KR20130041776A - Adhesive composition, adhesive sheet, and method for producing semiconductor device - Google Patents

Abstract

The present invention relates to a method for producing an adhesive composition, an adhesive sheet and a semiconductor device,
Adhesives used to fix semiconductor chips to chip mounting substrates include acrylic polymers (A), epoxy-based thermosetting resins (B), thermosetting agents (C) and organic chelating agents (D) or heavy metal deactivators (E) An adhesive composition is used, and a gettering function is provided to a semiconductor device obtained without giving special treatment to a semiconductor wafer or a chip.

Description

Adhesive composition, adhesive sheet, and manufacturing method of a semiconductor device {ADHESIVE COMPOSITION, ADHESIVE SHEET, AND METHOD FOR PRODUCING SEMICONDUCTOR DEVICE}

The present invention is an adhesive sheet having an adhesive composition particularly suitable for use in a process of dicing a semiconductor wafer or the like to obtain a semiconductor chip and die-bonding the semiconductor chip onto an organic substrate or a lead frame and an adhesive layer made of the adhesive composition. And a method for producing a semiconductor device using the adhesive sheet.

Semiconductor wafers such as silicon and gallium arsenide are manufactured in a state of large diameter. After forming a circuit on the surface, the semiconductor wafer is ground to a predetermined thickness by backside grinding, cut and separated (dicing) into an element element (semiconductor chip), and then shifted to the bonding process, which is the next step. . At this time, the semiconductor wafer is subjected to dicing, washing, drying, expanding, and picking up in a state where the semiconductor wafer is attached to the adhesive sheet in advance, and then transferred to the bonding step, which is the next step (for example, Patent Documents 1 to 4). Reference).

However, in recent years, it is required to reduce the thickness of a semiconductor chip by request for miniaturization of the device. In order to reduce the size of the device, the wafer is ground thinner by backside grinding. However, as the thickness of the wafer becomes thinner, the wafer strength decreases, and the wafer may be broken even by a slight impact. It is considered that the main cause of wafer breakage is a "crushing layer" in which a cutting trace, an oxide film, or the like of a grinder used for back grinding is combined.

The crushed layer is minute unevenness on the ground of the ground wafer, and it is considered that polycrystalline silicon or silicon is oxidized by a small amount of oxygen, and lattice defects are also included. Due to stress due to surface irregularities and composition changes, even a slight impact may cause cracking and damage to the wafer. For this reason, in order to remove a crushing layer after completion | finish of back surface grinding | polishing, it is common to apply chemical etching, plasma etching, etc. to a back surface. By removing the fractured layer, the strength of the wafer is improved, and even a very thinly ground wafer maintains good handling.

However, there is a concern that the contamination resistance to the metals of the wafers and chips obtained by removing the fractured layers is lowered.

The semiconductor wafer comes in contact with various members during the formation of the circuit, the back grinding and the mounting. At this time, metals, such as copper, are discharged from these other members, and a wafer may become metal contamination. The impurity metal can accumulate in the wafer, ionize under heating conditions such as reflow, and move within the wafer. In addition, the metal ions that reach the circuit surface inhibit the electrical operation of the product and cause malfunction. In addition, metal ions that reach the circuit surface can produce metal at the circuit surface (these can be called migration). In particular, when metal is formed on the surface of the semiconductor wafer where the wiring is miniaturized, the circuit is shorted and the yield of the product is reduced.

On the other hand, the fracture layer is fine irregularities as described above, and it is considered that the polycrystal or silicon of silicon is oxidized with a small amount of oxygen, and lattice defects are also included, and due to the nonuniformity of these compositions and structures, It is thought that an impurity metal is easy to be captured and there is an effect of reducing the influence of metal contamination. The function of such a crushing layer is also called a gettering function.

As described above, after the grinding of the back surface of the wafer is finished, the strength of the wafer is improved by removing the fractured layer, but the gettering function is impaired and the product yield is lowered. For this reason, the technique which gives a gettering function by performing various processes to a semiconductor wafer and a chip | tip after removing a crushing layer is proposed (refer patent document 5, 6).

Patent Document 1: Japanese Patent Application Laid-Open No. 2-32181 Patent Document 2: Japanese Patent Application Laid-open No. Hei 8-239636 Patent Document 3: Japanese Patent Application Laid-Open No. 10-8001 Patent Document 4: Japanese Unexamined Patent Publication No. 2000-17246 Patent Document 5: Japanese Unexamined Patent Publication No. 2005-277116 Patent Document 6: Japanese Laid-Open Patent Publication No. 2007-242713

However, as in Patent Documents 5 and 6, performing a process for imparting a gettering function to a semiconductor wafer and a chip increases the number of processes, which leads to a complicated process and an increase in cost.

This invention is made | formed in view of the said situation, and an object of this invention is to provide a gettering function to the semiconductor device obtained, without carrying out the special process which increases the number of processes and makes a process complicated.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, it was found that a gettering site can be introduce | transduced into a semiconductor device by mix | blending an organic chelating agent or a heavy metal deactivator with the adhesive agent used for fixing a semiconductor chip. With this in mind, the present invention has been completed.

This invention includes the following summary.

(1) Adhesive composition containing an acrylic polymer (A), an epoxy thermosetting resin (B), a hardening | curing agent (C), an organic chelating agent (D), or a heavy metal inactivating agent (E).

(2) Adhesive composition as described in (1) whose organic chelating agent (D) has polyhydric carboxylic acid as a functional group, and the acid value is 100-600 mg / g.

(3) Adhesive composition as described in (1) or (2) whose mass reduction start temperature by differential scanning thermal analysis (TG / DTA) of organic chelating agent (D) is 190 degreeC or more.

(4) The adhesive composition according to any one of (1) to (3), which contains 1 to 35 parts by weight of the organic chelating agent (D) per 100 parts by weight of the adhesive composition.

(5) Adhesive composition as described in (1) containing 1-30 weight part of heavy metal inactivating agents (E) per 100 weight part of adhesive compositions.

(6) The adhesive composition according to (1) or (5), wherein the copper ion adsorption capacity of the heavy metal inactivating agent (E) defined by the following is 30% or more:

0.1 g of a heavy metal deactivator was added to 50 g of a copper chloride aqueous solution having a copper ion concentration of 300 ppm, and the copper ion concentration of the copper ion aqueous solution after standing at 121 ° C. and 2 atm for 24 hours was measured,

Copper ion adsorption capacity is calculated | required by copper ion adsorption capacity = (300ppm-residual copper ion concentration (ppm)) x 100 / 300ppm.

(7) The adhesive composition according to any one of (1), (5) and (6), wherein the heavy metal inactivating agent (E) has the following structure in a part of the molecule.

(R is a hydrocarbon backbone that may contain hydrogen or a hetero atom.)

(8) The adhesive sheet in which the adhesive bond layer which consists of an adhesive composition in any one of said (1)-(7) is formed so that exfoliation is possible on a base material.

(9) A semiconductor wafer is attached to an adhesive layer of the adhesive sheet as described in (8) above, the semiconductor wafer is diced into a semiconductor chip, and the adhesive layer is fixed on the back surface of the semiconductor chip to be peeled off from the substrate. And mounting the semiconductor chip on a die pad portion or on another semiconductor chip with the adhesive layer interposed therebetween.

(10) The method for manufacturing a semiconductor device according to (9), wherein the semiconductor wafer reduces the fracture layer formed by backside grinding to 50 nm or less after backside grinding.

When fixing a semiconductor chip, by using the adhesive composition which concerns on this invention, it becomes possible to introduce a gettering site into the semiconductor device obtained, without giving a special process to a semiconductor wafer and a chip.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated further more concretely including the best form. The adhesive composition according to the present invention contains an acrylic polymer (A), an epoxy thermosetting resin (B), a thermosetting agent (C) and an organic chelating agent (D) or a heavy metal inactivating agent (E) as essential components, and further 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

An acrylic polymer (A) is used in order to give sufficient adhesiveness and film-forming property (sheet workability) to an adhesive composition. As the acrylic polymer (A), a conventionally known acrylic polymer can be used.

It is preferable that it is 10,000-2 million, and, as for the weight average molecular weight (Mw) of an acrylic polymer (A), it is more preferable that it is 100,000-1,500,000. If the weight average molecular weight of the acrylic polymer (A) is too low, the adhesive force between the adhesive layer and the substrate may be high, and pick-up failure may occur. If the weight average molecular weight is too high, the adhesive layer may not be able to follow the unevenness of the chip mounting portion. , Voids, etc.

The glass transition temperature (Tg) of the acrylic polymer (A) is preferably in the range of -60 ° C to 50 ° C, more preferably -50 ° C to 40 ° C, and particularly preferably -40 ° C to 30 ° C. If the glass transition temperature of the acrylic polymer (A) is too low, the peeling force of the adhesive layer and the substrate may be large, and pick-up failure of chips may occur. If the glass transition temperature is too high, the adhesive force for fixing the wafer may be insufficient.

(Meth) acrylic acid ester monomer or its derivative (s) is mentioned as a monomer which comprises the said acrylic polymer (A). For example, alkyl (meth) acrylate of 1-18 carbon atoms of an alkyl group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate etc. are mentioned; (Meth) acrylates having a cyclic skeleton, for example cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, etc. are mentioned; Hydroxymethyl (meth) acrylate which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. are mentioned; In addition, glycidyl (meth) acrylate etc. which have an epoxy group are mentioned. In these, the acrylic polymer obtained by superposing | polymerizing the monomer which has a hydroxyl group is preferable, since compatibility with the epoxy type thermosetting resin (B) mentioned later is good. The acrylic polymer (A) may be copolymerized with acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and the like.

(B) Epoxy Thermosetting Resin

As epoxy type thermosetting resin (B), a conventionally well-known epoxy resin can be used. Specifically as an epoxy type thermosetting resin (B), a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether, its hydrogenated substance, an allocresol novolak epoxy resin, a dicyclopentadiene type epoxy resin, and a biphenyl Epoxy compounds which have bifunctional or more in a molecule | numerator, such as a type | mold epoxy resin, a bisphenol A type | mold epoxy resin, a bisphenol F type | mold epoxy resin, and a phenylene skeleton type | mold epoxy resin, are mentioned. These can be used individually by 1 type or in combination of 2 or more type.

The epoxy composition of the present invention preferably contains 1 to 1500 parts by weight of epoxy-based thermosetting resin (B), and more preferably 3 to 1200 parts by weight, based on 100 parts by weight of the acrylic polymer (A). If the content of the epoxy-based thermosetting resin (B) is less than 1 part by weight, sufficient adhesiveness may not be obtained. If the content of the epoxy-based thermosetting resin (B) is greater than 1500 parts by weight, the adhesive force between the adhesive layer and the substrate may be increased, and pickup may occur.

(C) Curing agent

A hardening | curing agent (C) functions as a hardening | curing agent with respect to an epoxy type thermosetting resin (B). As a preferable hardening | curing agent (C), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned. Examples of the functional group include phenolic hydroxyl group, alcoholic hydroxyl group, amino group, carboxyl group and acid anhydride. Among these, phenolic hydroxyl group, amino group, acid anhydride, etc. are preferable, For example, More preferably, phenolic hydroxyl group and an amino group are mentioned. More preferably, a phenolic hydroxyl group and an amino group are mentioned.

As a specific example of a phenol type hardening | curing agent, a polyfunctional phenol resin, a biphenol, a novolak-type phenol resin, a dicyclopentadiene type phenol resin, a xyloxic phenol resin, an aralkyl phenol resin is mentioned. As a specific example of an amine curing agent, DICY (dicyandiamide) can be mentioned. 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 weight part with respect to 100 weight part of epoxy type thermosetting resins (B), and, as for content of a hardening | curing agent (C), it is more preferable that it is 1-200 weight part. When there is little content of a hardening | curing agent (C), adhesiveness may not be obtained by lack of hardening, and when excessive, the moisture absorption rate of an adhesive composition may become high and package reliability may be reduced.

(D) organic chelating agent

An organic chelating agent (D) is mix | blended with an adhesive composition. By mix | blending an organic chelating agent (D), a gettering function is provided to an adhesive composition.

Although an organic chelating agent (D) is not specifically limited, It is preferable that it has polyhydric carboxylic acid as a functional group, the acid value is 100-600 mg / g, and it is more preferable that it is 260-330 mg / g. If the acid value of the organic chelating agent (D) is less than 100 mg / g, the desired gettering function is insufficient, and if the acid value of the organic chelating agent (D) is larger than 600 mg / g, it may cause interaction with the base thermosetting agent.

Moreover, it is preferable that it is 190 degreeC or more, and, as for the mass reduction start temperature by differential scanning thermal analysis (TG / DTA) of an organic chelating agent (D), 196 degreeC or more is more preferable. If the mass reduction start temperature of the organic chelating agent (D) by differential scanning thermal analysis (TG / DTA) is lower than 190 ° C, the IR reflow resistance of the semiconductor package incorporating the semiconductor device may be deteriorated. .

In addition, the compounding quantity of the organic chelating agent (D) is preferably 1 to 35 parts by weight, more preferably 10 to 35 parts by weight, particularly preferably 20 to 30 parts by weight based on 100 parts by weight of the total amount of the adhesive composition. . When the blending amount of the organic chelating agent (D) is too low, the desired gettering function becomes insufficient, and when the blending amount is too large, the adhesive performance may be impaired.

A gettering site can be introduce | transduced into a semiconductor device by mix | blending such an organic chelating agent (D) with the adhesive composition used for fixing a semiconductor chip. For this reason, since the impurity metal accumulated in the wafer is captured by the organic chelating agent (D) of the adhesive layer even when moved under heating conditions such as reflow, migration on the circuit surface does not occur.

The gettering function of an organic chelating agent (D) can be evaluated by the following copper ion adsorption ability, for example.

That is, 1 g of an organic chelating agent was dissolved in 0.8 L of copper (II) chloride dihydrate manufactured by Kanto-Togaku Co., Ltd. in 1 L of ultrapure water, and diluted 100 times to 50 g of an aqueous copper chloride solution having a copper ion concentration of 3 ppm. After standing at 121 degreeC and 2 atmospheres for 24 hours, the copper ion concentration (residual copper ion concentration) of the said copper ion aqueous solution is measured, and it is based on the following formula from an initial copper ion concentration (3 ppm) and a residual copper ion concentration (ppm). The copper ion adsorption capacity is evaluated.

Copper ion adsorption capacity (%) = (3ppm-residual copper ion concentration (ppm)) x 100/3 ppm

Copper ion adsorption capacity shows the ratio of the amount of copper ion adsorbed or absorbed by the organic chelating agent, and it is thought that a gettering function is high, so that copper ion adsorption capacity is high. Copper ion adsorption capacity of the organic chelating agent (D) used by this invention becomes like this. Preferably it is 30% or more, More preferably, it is 50% or more, Especially preferably, it is 95% or more.

In addition, a gettering function can also be evaluated by the adsorption amount (henceforth "copper ion adsorption rate") of copper ion adsorbed per unit weight of an organic chelating agent. Specifically, the organic chelating agent is thrown into the copper ion aqueous solution similarly to the above, and a copper ion adsorption rate is calculated | required by the following formula.

Copper ion adsorption rate (%) = (3ppm-residual copper ion concentration (ppm)) x solution amount (g) x 10 ^-6 x 100 / sample weight (g)

Copper ion adsorption rate of the organic chelating agent (D) used by this invention becomes like this. Preferably it is 0.003% or more, More preferably, it is 0.010% or more, Especially preferably, it is 0.013% or more.

In general, the organic chelating agent (D) has a larger surface area per weight, so that the smaller the particle diameter, the easier it is to capture impurity metals and the higher the gettering function. In general, the smaller the particle diameter, the easier the tackiness of thin thickness. Therefore, the average particle diameter of the organic chelating agent (D) used by this invention becomes like this. Preferably it is 1 nm-30 micrometers, More preferably, it is 5 nm-10 micrometers, Especially preferably, it is the range of 10 nm-1 micrometer.

When the particle size is large in the state of the raw materials, it is pulverized in advance or by mixing at the time of setting the adhesive composition by a suitable method (ball mill, three rolls, etc.).

In addition, the average particle diameter of the organic chelating agent (D) calculated | required the arithmetic mean from 100 particle | grains by scanning electron microscope (SEM) observation. When particle shape was not spherical, the maximum length diameter was made into particle diameter.

(E) Heavy metal deactivator

A heavy metal deactivator (E) may be mix | blended with an adhesive composition instead of the said organic chelating agent (D). By mix | blending heavy metal deactivator (E), a gettering function is provided to an adhesive composition.

Heavy metal deactivator is an additive mix | blended in various quantities with various plastics in order to prevent plastic deterioration by metals, such as a catalyst residue. It is thought that the heavy metal deactivator captures a metal component, reducing the effect and preventing plastic deterioration. As such a heavy metal inactivating agent, various inactivating agents of inorganic type or organic type are known. In the present invention, an organic heavy metal deactivator is preferable. The organic heavy metal deactivator is excellent in dispersibility in the adhesive composition.

As such a heavy metal deactivator, especially the compound which has the following structure in a part of molecule | numerator is used preferably.

In the above formula (2), R is a hydrocarbon skeleton which may contain hydrogen or a hetero atom, and particularly preferably a hydrocarbon skeleton containing a nitrogen atom and / or an oxygen atom.

The following compound is mentioned as an especially preferable example of such a heavy metal deactivator.

3- (N-salicyloyl) amino-1,2,4-triazole (manufactured by ADEKA Corporation, CDA-1, CAS No. 36411-52-6)

Decamethylene dicarboxydisalicyloylhydrazide (product made by ADEKA Corporation, CDA-6, CAS No. 63245-38-5)

By blending such a heavy metal deactivator into the adhesive composition used for fixing the semiconductor chip, the gettering site can be introduced into the semiconductor device. For this reason, since the impurity metal accumulated in the wafer is captured by the heavy metal inactivating agent (E) of the adhesive layer even when moved under heating conditions such as reflow, migration does not occur on the circuit surface.

The gettering function of the heavy metal deactivator can be evaluated by the following copper ion adsorption capacity, for example.

That is, 0.1 g of a heavy metal deactivator was dissolved in 50 g of a copper chloride aqueous solution having a copper ion concentration of 300 ppm, prepared by dissolving 0.805 g of copper (II) chloride dihydrate made by Kanto Chemical Co., Ltd. in 1 L of ultrapure water. After standing at atmospheric pressure for 24 hours, the copper ion concentration (residual copper ion concentration) of the copper ion aqueous solution was measured, and the copper ion adsorption capacity was determined from the initial copper ion concentration (3 ppm) and the residual copper ion concentration (ppm) by the following equation. Evaluate.

Copper ion adsorption capacity (%) = (300ppm-residual copper ion concentration (ppm)) × 100 / 300ppm

The copper ion adsorption capacity represents the ratio of the amount of copper ions adsorbed or absorbed by the heavy metal deactivator, and the higher the copper ion adsorption capacity is, the higher the gettering function is. Copper ion adsorption capacity of the heavy metal deactivator (E) used by this invention becomes like this. Preferably it is 30% or more, More preferably, it is 50% or more, Especially preferably, it is 95% or more.

In addition, a gettering function can also be evaluated by the adsorption amount of copper ion adsorbed per unit weight of a heavy metal deactivator (henceforth "copper ion adsorption rate"). Specifically, heavy metal deactivator is thrown into the copper ion aqueous solution similarly to the above, and copper ion adsorption rate is calculated | required by the following formula.

Copper ion adsorption rate (%) = (300ppm-residual copper ion concentration (ppm)) × solution amount (g) x 10 ^-6 x 100 / sample weight (g)

The copper ion adsorption rate of the heavy metal deactivator (E) used by this invention becomes like this. Preferably it is 4% or more, More preferably, it is 7% or more, Especially preferably, it is 14.5% or more.

In general, as the particle diameter of the heavy metal inactivating agent (E) is smaller, the surface area per weight is wider, so that impurity metals are more easily captured, and the gettering function is increased. In general, the smaller the particle diameter, the easier the tackiness of thin thickness. Therefore, the average particle diameter of the heavy metal deactivator (C) used by this invention becomes like this. Preferably it is 1 nm-30 micrometers, More preferably, it is 5 nm-10 micrometers, Especially preferably, it is the range of 10 nm-1 micrometer.

When the particle size is large in the state of the raw materials, it is pulverized in advance or by mixing at the time of setting the adhesive composition by a suitable method (ball mill, three rolls, etc.).

In addition, the average particle diameter of the heavy metal deactivator (E) calculated | required the arithmetic mean from 100 particle | grains by scanning electron microscope (SEM) observation. When particle shape was not spherical, the maximum length diameter was made into particle diameter.

The blending amount of the heavy metal deactivator (E) of the adhesive composition of the present invention is preferably 1 to 30 parts by weight, more preferably 10 to 30 parts by weight, particularly preferably 20 to 100 parts by weight of the total amount of the adhesive composition. ˜30 parts by weight. When the blending amount of the heavy metal deactivator (E) is too small, the desired gettering function becomes insufficient, and when the blending amount is too large, the adhesive performance may be impaired.

(Other ingredients)

The adhesive composition according to the present invention may include not only the acrylic polymer (A), the epoxy-based thermosetting resin (B), the curing agent (C) and the organic chelating agent (D) or the heavy metal inactivating agent (E) but also the following components. .

(F) curing accelerator

A curing accelerator (F) is used to adjust the curing rate of the adhesive composition. A hardening accelerator (E) is used suitably especially when using together an epoxy type thermosetting resin (B) and a hardening | curing agent (C).

Preferable curing accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 Imidazoles such as hydroxymethylimidazole; 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 by 1 type or in mixture of 2 or more types.

The curing accelerator (F) is contained in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 1 part by weight based on 100 parts by weight of the total of the epoxy-based thermosetting resin (B) and the curing agent (C). By containing the hardening accelerator (F) in the quantity of the said range, it has the outstanding adhesive characteristic even when exposed to high temperature and high humidity, and high package reliability can be achieved even when exposed to strict reflow conditions. When the content of the curing accelerator (F) is small, insufficient adhesion characteristics are not obtained due to insufficient curing, and when the curing accelerator is excessively high, the curing accelerator having high polarity moves to the adhesive interface side through the adhesive layer under high temperature and high humidity and segregates. This lowers the reliability of the package.

(G) energy ray polymerizable compounds

In the adhesive composition of the present invention, an energy ray polymerizable compound may be blended. The energy ray polymerizable compound (G) contains an energy ray polymerizable group and is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams. Specific examples of such energy ray-polymerizable compound (G) include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy modified acrylate, polyether acrylate and itaconic acid An acrylate type compound, such as an oligomer, is mentioned. Such a compound has one or more polymerizable double bonds in a molecule, and usually a weight average molecular weight is 100-30000, Preferably it is about 300-10000. Although the compounding quantity of an energy-beam polymerizable compound (G) is not specifically limited, It is preferable to use in the ratio of about 1-50 weight part with respect to 100 weight part of whole quantities of an adhesive composition.

(H) photopolymerization initiator

When the adhesive composition of this invention contains the energy ray polymerizable compound (G) mentioned above, energy rays, such as an ultraviolet-ray, are irradiated at the time of its use, and an energy ray polymeric compound is hardened | cured. At this time, the polymerization curing time and the light irradiation amount can be reduced by including the photopolymerization initiator (H) in the composition.

As such a photoinitiator (H), specifically, benzophenone, acetphenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid Methyl, benzoin dimethyl ketar, 2,4-diethyl thioxane, α-hydroxycyclohexylphenyl ketone, benzyl diphenyl sulfide, tetramethyl thiuram monosulfide, azobisisobutylonitrile, benzyl, dibenzyl , Diacetyl, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide And β-croanthhraquinone. A photoinitiator (H) can be used individually by 1 type or in combination of 2 or more types.

It is preferable that 0.1-10 weight part is contained with respect to 100 weight part of energy ray polymeric compounds (G), and, as for the compounding ratio of a photoinitiator (H), it is more preferable that 1-5 weight part is contained. If it is less than 0.1 part by weight, satisfactory pick-up may not be obtained due to lack of photopolymerization, and if it is more than 10 parts by weight, residues that do not contribute to photopolymerization may be produced, resulting in insufficient curability of the adhesive composition.

(I) coupling agent

Coupling agent (I) may be used in order to improve adhesiveness and adhesiveness to the adherend of the adhesive composition. Moreover, by using a coupling agent (I), the water resistance can be improved, without impairing the heat resistance of the hardened | cured material obtained by hardening | curing an adhesive composition.

As a coupling agent (I), the compound which has group which reacts with the functional group which the said acrylic polymer (A), epoxy type thermosetting resin (B), etc. have is used preferably. As the coupling agent (I), a silane coupling agent is preferable. As such a coupling agent, (gamma)-glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propylmethyl diethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, and (gamma)-(methacryloxy) Propyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxy Silane, N-phenyl- (gamma)-aminopropyl trimethoxysilane, (gamma)-uraide propyl triethoxysilane, (gamma)-mercaptopropyl trimethoxysilane, (gamma)-melcaptopropyl methyl dimethoxysilane, bis (3-tri Ethoxy silyl propyl) tetrasulfane, methyl trimethoxysilane, methyl triethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc. are mentioned. These can be used individually by 1 type or in mixture of 2 or more types.

Coupling agent (I) is 0.1-20 weight part normally with respect to a total of 100 weight part of an acrylic polymer (A) and an epoxy type thermosetting resin (B), Preferably it is 0.2-10 weight part, More preferably, it is 0.3- It is included in the ratio of 5 parts by weight. When content of a coupling agent (I) is less than 0.1 weight part, the said effect may not be obtained, and when it exceeds 20 weight part, it may become a cause of outgas.

(J) thermoplastic resin

You may use a thermoplastic resin (J) for an adhesive composition. Thermoplastic resin (J) is mix | blended in order to maintain the flexibility of the adhesive bond layer after hardening. As a thermoplastic resin (J), it is preferable that weight average molecular weights are 1000-100,000, and it is more preferable that it is 3000-80,000. By containing the thermoplastic resin (J) of the said range, the interlayer peeling of the base material and an adhesive bond layer in the pick-up process of a semiconductor chip can be performed easily, and the adhesive bond layer to the unevenness | corrugation of a board | substrate follows, and generation | occurrence | production of a void etc. is carried out. Can be suppressed.

The glass transition temperature of the thermoplastic resin (J) becomes like this. Preferably it is -30 degreeC-150 degreeC, More preferably, it is the range of -20 degreeC-120 degreeC. If the glass transition temperature of the thermoplastic resin (J) is too low, the peeling force of the adhesive layer and the substrate may be large, and pick-up failure of the chip may occur, and if too high, the adhesive force for fixing the wafer may be insufficient.

Examples of the thermoplastic resin (J) include a polyester resin, urethane resin, phenoxy resin, polybutene, polybutadiene, polystyrene, and the like. These can be used individually by 1 type or in mixture of 2 or more types.

The thermoplastic resin (J) is usually 1 to 300 parts by weight, preferably 2 to 100 parts by weight, based on 100 parts by weight of the total of the acrylic polymer (A), the epoxy thermosetting resin (B) and the curing agent (C). do. When the content of the thermoplastic resin (J) is in this range, the above effects can be obtained.

(K) inorganic filler

By incorporating the inorganic filler (K) into the adhesive composition, it is possible to adjust the thermal expansion coefficient of the composition, optimize the thermal expansion coefficient of the adhesive layer after curing with respect to the semiconductor chip, metal or organic substrate to improve the package reliability. . Moreover, it becomes possible to reduce the moisture absorption rate after hardening of an adhesive bond layer.

Preferred inorganic fillers include silica, alumina, talc, calcium carbonate, titanium white, bengal, powders such as silicon carbide, boron nitride, beads, spherical particles, monocrystalline fibers and glass fibers. Among these, a silica filler and an alumina filler are preferable. The said inorganic filler (K) can be used individually or in mixture of 2 or more types. Content of an inorganic filler (K) can be adjusted to the range of 1 to 80 weight% normally with respect to the whole adhesive composition.

(L) crosslinking agent

In order to control the initial adhesive force and cohesion force of an adhesive composition, a crosslinking agent may be added. As a crosslinking agent (L), an organic polyvalent isocyanate compound, an organic polyvalent imine compound, etc. are mentioned, for example.

As said organic polyvalent isocyanate compound, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, an alicyclic polyvalent isocyanate compound, the trimer of these organic polyvalent isocyanate compounds, and the terminal isocyanate urethane prepolymer obtained by making these organic polyvalent isocyanate compounds react with a polyol compound Etc. can be mentioned.

As an organic polyvalent isocyanate compound, 2, 4- triene diisocyanate, 2, 6- triylene diisocyanate, 1, 3- xylene diisocyanate, 1, 4- xylene diisocyanate, diphenylmethane-4,4 ' -Diisocyanate, diphenylmethane-2,4'- diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane-4,4'- diisocyanate, dicyclo Hexyl methane-2,4'- diisocyanate, a trimethylol propane additive triene diisocyanate, and a ridine isocyanate are mentioned.

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -Tri-β-aziridinylpropionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylenemelamine, and the like.

The crosslinking agent (L) is usually used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the acrylic polymer (A).

(M) universal additive

Various additives may be mix | blended with the adhesive composition of this invention as needed other than the above. Examples of the various additives include plasticizers, antistatic agents, antioxidants, pigments, and dyes.

(Adhesive composition)

The adhesive composition which consists of each above components has pressure-sensitive adhesiveness and heat curability, and has the function to temporarily hold various to-be-adhered bodies in an uncured state. Finally, the cured product having high impact resistance can be imparted through thermal curing, and excellent adhesive strength can be maintained even under strict high temperature and high humidity conditions.

The adhesive composition which concerns on this invention is obtained by mixing each said component in an appropriate ratio. At the time of mixing, each component may be diluted with a solvent beforehand, and the solvent may be added at the time of mixing.

(Adhesive sheet)

The adhesive sheet which concerns on this invention forms the adhesive bond layer which consists of said adhesive composition so that exfoliation is possible on a base material. The shape of the adhesive sheet according to the present invention may take any shape such as a tape shape or a label shape.

As a base material of an adhesive sheet, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polyethylene naphthalate film, Polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene- (meth) acrylic acid copolymer film, ethylene- (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film , Transparent films such as polyimide films and fluororesin films are used. Moreover, these crosslinked films are also used. Moreover, these laminated | multilayer film may be sufficient. Moreover, the film, opaque film, etc. which colored these can be used.

The adhesive sheet according to the present invention is attached to various adherends, and after the required processing is carried out on the adherends, the adhesive layer adheres to the adherends and is peeled off from the substrate. That is, it is used for the process including the process of transferring an adhesive bond layer from a base material to a to-be-adhered body. For this purpose, the surface tension of the surface in contact with the adhesive layer of the substrate 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. The base material with such a low surface tension can be obtained by selecting a material suitably, and can also be obtained by apply | coating a peeling agent to the surface of a base material, and performing a peeling process.

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

In order to peel off the surface of the base material using the release agent, the release agent is applied as it is without solvent or by dilution or emulsification with a gravure coater, a Mayer coater, an air knife coater, a roll coater, or the like. What is necessary is just to harden | cure, or a laminated body may be formed by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion processing, etc.

The thickness of a base material is 10-500 micrometers normally, Preferably it is 15-300 micrometers, Especially preferably, it is about 20-250 micrometers. Moreover, the thickness of an adhesive bond layer is 1-500 micrometers normally, Preferably it is 5-300 micrometers, Especially preferably, it is about 10-150 micrometers.

The manufacturing method of an adhesive sheet is not specifically limited, You may apply | coat and dry the composition which comprises an adhesive bond layer on a base material, and also provide an adhesive bond layer on a peeling film, and transfer this to the said base material, and may manufacture it. In addition, in order to protect an adhesive bond layer before use of an adhesive sheet, you may laminate | stack a peeling film on the upper surface of an adhesive bond layer. As the release film, a release agent such as a silicone resin is applied to a plastic material such as a polyethylene terephthalate film or a polypropylene film. Moreover, in order to fix another jig | tool, such as a ring frame, in the surface outer peripheral part of an adhesive bond layer, an adhesive layer and an adhesive tape may be provided separately.

Then, the case where the said adhesive sheet is applied to manufacture of a semiconductor device is demonstrated about the usage method of the adhesive sheet which concerns on this invention as an example.

(Manufacturing Method of Semiconductor Device)

In the method of manufacturing a semiconductor device according to the present invention, a semiconductor wafer is attached to an adhesive layer of the adhesive sheet, the semiconductor wafer is diced into a semiconductor chip, and an adhesive layer is adhered to the back surface of the semiconductor chip to leave the adhesive layer. And depositing the semiconductor chip on the die pad portion of the organic substrate, the lead frame, or on the separate semiconductor chip through the adhesive layer in the case of stacking the chips.

Hereinafter, the manufacturing method of the semiconductor device which concerns on this invention is explained in full detail.

In the manufacturing method of the semiconductor device which concerns on this invention, a circuit is first formed in the surface, and the semiconductor wafer ground on the back surface is prepared.

The semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium arsenide. Formation of the 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. Subsequently, the opposite surface (rear surface) of the circuit surface of the semiconductor wafer is ground. The grinding method is not particularly limited and may be ground by a known means using a grinder or the like. In the case of back grinding, in order to protect the circuit of a surface, an adhesive sheet called a surface protection sheet is affixed on a circuit surface. Back surface grinding fixes the circuit surface side (namely, surface protection sheet side) of a wafer by a chuck table etc., and grinds the back surface side in which the circuit is not formed by a grinder. Although the thickness after grinding of a wafer is not limited, Usually, it is about 20-500 micrometers.

Then, the crushing layer which arose at the time of back surface grinding as needed is removed. The fracture layer is removed by chemical etching, plasma etching, or the like. Although the gettering function possessed by the wafer is reduced by the removal of the crushed layer, the gettering function is imparted to the semiconductor device obtained by using the adhesive composition of the present invention. Therefore, the manufacturing method of the semiconductor chip of this invention can be suitably applied especially to the semiconductor wafer from which the crushing layer was removed. In other words, the method for manufacturing a semiconductor chip of the present invention can be suitably applied to semiconductor wafers in which the thickness of the fracture layer is reduced to 50 nm or less, or 30 nm or less, particularly 10 nm or less.

Subsequently, the back frame side of the lead frame and the semiconductor wafer is placed on the adhesive layer of the adhesive sheet according to the present invention, and lightly pressed to fix the semiconductor wafer. Subsequently, when an energy ray polymerizable compound (G) is mix | blended with an adhesive bond layer, an energy ray is irradiated to the adhesive bond layer from a base material side, the energy ray polymerizable compound (G) is hardened, and the cohesion force of an adhesive bond layer is raised, The adhesive force between an adhesive bond layer and a base material is reduced. Examples of the energy rays to be irradiated include ultraviolet rays (UV), electron beams (EB), and the like, and preferably ultraviolet rays are used. Subsequently, the said semiconductor wafer is cut | disconnected using cutting means, such as a dicing saw, and a semiconductor chip is obtained. The cutting depth at this time is a depth obtained by adding the thickness of the semiconductor wafer, the total thickness of the adhesive layer and the wear of the dicing saw. The energy ray irradiation may be carried out at any stage after the deposition of the semiconductor wafer and before the peeling (pickup) of the semiconductor chip, for example, after dicing, or after the following expansion step. In addition, you may divide energy-beam irradiation into multiple times.

Subsequently, when the adhesive sheet is expanded as necessary, the interval between the semiconductor chips can be extended, and the pickup of the semiconductor chips can be performed more easily. At this time, a shift | offset | difference arises between an adhesive bond layer and a base material, the adhesive force between an adhesive bond layer and a base material decreases, and the pick-up property of a semiconductor chip improves. In this manner, when the semiconductor chip is picked up, the cut adhesive layer can be stuck to the back surface of the semiconductor chip to be peeled off from the substrate.

Subsequently, the semiconductor chip is placed on the die pad of the lead frame or on the surface of another semiconductor chip (lower chip) through the adhesive layer (hereinafter, the die pad on which the chip is mounted or the lower chip surface is referred to as a "chip mounting part"). Listed). The chip mounting portion is heated before placing the semiconductor chip or immediately after placing it. Heating temperature is 80-200 degreeC normally, Preferably it is 100-180 degreeC, Heating time is 0.1 second-5 minutes normally, Preferably it is 0.5 second-3 minutes, The pressure at the time of mounting is 1 kPa-200 MPa normally to be.

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

Moreover, you may make it the temporary adhesion state, without performing heat processing after mounting, and may harden an adhesive bond layer using the heating in resin sealing normally performed in package manufacture. Through this process, the adhesive layer is cured, and the semiconductor chip and the chip mounting portion can be firmly adhered to each other. Since the adhesive layer is fluidized under the die-bonding condition, the adhesive layer is sufficiently embedded in the unevenness of the chip mounting portion, and the generation of voids can be prevented, thereby increasing the reliability of the package.

The adhesive composition and the adhesive sheet of the present invention can be used for adhesion of semiconductor compounds, glass, ceramics, metals, etc. in addition to the above-mentioned usage methods.

(Example)

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In addition, in the following examples and the comparative examples, <copper ion adsorption capacity and copper ion adsorption rate>, <gettering performance evaluation>, and <mass reduction start temperature measurement> were performed as follows.

<Copper ion adsorption capacity and copper ion adsorption rate>

(1) Copper ion adsorption capacity and copper ion adsorption rate of organic chelating agent

1 g of the gettering agent prepared in Examples and Comparative Examples was dissolved in 0.8 L of copper chloride (II) dihydrate made by Kanto Chemical Co., Ltd. in 1 L of ultrapure water, and diluted to 100-fold to 50 g of an aqueous copper chloride solution having a copper ion concentration of 3 ppm. It put, and it was left to stand at 121 degreeC and 2 atmospheres for 24 hours. Then, it filtered using the membrane filter of 0.10 micrometer of pore diameters. The residual copper ion concentration of the said copper ion aqueous solution in filtration was measured by the atomic absorption spectrometry (The measuring apparatus: the Hitachi Seisakusho make, atomic absorption photometer Z5310, frame method), and initial copper ion concentration (3 ppm) and residual copper ion From the concentration (ppm), the copper ion adsorption capacity and the copper ion adsorption rate are evaluated by the following equation.

Copper ion adsorption capacity (%) = (3ppm-residual copper ion concentration (ppm)) x 100/3 ppm

Copper ion adsorption rate (%) = (3ppm-residual copper ion concentration (ppm)) x solution amount (g) x 10 ^-6 x 100 / sample weight (g)

(2) Copper ion adsorption capacity and copper ion adsorption rate of heavy metal deactivator

0.1 g of the heavy metal deactivator prepared in Examples and Comparative Examples was dissolved in 50 g of a copper chloride aqueous solution having a copper ion concentration of 300 ppm prepared by dissolving 0.805 g of copper chloride (II) dihydrate made by Kanto-Togaku Co., Ltd. in 1 L of ultrapure water. , 2 atm, left for 24 hours. Then, it filtered using the membrane filter whose hole diameter is 0.10 micrometer. The residual copper ion concentration of the said copper ion aqueous solution in filtration was measured by the atomic absorption spectrometry (The measuring apparatus: the Hitachi Seisakusho make, atomic absorption photometer Z5310, frame method), and initial copper ion concentration (300 ppm) and residual copper ion concentration. From (ppm), copper ion adsorption capacity and copper ion adsorption rate are evaluated by the following formula.

Copper ion adsorption capacity (%) = (300ppm-residual copper ion concentration (ppm)) × 100 / 300ppm

Copper ion adsorption rate (%) = (300ppm-residual copper ion concentration (ppm)) × solution amount (g) x 10 ^-6 x 100 / sample weight (g)

〈Gettering Performance Evaluation〉

The back surface of the silicon wafer was dry-polished (200 mm diameter, 75 micrometers in thickness, 10 nm in thickness of a crushing layer) using DGP8760 by Disco company. 1 g of copper (II) chloride powder (manufactured by Kanto Chemical Co., Ltd., product name: copper chloride (II) dihydrate) is uniformly dispersed on the dry polished surface (wafer back surface) of the silicon wafer, and pseudo reflow conditions ( 300 ° C., 30 minutes) to diffuse copper ions into the silicon wafer. Thereafter, the adhesive tape (Adwill D-675 manufactured by Lintech Co., Ltd. after UV curing) was attached and peeled off on the back surface of the wafer to remove copper chloride (II) powder from the back surface of the wafer.

The adhesive sheet prepared in the Example and the comparative example was affixed on the back surface of the silicon wafer contaminated with this copper ion at 40 degreeC. After 30 minutes, ultraviolet irradiation (230 mW / cm 2, 120 mJ / cm 2) was performed from the substrate surface using an ultraviolet irradiation device (Adwill RAD-2000 m / 12, manufactured by Rintech Co., Ltd.), and the substrate was peeled off. Then, it thermosetted (140 degreeC, 1 hour), and it put in pseudo reflow conditions (300 degreeC, 30 minutes) continuously.

The wafer surface (mirror surface, non-adhesive sheet non-adhesive surface) was cleaned in advance with hydrofluoric acid to remove contamination and natural oxide film (about 10 nm) adhered to the surface. Thereafter, 10 mm of the outer circumference of the wafer was masked with a mold sandwiched by a teflon (registered trademark) jig, and 5 µm was etched from the wafer surface with a nitric acid / fluoric acid mixture (ratio 3: 1). The whole amount of the obtained etching liquid was extract | collected to the evaporating dish. After the collected etching solution was heated and evaporated to dryness, the residue was dissolved in a fixed amount of nitric acid / fluoric acid mixed solution to obtain a sample for measuring copper ion concentration. In addition, sample preparation was performed in the clean draft (class 10) installed in the clean room (class 100).

The concentration of copper ions in the silicon wafer was quantitatively measured by ICP-MS measurement.

Device: Perlan Elmer ELAN6100DRC Plus

Condition etc .: plasma power 1500W. The lower limit of determination of copper ions is 3.0 × 10 ¹² atoms / cm 3 (number of atoms per unit volume).

The copper ion concentration eluted in the etching liquid was measured, and the gettering performance of the adhesive sheet was evaluated. The smaller the amount of copper ions eluted in the etching solution, the higher the amount of copper ions captured by the adhesive sheet and the higher the gettering performance. 50 * 10 <^12> atoms / cm <3> or less were made favorable for the copper ion detection amount, and it was made into defect that the copper ion detection amount exceeded 50 * 10 <^12> atoms / cm <3>.

In addition, you may perform the quantitative analysis method of copper ion concentration by methods, such as atomic absorption spectrometry, ICP-OES, and TOF-SIMS.

<Mass reduction start temperature measurement>

The measurement of the mass reduction start temperature was performed using a differential thermal analysis device (manufactured by Shimadzu Corporation, TG / DTA Analyzer DTG-60). Using the organic chelating agent prepared in the Example and the comparative example as a measurement sample, about 10 mg of the measurement sample was precisely weighed. The measurement sample was heated up to 40-500 degreeC by the temperature rising temperature of 10 degreeC / min, and the mass reduction start temperature was measured.

<Adhesive composition>

Each component which comprises an adhesive composition is shown below.

(A) Acrylic polymer: A copolymer consisting of 55 parts by weight of n-butyl acrylate, 10 parts by weight of methyl acrylate, 20 parts by weight of glycidyl methacrylate, and 15 parts by weight of 2-hydroxyethyl acrylate (weight average molecular weight : 900,000, glass transition temperature: -28 ℃)

(B) epoxy-based thermosetting resin:

(B1) Bisphenol A epoxy resin (jER828, the epoxy equivalent 235 g / eq made in Japan epoxy resin company)

(B2) novolak-type epoxy resin (EOCN-104S made by Nippon Kayaku Co., epoxy equivalent 218 g / eq)

(B3) Bisphenol A type epoxy resin (BPA328 made by Nippon Shokubai Corporation)

(B4) Phenylene skeleton type epoxy resin (EPPN-502H made by Nippon Kayaku Co., Ltd.)

(C) Curing agent: Novolak-type phenolic resin (Shonol BRG-556, phenolic hydroxyl group equivalent 103 g / eq made by Showa Kobun-shi)

(D) Organic chelating agent: Organic chelating agent which has polyhydric carboxylic acid as a functional group (Techlan DO by Nagase ChemteX Corp., acid value 260-330 mg / g, particle diameter 1 micrometer, mass reduction start temperature 196 degreeC)

(E) Heavy metal deactivator:

(E1) 3- (N-salicyloyl) amino-1,2,4-triazole (manufactured by ADEKA Corporation, CDA-1, CAS No. 36411-52-6, particle diameter 1 μm)

(E2) decamethylene dicarboxydisalicyloylhydrazide (manufactured by ADEKA Corporation, CDA-6, CAS No. 63245-38-5, particle diameter 0.5 μm)

(F) Curing accelerator: Imidazole (Curazole 2PHZ manufactured by Shikoku Chemical Co., Ltd.)

(G) energy ray polymerizable compounds:

(G1) polyfunctional acrylate oligomer (KAYARADR-684, molecular weight made by Nippon Kayaku Co., Ltd.)

(G2) polyfunctional acrylate oligomer (NK ester A-DPH, molecular weight 580 made by Shin-Nakamura Chemical Co., Ltd.)

(H) Photoinitiator: 1-hydroxy cyclohexyl phenyl ketone (The Chiba Specialty Chemicals make: Irgacure 184)

(I) coupling agent:

(I1) Silane coupling agent (KBE-403 made by Shin-Etsu Chemical Co., Ltd.)

(I2) Silane coupling agent (MKC silicate MSEP2 made by Mitsubishi Chemical Corporation)

(J) Thermoplastic resin: Polyester resin (Byron 220 made by Toyou Bow Co., Ltd.)

(K) Inorganic filler: Silica filler (made by Ado-Matex Corporation: adomafine SC2050)

A-1110 (product made by Nippon Unicar Corporation)

(Examples and Comparative Examples)

Each said component was mix | blended in the quantity shown in following Table 1, and the adhesive composition was obtained. The methyl ethyl ketone solution (solid concentration 61 wt%) of the obtained adhesive composition was applied onto a siliconized release film (SP-PET381031 manufactured by Rintech Co., Ltd.) after drying to a thickness of 30 μm, and dried (drying). Conditions: After 100 degreeC in oven for 1 minute, it adhered with the base material (polyethylene film, thickness 100micrometer, surface tension 33mN / m), and the adhesive bond layer was transferred on the base material, and the adhesive sheet was obtained.

<Copper ion adsorption ability and copper ion adsorption rate> and <Gettering performance evaluation> were performed using the obtained adhesive sheet. The content and results of the organic chelating agent or heavy metal deactivator with respect to 100 parts by weight of the adhesive composition are shown in Table 2 below.

In addition, the gettering performance of the wafer which did not perform copper ion contamination (Reference Example 1) and the thing which did not adhere the adhesive sheet of the wafer which performed copper ion contamination (Reference Example 2) was measured.

The adhesive sheet of the Example showed excellent copper ion adsorption capacity, copper ion adsorption rate, and gettering performance. From this result, it was confirmed that a highly reliable semiconductor device is obtained by using an organic chelating agent (D) or a heavy metal deactivator (E) for an adhesive composition.

Claims (10)

An adhesive composition comprising an acrylic polymer (A), an epoxy thermosetting resin (B), a curing agent (C) and an organic chelating agent (D) or a heavy metal inactivating agent (E). The method of claim 1,
The organic chelating agent (D) has polyhydric carboxylic acid as a functional group, and the acid value is 100-600 mg / g, The adhesive composition characterized by the above-mentioned. 3. The method according to claim 1 or 2,
Adhesive composition characterized in that the mass reduction start temperature by differential scanning thermal analysis (TG / DTA) of the organic chelating agent (D) is 190 ° C or more. The method according to any one of claims 1 to 3,
An adhesive composition comprising 1 to 35 parts by weight of an organic chelating agent (D) per 100 parts by weight of the adhesive composition. The method of claim 1,
Adhesive composition characterized by containing 1-30 weight part of heavy metal deactivators (E) per 100 weight part of adhesive compositions. 6. The method according to claim 1 or 5,
Adhesive composition, characterized in that the copper ion adsorption capacity of the heavy metal deactivator (E) is defined by the following:
0.1 g of a heavy metal deactivator was added to 50 g of a copper chloride aqueous solution having a copper ion concentration of 300 ppm, and the copper ion concentration of the copper ion aqueous solution after standing at 121 ° C. and 2 atm for 24 hours was measured,
Copper ion adsorption capacity = (300ppm-residual copper ion concentration (ppm)) x 100/300 ppm, The copper ion adsorption capacity is calculated | required. The method according to any one of claims 1, 5 and 6,
Adhesive composition, characterized in that the heavy metal deactivator (E) has the following structure in part of the molecule.
(Formula 1)

(R is a hydrocarbon backbone that may contain hydrogen or a hetero atom.) The adhesive sheet which consists of an adhesive bond layer which consists of an adhesive composition as described in any one of Claims 1-7 on the base material so that peeling is possible. The semiconductor wafer is attached to the adhesive layer of the adhesive sheet according to claim 8, the semiconductor wafer is diced into a semiconductor chip, the adhesive layer is fixed on the back surface of the semiconductor chip, and is peeled off from the substrate. A method of manufacturing a semiconductor device, comprising the step of mounting on a die pad portion or another semiconductor chip via the adhesive layer. The method of claim 9,
The semiconductor wafer is a method for manufacturing a semiconductor device, wherein after the backside grinding, the fracture layer formed by backside grinding is reduced to a thickness of 50 nm or less.