio. In the case of mixing, you may dilute each component with a solvent previously, and may add a solvent at the time of mixing.

[Adhesive Adhesive Sheet of the Present Invention]

The adhesive agent layer which becomes the said adhesive agent composition is formed on the base material of the adhesive agent sheet of this invention. The shape of the adhesive sheet of this invention can take all shapes, such as a tape form and a label form.

As a base material of an adhesive adhesive sheet, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethyl pentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polyethylene naphthalate, for example Film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene (meth) acrylic acid copolymer film, ethylene (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film , Transparent films such as polyimide films and fluororesin films are used.

Moreover, these crosslinked films are also used. Furthermore, these laminated | multilayer film may be sufficient. Moreover, in addition to said transparent film, the opaque film which colored these can be used.

The adhesive sheet of this invention is affixed to various to-be-adhered bodies, and after performing required processing to a to-be-adhered body, an adhesive agent layer is transcribe | transferred to a to-be-adhered body and peels from a base material. That is, the adhesive sheet of this invention is used for the process including the process of transferring an adhesive layer from a base material to a to-be-adhered body.

For this reason, the surface tension of the surface which contacts the adhesive agent layer of a base material becomes like this. Preferably it is 40 mN / m or less, More preferably, it is 37 mN / m or less, Especially preferably, it is 35 mN / m or less. In addition, the surface tension needs to be 5 mN / m or more so that the adhesive agent layer does not peel from a chip | tip or a base material until a pick-up process. A substrate having such a low surface tension can be obtained by appropriately selecting a material, and can also be obtained by applying a release agent to the surface of the substrate and subjecting the release treatment.

Alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, wax-based, etc. are used as the release agent used for the stripping treatment of the base material, but the alkyd-based, silicone-based, and fluorine-based release agents are preferable because they have heat resistance.

In addition, when using a silicone type | system | group release agent, since the silicone type release agent apply | coated to the base material may adhere to an adhesive agent layer, and the effect of this invention may become impossible, the usage-amount should only be the minimum required. do.

In order to peel-off the surface of a base material using said peeling agent, a peeling agent is used as it is, without solvent, or solvent dilution or emulsification is apply | coated to a base material with a gravure coater, a Meyer bar coater, an air knife coater, a roll coater, etc., and room temperature What is necessary is just to form a laminated body of a base material layer and a peeling agent layer by hardening by heating or an electron beam, or by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion processing, etc.

The film thickness of a base material is 10-500 micrometers normally, Preferably it is 15-300 micrometers, Especially preferably, it is about 20-250 micrometers.

In addition, the thickness of an adhesive agent layer is 1-500 micrometers normally, Preferably it is 5-300 micrometers, Especially preferably, it is about 5-150 micrometers.

The manufacturing method of the adhesive bonding sheet of this invention is not specifically limited, It can manufacture by a well-known method. For example, you may manufacture by apply | coating and drying the adhesive agent composition which comprises an adhesive agent layer on a base material, and you may manufacture by providing an adhesive agent layer on a peeling film, and transferring this to the said base material. In addition, in order to protect an adhesive layer before use of an adhesive sheet, you may laminate | stack a peeling film on the upper surface of an adhesive agent layer. Moreover, in order to fix another jig | tool, such as a ring frame, the pressure-sensitive adhesive layer may be provided in the surface outer peripheral part of an adhesive agent layer separately.

[Method of Manufacturing Semiconductor Device]

Next, the use method of the adhesive sheet of this invention is demonstrated taking the case where this adhesive sheet is applied to manufacture of a semiconductor device as an example.

In the semiconductor device manufacturing method of the present invention, first, the adhesive sheet of the present invention is fixed on a dicing apparatus by a ring frame, and one surface of the semiconductor wafer is placed on the adhesive layer of the adhesive sheet. Press lightly to fix the semiconductor wafer.

Subsequently, the said semiconductor wafer is cut | disconnected using cutting means, such as a dicing blade, and a chip is obtained. The depth of cut at this time is made into the depth which added the thickness of the semiconductor wafer, the sum total of the thickness of an adhesive agent layer, and the abrasion of a dicing blade.

Subsequently, if necessary, when the adhesive sheet is expanded, the chip spacing is extended, so that the pick-up of the chip can be performed more easily. At this time, a deviation occurs between the adhesive layer and the base material, the adhesive force between the adhesive layer and the base material decreases, and the pick-up property of the chip is improved. In addition, in the case where the adhesive layer contains the energy ray-polymerizable compound (I), the pick-up force may be reduced by irradiating the energy ray after dicing, or by irradiating the energy ray before dicing. Adhesion can be exhibited.

When the chip is picked up in this manner, the cut adhesive layer can be transferred to the back surface of the chip to be peeled off from the substrate.

Since the adhesive agent composition of this invention contains a silicone compound (D) as mentioned above, pick-up force is low and for this reason, a good product can be obtained with a high yield as a chip, without chip | cracking or chipping.

The chip is then placed on the die pad portion of the substrate via the adhesive layer. The die pad portion is heated before or after placing the chip. The heating temperature 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, and the mounting pressure is usually 1 kPa. ˜200 MPa.

After placing a chip on a die pad part, you may heat further as needed. The heating conditions at this time are the range of the said heating temperature, and heating time is 1 to 180 minutes normally, Preferably it is 10 to 120 minutes.

In addition, you may make it the temporary adhesive state, without performing the heat processing after mounting, and harden an adhesive agent layer using the heating in the resin sealing performed by a post process.

By passing through such a process, an adhesive agent layer hardens | cures and a chip and a die pad part can be adhere | attached firmly. Since the adhesive agent layer is fluidized under die bonding conditions, the unevenness of the die pad portion is also sufficiently filled, so that generation of voids can be prevented.

That is, in the obtained packaged product, the adhesive agent, which is a chip fixing means, is cured, and the concave and convexities of the die pad portion are sufficiently filled, so that sufficient semiconductor device reliability and board mountability are achieved even under severe conditions.

In this way, after bonding the chip to the substrate, wire bonding may be further performed. As mentioned above, since the silicone compound (D) used by this invention has an aromatic ring containing group in a side chain, it is high in compatibility with an epoxy resin, and it is hard to bleed out to an exterior of an adhesive agent layer, or to generate | occur | produce as an outgas. Therefore, the wire pad portion is not contaminated in the wire bonding step of the chip, and stable wire bonding property is realized.

Moreover, the adhesive agent composition and adhesive sheet of this invention can also be used for adhesion | attachment of a semiconductor compound, glass, ceramics, a metal, etc. other than the usage method as mentioned above.

Example

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

In addition, in the following example and the comparative example, "pickup load measurement", "pickup test", and "wire pull test" were performed as follows.

`` Pickup Load Measurement ''

On the back side of a 6-inch wafer (thickness; 350 µm, back side; # 2000 grinding), the adhesive sheets of Examples and Comparative Examples were affixed to fix the wafer to a ring frame (2-6-1 manufactured by Disco), and The wafer was subjected to the use of a sawing device (Disco; DFD651, Dicing Blade; 27HECC, manufactured by Disco) under conditions of a blade feeding speed of 50 mm / sec, rotational speed of 30000 rpm, and an amount of cut to an adhesive sheet of 50 μm. Full cut to 5 mm square.

This is stretched 12 mm overall (expanded) parallel to the wafer abutment surface along the inner diameter of the ring frame, and the pushed gauge (a CPU gauge manufactured by Aiko Corporation) is pressed at the rear to press the separated chip, The force required for peeling a chip | tip in the state which affixed the adhesive bond layer was measured for 30 pieces, and the average was calculated | required.

`` Pickup Test ''

The dicing apparatus was affixed on the back of an 8-inch wafer (thickness; 75 µm, backside; dry polish), and the adhesive sheets of Examples and Comparative Examples were fixed to the ring frame (Disco 2-8-1). (Disco; DFD651, Dicing Blade; Disco Co., Ltd. 27HECC), the wafer was subjected to 8 mm square under a condition of a blade feeding speed of 50 mm / sec, a rotational speed of 30000 rpm, and an amount of cut to an adhesive sheet of 50 µm. It was separated into pieces (chips) by full-cutting.

By using a full auto die bonder (Canon Machinery; BESTEM-DOII), a 4 plus 1 pin push jig and a hollow collet are used for a total pin lift amount of 600 µm and a push speed of 10 mm / s. When each 20 pieces were pushed up, the chip was not lifted and the device stopped, or the chip was picked up without a defect that the chip was broken, and the number of chips that could be placed on the substrate was determined.

`` Wire pool test ''

Tape-mounted adhesive adhesive sheets of Examples and Comparative Examples were polished on a polished surface of a # 2000 polished TEG wafer (manufactured by Hitachi ULSI system; PHASEO (polyimide coating, aluminum pad opening 80 μm □, diameter 150 mm, thickness 350 μm)) (Made by Lintec; Adwill RAD2500), it affixed and fixed to the ring frame for wafer dicing. Subsequently, using a dicing apparatus (Disco Co., Ltd .; DFD651, Dicing Blade; Disco Co., Ltd. 27HECC), the blade was subjected to a feed rate of 50 mm / sec, a rotational speed of 40,000 rpm, and a cut amount of 50 µm to the adhesive sheet. The wafer was diced to obtain a chip of 8.52 mm square size.

Using this, BT resin (manufactured by Mitsubishi Gas Chemical Co., Ltd .; CCL-HL832HS) as an insulating adhesive layer, a circuit pattern was formed on the copper foil of the laminated substrate with copper foil, and had a solder resist (PSR4000 AUS303 made by Daiyo Ink) on the pattern. The die-bonding was carried out to the board | substrate (made by Hitachi ULSI system; 0.4 micrometers of bonding pads Ni / Au alloy) using the full auto die bonder apparatus (made by Canon machine; BESTEM-DOII).

After heat-hardening an adhesive layer by applying this heat in oven at 120 degreeC for 1 hour, and further at 140 degreeC for 1 hour, the wire bonder (made by Shinkawa Co., Ltd .; UTC-470 (φ25 micrometer Au wire wire, the product made by K & S Corporation) 486FC-2052-R34 capillary)) was bonded at 180 ° C. for 10 milliseconds with a load of 25 gf and an ultrasonic output of 30 PLS using 236 wires to bond the chip and the substrate. For each of the 20 pieces, the wire center portion was pulled vertically with respect to the chip surface (wire pull test) to measure the tensile strength when the wire was broken, and the connection portion on the chip side did not fall, and the wire portion was broken. And the number of wires showing a tensile strength of 7.0 gf or more. The above-mentioned "pulling the wire center part in the vertical direction with respect to the chip surface" is shown in FIG.

In addition, each component which comprises the adhesive agent composition of the adhesive sheet of an Example and a comparative example is as follows.

(A) Acrylic polymer: Nippon Synthetic Chemical Co., Ltd. make, Coponyl N-2359-6 (Mw: about 300,000, Tg: -28 degreeC)

(B-1) Liquid epoxy resin: Bisphenol A type epoxy resin 20 phr Acrylic particle-containing product (Nippon Shokubai Co., Ltd .: Eposet BPA328, Epoxy equivalent 235 g / eq)

(B-2) Solid epoxy resin: Bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd .: EPICRON 1050, epoxy equivalent 850 g / eq)

(B-3) Solid epoxy resin: DCPD type epoxy resin (Dainippon Ink Chemical Co., Ltd .: EPICRON HP-7200HH, epoxy equivalent 278 g / eq)

(C) Thermosetting agent: novolak-type phenol resin (Showa Polymer Co., Ltd .: Shool BRG-556, phenolic hydroxyl equivalent 104 g / eq)

(D-1) Side chain alkyl, an aralkyl modified silicone compound (Organopolysiloxane which has an aralkyl group in a side chain; Momentive performances material loose rouge Japan company: XF42-334; Kinematic viscosity (1,300 mm <2> / s))

(D-2) Unmodified Silicone Compound (Polydimethylsiloxane Momentive Performance Materia Rouge Japan High-Grade: TSF-451-1000, Kinematic Viscosity (1,000 mm 2 / s))

(E) Curing accelerator: 2-phenyl-4-methyl-5-hydroxymethylimidazole (Shikoku Kasei Kogyo Co., Ltd .: Cursol 2PHZ-PW)

(F) Silane coupling agent (Mitsubishi Chemical Corporation make: MKC silicate MSEP2)

(H) Silica filler (Admertex Co., Ltd .: Admerfine SC2050)

(I) Energy-beam polymerizable compound: Dicyclopentadiene dimethoxy diacrylate (Nippon Kayaku Co., Ltd .: KAYARAD R-684)

(J) Photoinitiator: (alpha) -hydroxycyclohexyl phenyl ketone (Siba Specialty Chemicals Corporation make: Irgacure 184)

As the base material of the adhesive sheet, a polypropylene film (thickness 100 m, surface tension 31 mN / m) was used.

(Examples and Comparative Examples)

Table 1 The adhesive composition of the base material composition was used. In a table | surface, a numerical value shows the weight part of conversion of a nonvolatile matter. Table 1 The adhesive composition of the substrate composition was applied on a siliconized release film (SP-PET381031C manufactured by Lintec Co., Ltd.) to a thickness of 30 μm, dried (100 ° C. in a drying condition oven for 1 minute), and then bonded to the substrate ( The adhesive sheet was obtained by bonding together and transferring an adhesive layer onto a base material.

The said three types of tests were done using the obtained adhesive sheet. The results are shown in Table 2.

According to the adhesive sheet using the adhesive agent composition of this invention, even if a chip becomes thin, the wire bonding process performed after die bonding can obtain a good product with a high yield, without a chip being split or broken in a pick-up process. WHEREIN: A wire can be connected stably without polluting the wire pad part which exists in the periphery of an adhesive surface. Thereby, a good product can be obtained with a high yield as a semiconductor device.

Moreover, according to this invention, the manufacturing method of the semiconductor device using this adhesive sheet is provided.

1 shows the shape of pulling the center of the wire in the direction perpendicular to the chip surface in the wire pull test.

Claims (7)

As an adhesive agent composition containing an acrylic polymer (A), an epoxy resin (B), a thermosetting agent (C), and a silicone compound (D), The silicone compound (D) is an organopolysiloxane having an aromatic ring-containing group (excluding reactive organic functional groups) as a side chain, and has a kinematic viscosity at 25 ° C. of 50 to 100,000 mm 2 / s. Composition. The method of claim 1, An adhesive composition, wherein said aromatic ring-containing group is an aralkyl group. The method according to claim 1 or 2, The adhesive agent composition whose said thermosetting agent (C) is a thermosetting agent which has a phenolic hydroxyl group and / or an amino group. The adhesive sheet in which the adhesive agent layer which consists of an adhesive agent composition of Claim 1 or 2 is formed on a base material. The adhesive agent layer in which the adhesive agent layer which consists of an adhesive agent composition of Claim 3 is formed on a base material. Bonding a semiconductor wafer to the adhesive layer of the adhesive sheet of claim 4, and Dicing this semiconductor wafer into chips; Peeling the chip from the base material of the adhesive sheet by transferring the adhesive layer to the back surface thereof; Process of thermocompression bonding the peeled chip on the die pad part through the adhesive agent layer transferred to the back side of the chip Method for manufacturing a semiconductor device comprising a. Bonding a semiconductor wafer to the adhesive layer of the adhesive sheet of claim 5; Dicing this semiconductor wafer into chips; Peeling the chip from the base material of the adhesive sheet by transferring the adhesive layer to the back surface thereof; Process of thermocompression bonding the peeled chip on the die pad part through the adhesive agent layer transferred to the back side of the chip Method for manufacturing a semiconductor device comprising a.

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