KR20140129922A - An adhesive composition for semiconductor, an adhesive film for semiconductor and a semiconductor device prepared from the composition - Google Patents

Abstract

The present invention relates to an adhesive composition for a semiconductor characterized by including a metal ion scavenger of formula 1, to an adhesive film for a semiconductor, and to a semiconductor device manufactured by using the adhesive film for a semiconductor. formula 1: X_(m)Y_(n)Z_(1-m-n)·(H_2O)_p. In the formula 1: X, Y and Z are different to each other, and are one among Zr, Sn, Mg, Ti, Al, Bi, and Sb, or a carbonate, a phosphate or an oxide of the metal; m and n are a number greater than 0 but less than 1, respectively; 1-m-n does not satisfy 0; and p is a number of 0 or more.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an adhesive composition for a semiconductor, an adhesive film for a semiconductor manufactured using the same, and an adhesive composition for a semiconductor device,

The present invention relates to a bonding composition for a semiconductor comprising a metal ion capturing agent capable of reducing a metal ion or reducing the mobility of a metal ion, and an adhesive film for semiconductor produced using the same.

Dicing-die bonding tapes for semiconductor package processing generally consist of a dicing tape that supports the semiconductor chip during chip separation and facilitates peeling during pick-up, and a die bonding tape used for laminating chips.

The semiconductor device slices a high-purity silicon single crystal to obtain a semiconductor wafer, forms an integrated circuit, adheres a pressure-sensitive adhesive film for protecting a semiconductor wafer surface to a circuit forming surface, and grinds the back surface by means of grinding, rubbing or polishing After roughing, it is attached and fixed to a semiconductor use tape, diced according to the shape of the chip, peeled therefrom and fixed to the substrate with an adhesive, and if necessary, wafers are laminated and molded with an epoxy resin to manufacture a semiconductor chip.

There is a problem in that the die and the die bonding tape must be dropped at the same time in the pickup process of peeling off after dicing. In the process of bonding the die bonding tape to the back surface of the semiconductor wafer, (Void) may occur. This is because voids remain between the chip and the interface after assembly, and when exposed to a high temperature environment, gaps and voids may cause volume expansion and cracking, which may lead to malfunction of the device in the reliability process.

Thus, there is a need to minimize the occurrence of voids between interfaces during all processes of semiconductor fabrication. For this purpose, a method of increasing the content of the hardened portion has been proposed. However, in the above method, since the tensile strength of the film is decreased by increasing the content of the hardened portion, the film is broken during the precutting process of cutting the semiconductor wafer into a size suitable for the semiconductor wafer, or in the chip- Burr or chipping phenomenon may occur. In addition, due to its high modulus of elasticity with low modulus, there is a high possibility that the adhesive film is deformed and the pickup success rate is reduced. Particularly, in the case of a semiconductor material using two or more semiconductor chips of the same size, a semiconductor chip having a separate adhesive film is further laminated on a lower semiconductor chip having concavo-convexes caused by the wires. There is also a demand for an adhesive film capable of ensuring insulation with an upper semiconductor chip while minimizing the formation of gaps and voids by embedding unevenness.

An adhesive composition comprising an epoxy resin as a main component is mainly used as an adhesive film satisfying the above conditions. However, since the epoxy resin is a relatively highly absorbent resin, there is a risk that many ionic impurities will penetrate into the adhesive interface during the semiconductor chip laminating process. Especially, metal ions among ionic impurities have thermal conductivity and electrical conductivity, which may cause damage to the semiconductor chip or cause abnormal operation of the circuit.

In order to remove metal ions, Korean Patent Laid-Open No. 10-2010-0075213 has increased the metal capturing power by using a multi-layered adhesive having a different polymer content. However, there arises a problem that an additional manufacturing process is required due to the multi-layer structure. Korean Patent Application Publication No. 2010-0113764 discloses that an ion trapping agent is added to improve ion trapping ability, but the reliability is not sufficient.

Korean Patent Publication No. 10-2010-0075213 Korean Patent Application Publication No. 2010-0113764

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An object of the present invention is to provide a bonding composition or film for semiconductor which can solve the reliability deterioration of a semiconductor chip caused by a metal or a metal ion remaining on the surface of the semiconductor chip as impurities or penetrating the bonding interface.

It is also an object of the present invention to provide a bonding composition or film for semiconductor which minimizes the generation of voids in the lamination of semiconductor chips and has high connection reliability and low rate of surface energy reduction before and after curing, thereby providing excellent adsorption of metals or metal ions.

One embodiment of the present invention relates to a bonding composition for semiconductor comprising a metal ion scavenger of the formula (1).

[Formula 1]

_{X (m) Y (n)} Z (1-mn) · (H 2 O) p

In Equation (1)

X, Y and Z are different from each other, and m and n independently of one another are each an integer of more than 0 and less than 1, and Zr, Sn, Mg, Ti, Al, Bi and Sb or an oxide, carbonate, 1-mn is not 0, and p is a number of 0 or more.

Another aspect of the present invention is a bonding film for a semiconductor comprising a metal ion capturing agent, wherein when a thickness of the adhesive film for semiconductor is a and a particle diameter of the metal ion capturing agent is b, b / a is 0.001 to 0.5 And the like.

In another aspect of the present invention,

(T) of the copper ion concentration change according to the formula (2) of the adhesive film for semiconductor is 8% or more and less than 90%.

[Formula 2]

T = (T ₀ -T ₁ ) / T ₀ 100

T ₀ is the initial concentration of copper ion in the copper ion aqueous solution before adding to the adhesive film for semiconductor, T ₁ is the initial concentration of copper ion after curing the adhesive film for semiconductor at 125 ° C for 1 hour and 175 ° C for 2 hours, It is the copper ion concentration of the aqueous solution when left at 120 캜 for 24 hours in the aqueous solution.

The adhesive film for a semiconductor may have a void area (V) of 10% or less when compressed by a force of 1.0 kgf for 1.0 second between two wafers.

Another aspect of the present invention relates to a dicing die-bonding film comprising the adhesive composition for semiconductor or the adhesive film for semiconductor disclosed in the present invention.

The adhesive composition or film for semiconductor according to the present invention can effectively trap metal or metal ions that remain on the surface of the semiconductor chip as impurities or penetrate into the bonding interface, both before and after curing, It is possible to solve the problem of lowering the reliability of the chip. In addition, since the generation of voids is minimized in the semiconductor chip lamination, the connection reliability is high, the bonding strength is high, and the storage stability is excellent because the adhesive force and the rate of change of the melting point are low even when stored at room temperature for a long time.

One embodiment of the present invention relates to a bonding composition for semiconductor comprising a metal ion scavenger of the formula (1).

[Formula 1]

_{X (m) Y (n)} Z (1-mn) · (H 2 O) p

In Equation (1)

X, Y and Z are different from each other, and m and n independently of one another are each an integer of more than 0 and less than 1, and Zr, Sn, Mg, Ti, Al, Bi and Sb or an oxide, carbonate, 1-mn is not 0, and p is a number of 0 or more.

Preferably, the metal ion scavenger of the formula 1 has a spherical or amorphous form in which X, Y and Z are each independently an oxide, carbonate or phosphate of Zr, Sn, Mg, Ti, Al, Inorganic compound.

By using the metal ion capturing agent of Formula 1, diffusion of metal ions toward semiconductor devices is suppressed due to strong binding with metal ions, and prevention of surface energy degradation after curing of the film prevents adhesion of metal ions, , And the characteristics of voids in compression can all be satisfied.

As the metal ion trapping agent of the above formula 1, X, Y and Z are oxides, carbonates or phosphates of Zr, Mg and Al, respectively; Oxides, carbonates or phosphates of Zr, Sn and Al; Oxides, carbonates or phosphates of Zr, Mg and Bi; Oxides, carbonates or phosphates of Zr, Mg and Sb; Oxides, carbonates or phosphates of Sn, Mg and Al; Oxides, carbonates or phosphates of Sn, Mg and Bi; Oxides, carbonates or phosphates of Sn, Mg and Sb; Oxides, carbonates or phosphates of Mg, Al and Bi; Oxides, carbonates or phosphates of Mg, Al and Sb; And oxides, carbonates, phosphates and the like of Al, Bi and Sn, and m and n independently of one another are more than 0 and less than 1, 1-m-n is not 0 and p is 0 or more. p is preferably a natural number greater than 0 and less than 100

Preferably, X, Y and Z are oxides, carbonates or phosphates of Zr, Mg, and Al, respectively.

Especially preferably, X, Y and Z are oxides of Zr, Mg and Al, respectively.

The ion trapping agent of Formula 1 may be contained in an amount of 0.01 to 20% by weight, preferably 0.01 to 10% by weight based on the total solid weight of the adhesive composition for semiconductor. Within this range, reactivity with transition metal ions, workability, and film forming properties can be good.

The adhesive composition for semiconductor according to the present invention may include a binder, an epoxy resin, a curing resin, a curing catalyst, a silane coupling agent and a filler.

The adhesive composition for semiconductor according to the present invention contains 10 to 80% by weight of a binder, 10 to 45% by weight of an epoxy resin, 3 to 30% by weight of a cured resin, 0.01 to 5% by weight of a curing catalyst By weight, the silane coupling agent in an amount of 0.1 to 7% by weight, and the filler in an amount of 1 to 25% by weight.

Another aspect of the present invention is an adhesive film for semiconductors comprising a metal ion capturing agent wherein b / a is in the range of 0.001 to 0.5, where a is the thickness of the adhesive film for semiconductor and b is the particle diameter of the metal ion capturing agent. And the like. When b / a is in the above range, the dispersibility of the adhesive composition is improved, the adhesive strength is excellent, and the surface flatness of the adhesive film can be improved. b / a can be preferably 0.01 to 0.2, and particularly preferably 0.01 to 0.1. In the present invention, the thickness a of the adhesive film for semiconductor means the thickness of only the adhesive layer excluding the base film. The particle diameter b of the metal ion trapping agent herein means the particle diameter measured by the light scattering method.

The thickness of the adhesive film for semiconductor may be 1 to 100 m, and the thickness of the metal ion scavenger may be 0.001 to 50 m. Preferably, the thickness of the adhesive film for semiconductor may be 10 to 50 m, and the thickness of the metal ion scavenger may be 0.01 to 10 m.

The metal ion scavenger that can be used in the above embodiment may be selected from the group consisting of zirconium oxide, antimony oxide, bismuth oxide, magnesium oxide, aluminum oxide, antimony bismuth oxide, zirconium bismuth oxide, zirconium magnesium oxide, (Oxides), bismuth magnesium-based (oxides), and bismuth-aluminum-based oxides (oxides), antimony oxides, aluminum antimony oxides, antimony magnesium antimony oxides, antimony aluminum antimony oxides, antimony zirconium antimony oxides, zirconium aluminum antimony oxides, Lt; / RTI >

These products include IXE-100, IXE-300, IXE-600, IXE-700F, IXE-770D, IXEPLAS-A1, IXEPLAS-A2, IXEPLAS-A3, IXEPLAS- 4A, DHT-4A-2, Kyowa-200, Kyowa-500, Kyowa-1000, and the like.

The metal ion scavenger that may be used in this embodiment may be a metal ion scavenger of formula 1:

[Formula 1]

_{X (m) Y (n)} Z (1-mn) · (H 2 O) p

In Equation (1)

X, Y and Z are different from each other, and m and n independently of one another are each an integer of more than 0 and less than 1, and Zr, Sn, Mg, Ti, Al, Bi and Sb or an oxide, carbonate, 1-mn is not 0, and p is a number of 0 or more.

The adhesive film for semiconductor may include a binder, an epoxy resin, a curing resin, a curing catalyst, a silane coupling agent, and a filler.

The adhesive film for semiconductor produced from the adhesive composition for semiconductor of the present invention is characterized in that the rate of change (T) of the copper ion concentration according to Formula 2 is 8% or more and less than 90%.

[Formula 2]

T = (T ₀ -T ₁ ) / T ₀ 100

T ₀ is the initial concentration of copper ion in the copper ion aqueous solution before adding to the adhesive film for semiconductor, T ₁ is the initial concentration of copper ion after curing the adhesive film for semiconductor at 125 ° C for 1 hour and 175 ° C for 2 hours, It is the copper ion concentration of the aqueous solution when left at 120 캜 for 24 hours in the aqueous solution.

When the copper ion concentration change rate (T) is 8% or more, the surface adhesive energy of the semiconductor adhesive film remains high even after curing, so that the metal ion is strongly bound to a metal ion such as copper ion to prevent the metal ion from diffusing toward the semiconductor element . If the copper ion concentration change rate (T) is less than 90%, it is possible to prevent the adhesion force due to the surface energy or the decrease of the melt viscosity, and to prevent the void defect from occurring during the pressing. The adhesive film for semiconductors according to the present invention can have an appropriate surface energy for capturing metal ions while reducing the generation of void defects during compression.

The copper ion concentration change rate (T) is preferably 10% or more and less than 80%, more preferably 15% or more and less than 70%, particularly preferably 20% or more and less than 70%.

The adhesive film for semiconductors according to the present invention is characterized in that it is placed between two wafers and has a void area (V) of 10% or less when compressed by a force of 1.0 kgf for 1.0 second.

The adhesive composition for semiconductor of the present invention may comprise a binder, a curing portion and an organic solvent. As the binder of the present invention, an acrylic polymer, an NCO-added polymer, an epoxy-added polymer, or the like can be used. In the present invention, by adding two or more functional groups capable of oxidizing or reducing the transition metal or inhibiting the mobility of the transition metal, the function of controlling the movement of the transition metal while maintaining the overall adhesive film function is imparted.

As the curing portion of the present invention, those containing an epoxy resin, a urethane resin, a silicone resin, a polyester resin, a pulmonary type curing resin, an amine type curing resin, a melanin curing resin, an urea resin and an acid anhydride type curing resin may be used .

In addition, the adhesive composition according to the present invention may include a curing catalyst, a silane coupling agent, a filler, and the like.

Hereinafter, each of the preferable components constituting the composition of the present invention will be described in more detail.

Organic solvent

The organic solvent of the present invention lowers the viscosity of the adhesive composition for semiconductor to facilitate the production of the film. At this time, since residual organic solvent is present and may affect the physical properties of the film, it is preferable that the residual organic solvent is less than 2% in the film. The organic solvent that can be used in the present invention is preferably at least one selected from the group consisting of benzene, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformaldehyde, cyclohexane, propylene glycol monomethyl ether acetate or cyclohexanone, But is not necessarily limited thereto.

These organic solvents serve to alleviate the voids that can occur in the process by inducing a uniform mixture composition during the formation of the adhesive film. In addition, after forming the adhesive film, a small amount of the film remains in the film to soften the film.

bookbinder

Examples of the binder resin include polyimide resin, polystyrene resin, polyethylene resin, polyester resin, polyamide resin, butadiene rubber, acrylic rubber, (meth) acrylate resin, urethane resin, polyphenylene ether resin, A phenol resin, a polycarbonate resin, a polyphenylene ether resin, a modified polyphenylene ether resin, a mixture thereof, and the like can be used, but the present invention is not limited thereto. Preferably, the binder resin may contain an epoxy group. In the specific examples, an epoxy group-containing (meth) acrylic copolymer is preferably applicable.

 The binder resin may have a glass transition temperature of -30 to 80 캜, preferably 5 to 60 캜, more preferably 5 to 35 캜. It is possible to secure high flowability in the above range, to have excellent void removal ability, and to obtain an adhesive force and reliability.

In the specific examples, the binder resin having a weight average molecular weight of 50,000 to 5,000,000 g / mol may be used.

The content of the binder is preferably 10 to 80% by weight based on the total solid weight of the adhesive composition for semiconductor. And more preferably 15 to 70% by weight. The above range is advantageous in terms of reliability and film formability.

Epoxy resin

The epoxy resin used in the present invention is not particularly limited as long as it exhibits hardening and adhesive action, and liquid epoxy resin, solid epoxy resin or a mixture thereof can be applied.

Examples of the liquid epoxy resin include biphenyl type epoxy resin, bisphenol A type liquid epoxy resin, bisphenol F type liquid epoxy resin, trifunctional or higher polyfunctional liquid epoxy resin, rubber modified liquid epoxy resin, urethane modified liquid epoxy resin, An acryl-modified liquid epoxy resin and a photosensitive liquid epoxy resin may be used alone or in combination. Of these, bisphenol A type liquid epoxy resin is preferable.

An epoxy equivalent of about 100 to about 1500 g / eq may be used for the liquid epoxy resin. Preferably from about 150 to about 800 g / eq, and more preferably from about 150 to about 400 g / eq. Within the above range, the cured product is excellent in adhesiveness, the glass transition temperature is maintained, and excellent heat resistance can be obtained.

The weight average molecular weight of the liquid epoxy resin may be 100 to 1,000 g / mol. There is an advantage in that the flowability is excellent in the above range.

The epoxy resin having at least one functional group may be used as the epoxy resin near the solid or solid phase at room temperature. Preferably, the epoxy resin has a softening point (Sp) of 30 to 100 ° C. Examples thereof include epoxy resins such as bisphenol type epoxy, phenol novolac type epoxy, o-cresol novolac type epoxy, polyfunctional epoxy, amine type epoxy, heterocyclic type epoxy, substituted epoxy, naphthol type epoxy And derivatives thereof.

YD-019K, YD-019K, YD-019K, YD-019K, YD-014H, YD-020, YD020-L, YD-014, YD-014ER, YD-013K, YD-019K, and YD-019K of the bisphenol- YD-017R, YD-017, YD-012, YD-011H, YD-011S, YD-011, YDF-2004 and YDF-2001. Examples of the phenol novolac series include Yuka Shell Epoxy Co., YDPN-638, YDPN-637, YDPN-644, YDPN-644, YDPN-641, YDPN-638A80, YDPN-638, EPPN-501, EPPN-501H, Dow Chemical DN- YDPN-5001P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, and YDCN-500P are available as o-cresol novolac , YDCN-500-8P, YDCN-500-10P, YDCN-500-80P, YDCN-500-80PCA60, YDCN-500-80PBC60, YDCN-500-90P, YDCN- YDCN-702, YDCN-703, YDCN-704, and YDCN-1024 of Dokdo Chemical Co., KBPN-120, KBPN-115, etc. of Kukdo Chemical Co., Ltd. and Epon 1031S (epoxy resin) of Yucca Shell Epoxy Co., Ltd. are available as bisphenol- , Araldioto 0163 of Ciba Specialty Chemicals Co., Ltd., Detacol EX-611, DataCol EX-614, DataCol EX-614B, DataCol EX-622, DataCol EX- EP-5200R, KD-1012, EP-5100R, KD-1011, KDT-4400A70, KDT-4400, YH of Datacol EX-411, YH-434, YH-434 and YH-300. Examples of the amine-based epoxy resin include Epikote 604 manufactured by Yucca Shell Epoxy Co., Ltd., YH-434 manufactured by Dokdo Chemical Co., Ltd., TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., ELM-120, etc., and PT-810 of Ciba Specialty Chemicals Co., Ltd. as a heterocyclic ring-containing epoxy resin and UCC ERL-4234, ERL-4221, ERL-4206, and Naphthol epoxy of Epiklor HP-4032, Epiclon HP-4032D, Epiclon HP-4700, Epiclon 4701, Examples of the phenyl-based epoxy resin include YX-4000H of Japan Epoxy Resin, YSLV-120TE, GK-3207 of Nippon Steel Chemical Co., and NC-3000 of Nippon Kayaku. These epoxy resins may be used singly or in combination of two or more.

The content of the epoxy resin is preferably 10 to 45% by weight, more preferably 15 to 40% by weight based on the total weight of the adhesive composition for semiconductor. When the content of the epoxy resin is within the above range, it is advantageous in terms of reliability, compatibility of the film, and tackiness of the adhesive film at room temperature.

Hardened resin

The curing resin which can be used in the present invention is preferably a resin having a hydroxyl group or an amino group, and an amine type, acid anhydride type and phenol type are preferable. More preferably a phenolic resin.

Examples of phenolic resins that can be used in the present invention include bisphenol-based resins such as bisphenol A, bisphenol F, and bisphenol S; Phenol novolac resins; Bisphenol A novolac resins; Phenolic resins such as xylyl type resins, cresol type novolac resins and biphenyl type resins. H-1, H-4, HF-1M (hydroxyl equivalent: 106), HF-3M, and HF-3 of the simple phenol type curing agent are commercially available as these phenol type epoxy resin curing agents. MEH-7800S, MEH-7800M, MEH-7800H, and MEH-78004S (hydroxyl equivalents: 175), MEH- MEH-7851H, MEH-78513H, MEH-78514H, MEH-78514H, and Kolon Kikai KK of MEI-7851H, MEH-78003H, MEH-78003H, Kolon Kikai K.K. KPH-F4500 and triphenylmethyl MEH-7500, MEH-75003S, MEH-7500SS, MEH-7500S and MEH-7500H manufactured by Meiwa Plastic Industries,

The hydroxyl group equivalent of the phenol-type cured resin is preferably 100 to 600 g / eq, and more preferably 170 to 300 g / eq.

If the hydroxyl group equivalent is less than 100 g / eq, the water absorption rate tends to be high and the flow resistance tends to deteriorate. If the hydroxyl equivalent is more than 600 g / eq, the glass transition temperature tends to deteriorate and the heat resistance tends to deteriorate.

The curable resin of the present invention is preferably 3 to 30% by weight, more preferably 5 to 20% by weight based on the total weight of the adhesive composition for semiconductor.

Curing catalyst

The curing catalyst that can be used in the present invention can shorten the curing time so that the epoxy resin can be completely cured during the semiconductor process. The type of the curing catalyst is not particularly limited, but may be melamine, imidazole or triphenylphosphine catalyst One or more of them may be selected and used.

2M-OK, 2MAOK-PW, and 2P4MHZ of Ajinomoto Precision Technology Co., Ltd., PNK-23, PN-40, and Sankoku Chemical Co., Ltd. as the imidazole system. HOKKO TPP-K and TPP-MK of CHEMICAL INDUSTRY CO., LTD., Which may be used alone or in combination of two or more.

In the present invention, the curing catalyst content is preferably 0.01 to 5% by weight based on the total weight of the adhesive composition for semiconductor. More preferably, the content of the curing catalyst is preferably 0.01 to 2% by weight based on the total weight of the adhesive composition for semiconductor. The above range is advantageous in terms of storage stability.

Silane Coupling agent

In the present invention, the silane coupling agent is not particularly limited and may be a commonly used silane coupling agent for improving the adhesion between the surface of the inorganic material such as silica and the resin of the adhesive film when the composition is mixed.

As the silane coupling agent, an epoxy-containing silane or a mercaptan-containing silane can be used. Examples of the epoxy-containing silane coupling agent include 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3-glycidoxytrimethoxysilane , 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, and N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (Aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- Ethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, and N-phenyl-3-aminopropyltrimethoxysilane, and those containing maltotriose include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, isocyanate-containing 3-isocyanate Propyltriethoxysilane. These may be used singly or in combination of two or more. The silane coupling agent is preferably 0.1 to 7% by weight based on the total weight of the adhesive composition for semiconductor.

Filler

The composition of the present invention includes a filler to control thixotropic properties and control melt viscosity. The filler may be an inorganic filler or an organic filler. The inorganic filler may be a metal powder such as gold powder, silver powder, copper powder, or nickel. The non-metal alumina, Silica, aluminum nitride, silica, boron nitride, titanium dioxide, glass, iron oxide, ceramics and the like can be used. Examples of the organic filler include carbon, rubber filler, polymer, etc. Can be used. The shape and size of the filler are not particularly limited, but spherical silica is preferred in the present invention, and a filler having a spherical surface having hydrophobic characteristics may be used depending on the application.

The size of the spherical silica used in the present invention is preferably in the range of 500 nm to 5 mu m. If the particles of the inorganic filler are 10 mu m or more, there is a possibility of circuit damage due to collision with the semiconductor circuit.

The amount of the filler to be used in the present invention is preferably 1 to 25% by weight based on the total weight of the adhesive composition for semiconductor. The above range is advantageous in terms of film formability and tensile strength of the film.

Another aspect of the present invention relates to an adhesive film for semiconductor formed from the above adhesive composition for semiconductor.

Another aspect of the present invention relates to a semiconductor device connected with the adhesive film for semiconductor.

The adhesive film was pressed at a force of 1.0 kgf for 1.0 second, cured at 125 ° C for 1 hour and 175 ° C for 2 hours, absorbed at 85 ° C / 85% RH for 48 hours, At 7 kgf and less than 20 kgf.

The adhesive film may have a melt viscosity of 100 to 100,000 P at 140 ° C.

In another aspect, the present invention includes a dicing die-bonding film comprising an adhesive film for a semiconductor. The present invention provides a dicing die bonding film in which a pressure-sensitive adhesive layer and an adhesive film layer are sequentially laminated on a base film, wherein the adhesive film layer of the present invention provides an adhesive film of a dicing die-bonding film . The pressure-sensitive adhesive layer may be a conventional pressure-sensitive adhesive composition. As one example, the pressure-sensitive adhesive layer may contain 20 to 150 parts by weight of UV-curable acrylate per 100 parts by weight of the polymeric binder having adhesive properties, 0.1 to 5 parts by weight based on 100 parts by weight may be used.

The base film preferably has radiation transmittance, and a substrate having good light transmittance can be selected when a radiation-curable pressure-sensitive adhesive that reacts with ultraviolet radiation is applied. Examples of the polymer that can be selected as such a base material include homopolymers or copolymers of polyolefins such as polyethylene, polypropylene, propylene ethylene copolymer, ethylene ethyl acrylate copolymer, ethylene acrylic acid methyl copolymer and ethylene vinyl acetate copolymer, polycarbonate . Polymethyl methacrylate, polyvinyl chloride, polyurethane copolymer, and the like. The thickness of the base film is suitably from 50 to 200 占 퐉 in consideration of tensile strength, elongation, and radiation permeability.

Hereinafter, advantages and features of the present invention and methods of achieving them will be made clear with reference to the embodiments described in detail below. However, it is to be understood that the present invention is not limited to the embodiments disclosed herein but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Example

Example  1-3: Manufacture of adhesive film for semiconductor

A binder resin, an epoxy resin, a phenol-type curing resin, a curing catalyst, a filler, an ion capturing agent and a silane coupling agent having the compositions shown in the following Table 1 were dissolved in a solvent, cyclohexanone was added to a high-speed stirring rod And the mixture was dispersed at a low speed of 3000 rpm for 20 minutes and at a high speed of 4000 rpm for 5 minutes for 20 minutes to prepare a composition. The composition was filtered using a 50 mu m capsule filter and then coated with an applicator to a thickness of 20 mu m Adhesive films were prepared and dried at 110 ° C for 15 minutes and then stored at 25 ° C for 1 day to prepare adhesive films for semiconductors of Examples 1 to 3.

Comparative Example  1-2: Production of adhesive film for semiconductors

The adhesive films for semiconductors of Comparative Examples 1 and 2 were prepared in the same manner as in Example 1-3, except that the ion trapping agent was not added or not listed in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 bookbinder
(%) SG-P312L 38 38 38 38 38 Epoxy resin
(%) EPPN-501H 27 27 27 27 27 Phenolic resin
(%) MEH-8005 20 20 20 20 20 Curing catalyst
(%) 2MZ-H 0.2 0.2 0.2 0.2 0.2 Silane coupling agent
(%) KBM-303 1.0 1.0 1.0 1.0 1.0 Filler
(%) SO-25H 12 12 12 12 12 Ion trap
(%) IXEPLAS-A1 3.8 IXEPLAS-A2 3.8 IXEPLAS-A3 3.8 IXE-770D 3.8 Coating Thickness (um) 10 10 10 20 10

(1) Polymer binder: SG-P312L (manufactured by Nagase Co., Ltd.)

(2) Epoxy resin: EPPN-502H (manufactured by Nippon Chemical)

(3) Phenol resin: MEH-8005 (manufactured by Meiwa Plastic Industries, Ltd.)

(4) Curing catalyst: 2MZ-H (manufactured by Shikoku Chemical),

(5) Silane coupling agent: KBM-303 (manufactured by Shin-Etsu Co., Ltd.)

(6) Filler: SO-25H (manufactured by Tatsumori Co., Ltd.)

(7) Ion capturing agent:

IXE-770D (manufactured by Toagosei Co., Ltd., component: Mg, Al, particle diameter: 6.4 m)

IXEPLAS-A1 (manufactured by Toagosei Co., Ltd., Zr, Mg, Al, particle diameter: 0.72 μm)

IXEPLAS-A2 (manufactured by Toagosei Co., Ltd., Zr, Mg, Al, particle diameter: 0.26 m)

IXEPLAS-A3 (manufactured by Toagosei Co., Ltd., Zr, Mg, Al, particle size: 0.58 m)

Experimental Example : Example  And In the comparative example  Evaluation of physical properties of the prepared adhesive composition film

The properties of the adhesive films prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated by the following methods, and the results are shown in Table 2 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Adhesion (kgf) 10.1 9.7 10.2 7.8 11.5 Melting point (10 ⁴ P @ 140 degrees) 5.6 6.5 6.3 5.7 4.3 Device operability pass pass pass fail fail Storage stability Adhesion (kgf) -0.4 -0.3 -0.1 -0.8 -0.4 The melt viscosity (10 ⁴ P) -0.5 -0.4 -0.3 -0.7 -0.3 Decrease in copper ion concentration (%) 35.8 33.1 38.9 28.8 5.5 Additive particle size / coating thickness
(b / a) 0.32 0.036 0.013 0.64 - Coating Flatness Good Good Good Bad Good

(1) Adhesive strength measurement

A 725 μm thick wafer coated with a SiO 2 film was cut into a size of 5 mm × 5 mm and laminated at 60 ° C. together with the adhesive film. A wafer having a thickness of 725 μm and a size of 10 mm × 10 mm and coated with a photosensitive polyimide on a hot plate at a temperature of 100 ° C. was placed on the wafer and the wafer piece laminated with the adhesive was pressed thereon for 1.0 second under a force of 1.0 kgf. Hour and 175 ° C for 2 hours, and the fracture strength at 270 ° C after moisture absorption at 85 ° C / 85% RH for 48 hours was measured.

(2) Measurement of melt viscosity

In order to measure the viscosity of the film, each of the films was laminated several times at 60 DEG C so as to have a thickness of 400 to 1000 mu m and cut into a circle with a diameter of 25 mm. An ARES rheometer (manufactured by TA instruments) was used. The viscosity range was measured from 30 ° C to 130 ° C and the temperature was 5 ° C / min. The value of Eta at 100 ℃, which measures the flowability at the die attach temperature, is presented.

(3) Device operation measurement

In order to investigate the device operability, a PCB substrate with an electrode pattern of 50 x 30 mm was prepared using an adhesive film. The line / space width of the electrode pattern is formed to be 30/70 μm. Five semiconductor chips were laminated on the electrode patterns under the conditions of 120 deg., 0.2 MPa, and 10 mm / sec. The obtained sample was cured by heating at 125 degrees for 1 hour and 175 degrees for 2 hours. The positive electrode and the negative electrode were respectively connected to the wires of the HAST test by soldering, and it was confirmed whether or not the electric resistance decreased after 100 hours under the conditions of 130 °, 85RH, and 50V. When the number of those in which the sharp decrease of 40% Pass "and" fail "in the case of more than two.

(4) Storage stability measurement

After storing at room temperature for 30 days, 100 degree of melting point and adhesive strength were measured, and each value was compared with the initial measured values and summarized as the change amount.

(5) Measurement of copper ion concentration

(II) aqueous solution of 10.0 ppm (T ₀ ) was prepared by dissolving the copper chloride compound in distilled water and 1.5 g of the film obtained by curing at 125 ° C. for 1 hour and 175 ° C. for 2 hours was dissolved in 35 ml of the copper ion (II) aqueous solution prepared above And sealed. The ion concentration (T ₁ ) of the aqueous solution was measured by ICP-OES (Perkin Elmer, OPTIMA 7300DV) after being left at 120 ° C. for 24 hours in a constant-temperature drier.

(6) Coating flatness

The thicknesses of the films coated in Examples 1 to 4 and Comparative Examples 1 and 2 were measured at 30 cm intervals at intervals of 5 cm using a thickness gauge (KLA, Tenkor P 16)) to determine the difference between the minimum value and the maximum value , And if the difference is within 20% of the average thickness, the result is good or, if not, it is marked as bad.

In Examples 1 to 3 and Comparative Examples 1 and 2, the adhesive force between the die bonding film and the wafer was excellent, i.e., 6.0 kgf or more, and the melt viscosity was good at 15.0 × 10 ⁴ or less. In Examples 1 to 3 at the time of disappearance, the adhesive strength, the melting point, the device operability and the storage stability were good, and the decrease in the copper ion concentration was excellent in the content of 10% or more. This is because the inorganic ion trapping agent effectively captures copper ions. In Comparative Examples 1 and 2, the adhesive strength, melt viscosity, and storage stability were good, but failed in device operability. This is because the coating flatness was poor in Comparative Example 1, and in Comparative Example 2, it was judged that the copper ion concentration reduction amount was less than 7%.

Claims (22)

1. A bonding composition for semiconductor comprising a metal ion capturing agent represented by the following formula (1).
[Formula 1]
_{X (m) Y (n)} Z (1-mn) · (H 2 O) p
In Equation (1)
X, Y and Z are different from each other, and m and n independently of one another are each an integer of more than 0 and less than 1, and Zr, Sn, Mg, Ti, Al, Bi and Sb or an oxide, carbonate, 1-mn is not 0, and p is a number of 0 or more. The bonding composition for semiconductor according to claim 1, wherein X, Y and Z are each independently an oxide, carbonate or phosphate of Zr, Sn, Mg, Ti, Al, Bi or Sb. The bonding composition for semiconductor according to claim 1, wherein the metal ion capturing agent is in a spherical or amorphous form. The bonding composition for semiconductor according to claim 1, wherein the bonding composition for semiconductor comprises a binder, an epoxy resin, a curing resin, a curing catalyst, a silane coupling agent and a filler. The bonding composition for semiconductor according to claim 1, wherein the metal ion capturing agent is contained in an amount of 0.01 to 20% by weight based on the total weight of the adhesive composition for semiconductor. 6. The method according to any one of claims 1 to 5, wherein X is an oxide, carbonate or phosphate of Zr, Y is an oxide, carbonate or phosphate of Mg, and Z is an oxide, carbonate or phosphate of Al Adhesive composition. The adhesive composition according to claim 4, wherein the binder is 10 to 80% by weight, the epoxy resin is 10 to 45% by weight, the curing resin is 3 to 30% by weight based on the total solid weight of the adhesive composition for semiconductor, Wherein the catalyst is 0.01 to 5 wt%, the silane coupling agent is 0.1 to 7 wt%, and the filler is 1 to 25 wt%. An adhesive film for semiconductor comprising a metal ion capturing agent,
Characterized in that b / a is 0.001 to 0.5 when the thickness of the semiconductor adhesive film is a and the particle diameter of the metal ion capturing agent is b. The adhesive film for semiconductor according to claim 8, wherein the thickness of the adhesive film for semiconductor is 1 to 100 m. The adhesive film for semiconductor according to claim 8, wherein the coating thickness of the adhesive film for semiconductor is measured at 30 points at 5 cm intervals and the difference between the maximum value and the minimum value is 20% or less of the average value of the 30 measured values. The method of claim 8, wherein the metal ion trapping agent is selected from the group consisting of zirconium, antimony, bismuth, magnesium, aluminum, antimony bismuth, zirconium bismuth, zirconium magnesium, magnesium aluminum, antimony magnesium, antimony aluminum, Aluminum, bismuth magnesium and bismuth aluminum oxides, carbonates and phosphates. The adhesive film for semiconductor according to claim 8, wherein the metal ion capturing agent is a metal ion capturing agent represented by the following formula (1).
[Formula 1]
_{X (m) Y (n)} Z (1-mn) · (H 2 O) p
In Equation (1)
X, Y and Z are each different from each other, and m, n and n are independently from each other more than 0 to 1 1-mn is not 0, and p is a number of 0 or more. The adhesive film for semiconductor according to claim 12, wherein X, Y and Z are each independently an oxide, carbonate or phosphate of Zr, Sn, Mg, Ti, Al, Bi and Sb. The adhesive film for semiconductor according to any one of claims 8 to 13, wherein the metal ion capturing agent is in a spherical or amorphous form. The adhesive film for semiconductor according to any one of claims 8 to 13, wherein the adhesive film for semiconductor comprises a binder, an epoxy resin, a cured resin, a curing catalyst, a silane coupling agent and a filler. Wherein the copper ion concentration change rate (T) of the adhesive film for semiconductor is not less than 8% and less than 90% according to the formula (2).
[Formula 2]
T = (T ₀ -T ₁ ) / T ₀ 100
In the formula 1, T ₀ is the initial concentration of the copper ions in the semiconductor adhesive film added before copper ion aqueous solution, T ₁ is after 2 hours curing at one hour and 175 ℃ at 125 ℃ the adhesive film for a semiconductor of the copper ion It is the copper ion concentration of the aqueous solution when left at 120 캜 for 24 hours in the aqueous solution. The adhesive film for semiconductor according to claim 16, wherein the adhesive film for semiconductor is placed between two wafers and has a void (V) area of 10% or less when compressed by a force of 1.0 kgf for 1.0 second. The adhesive film for semiconductor according to claim 16, wherein the adhesive film for semiconductor comprises a metal ion capturing agent of formula (1).
[Formula 1]
_{X (m) Y (n)} Z (1-mn) · (H 2 O) p
In Equation (1)
X, Y and Z are different from each other, and m and n independently of one another are each an integer of more than 0 and less than 1, and Zr, Sn, Mg, Ti, Al, Bi and Sb or an oxide, carbonate, 1-mn is not 0, and p is a number of 0 or more. The adhesive film for semiconductor according to claim 18, wherein X, Y and Z are each independently an oxide, a carbonate or a phosphate of Zr, Sn, Mg, Ti, Al, Bi and Sb. The adhesive film for semiconductor according to claim 18 or 19, wherein the metal ion capturing agent is in a spherical or amorphous form. A bonding film for semiconductor produced by a bonding composition for a semiconductor according to any one of claims 1 to 5 or a film for a semiconductor according to any one of claims 8 to 13 and 16 to 19 Wherein the adhesive film for semiconductors according to claim 1, An adhesive film for semiconductor produced by the adhesive composition for semiconductor according to any one of claims 1 to 5, or a film for semiconductor according to any one of claims 8 to 13, 16, and 19 A semiconductor device connected by an adhesive film for semiconductor.