TWI458798B - Adhesive composition for semiconductor and adhesive film comprising the same - Google Patents

Description

Adhesive composition for semiconductor and adhesive film containing the same Field of invention

The present invention relates to an adhesive composition for a semiconductor and an adhesive film comprising the composition. More particularly, the present invention relates to an adhesive composition for a semiconductor which ensures a minimum modulus in wire bonding after die bonding to have excellent initial reliability, and achieves wafer bonding by an amine curing agent Subsequent multiple curing procedures provide a residual cure rate over a higher reaction temperature range, thereby facilitating the elimination of voids in EMC molding. The invention also relates to an adhesive film comprising the composition.

Background of the invention

In order to realize a semiconductor device having a high capacity, a qualitative high integration method of increasing the number of cells per unit area and a quantitative encapsulation method of placing a plurality of wafers to increase the capacity are used.

As a packaging method, a multi-chip package (MCP) is generally used in which a plurality of wafers are placed with an adhesive, and the upper and lower wafers are electrically connected by wire bonding.

In placing a semiconductor package wafer, when wafers of the same size are vertically mounted, spacers are usually attached in advance to secure a space for bonding the leads, resulting in inconvenience of an additional procedure for attaching the spacers. Recently, it is preferable to provide the lower bonding wire directly to the adhesive film attached to the lower surface of the upper wafer to simplify the program. Therefore, the adhesive layer requires a fluidity sufficient to pass the bonding wires therethrough at a wafer bonding temperature of about 100 to 150 °C. If the adhesive layer is not sufficiently fluid, quality defects such as lead collapse or compression may occur.

Therefore, a high fluidity adhesive is introduced to solve the problem that the low flow adhesive cannot be adapted to the bonding wires. However, high flow adhesive layers can result in inconsistent bonds because the wafer can bend in the wafer bonding process due to excessive bonding properties resulting from high flow. Meanwhile, if the adhesive substrate has an inconsistent portion on the surface, the void is formed at the interface between the adhesive layer and the substrate. Once formed, the voids cannot be removed and can be fixed during the adhesive cure or epoxy molding (EMC molding) process, resulting in defects in the semiconductor wafer package and reducing reliability under severe conditions. Therefore, it is recommended to use a semi-curing procedure after bonding the same type of wafer. However, this approach is disadvantageous due to additional procedures and reduced productivity.

Summary of invention

The present invention provides an adhesive composition for a semiconductor and an adhesive film comprising the same, which can shorten or eliminate a semi-curing process, eliminate or minimize voids, and multiple after wafer bonding The procedure provides a residual curing rate to eliminate voids in EMC molding and effectively remove voids created in semiconductor fabrication processes including wafer placement and molding to improve processability and reliability. Further, the adhesive composition can be applied to the FOW, which requires the pass-through property of the bonding wires and has the ability to eliminate voids in the EMC molding, thereby obtaining workability and reliability in bonding the same kind of wafer, wherein The adhesive film includes the bonding wires.

One aspect of the present invention provides an adhesive composition for a semiconductor. The adhesive composition may have a compressive strength of 100 to 1500 gf/mm ² at 150 ° C after curing at 125 ° C for 30 minutes. Preferably, the adhesive composition for a semiconductor has a compressive strength of 500 to 1000 gf/mm ² .

The adhesive composition for a semiconductor may include a binder resin, an epoxy resin, and an amine curing agent. The binder resin is a (meth) acrylate copolymer, and the amine curing agent includes a first amine curing agent represented by Formula 1 and a second amine curing agent represented by Formula 2:

Wherein A represents a C1 to C6 straight or branched alkylene group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent hydrogen. a C1 to C4 alkyl group, a C1 to C4 alkoxy group, or an amino group, and at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ Two include an amino group;

Wherein B represents -SO ₂ -, -NHCO- or -O-, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent hydrogen. a C1 to C4 alkyl group, a C1 to C4 alkoxy group, or an amino group, and at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ Both include an amino group.

The adhesive composition for a semiconductor may have a first void (Vc) area ratio of less than 15% on the adhesive after one cycle of curing at 150 ° C for 30 minutes.

The (meth) acrylate copolymer may have a viscosity of from 1000 to 300,000 cps at 25 °C.

The (meth) acrylate copolymer may include 1 to 20% by weight of glycidyl (meth) acrylate.

The content of the binder resin may be from 35 wt% to 70 wt% (in terms of solid content) based on the total amount of the adhesive composition for the semiconductor.

The epoxy resin may include a biphenyl-containing epoxy resin. In a specific embodiment, the epoxy resin may include 3 to 100% by weight of the biphenyl-containing epoxy resin.

The amine curing agent may include 0.5 to 50% by weight of the first amine curing agent and 50 to 99.5% by weight of the second amine curing agent.

The weight ratio of the first amine curing agent to the second amine curing agent may be from 1:1.1 to 1:100.

The adhesive composition for a semiconductor may be cured at 150 ° C for 30 minutes and after EMC molding at 175 ° C for 60 seconds, may have a second void (Vm) area ratio of less than 15% on the adhesive.

The content of the binder resin may be greater than the total amount of the epoxy resin and the amine curing agent.

The adhesive composition may further include a decane coupling agent and a filler.

The adhesive composition for a semiconductor may include 25 to 70% by weight of the binder resin, 5 to 35% by weight of the epoxy resin, 1 to 15% by weight of the amine curing agent, 0.01 to 5% by weight The decane coupling agent and 10 to 55 wt% of the filler.

Another aspect of the present invention provides an adhesive film for a semiconductor formed of the adhesive composition.

Detailed description of the preferred embodiment

Exemplary embodiments are described in detail below. However, it is to be understood that the following specific examples are provided by way of illustration only and are not to be construed as limiting. The scope of the invention is to be limited only by the scope of the appended claims and their equivalents.

In the text, unless otherwise stated, the content of each component will be stated based on the solid content.

The adhesive composition for a semiconductor according to an exemplary embodiment of the present invention has a compressive strength of 100 to 1500 gf/mm ² at 150 ° C after curing at 125 ° C for 30 minutes. Herein, the term "compressive strength" means a laminate having a thickness of 400 μm formed by curing the adhesive composition at 125 ° C for 30 minutes and pressing at a temperature of 150 ° C and 0.1 mm/sec with ARES at a pressed distance of 0.05 mm. Under the strength. Specifically, the adhesive composition may have a compressive strength of 500 to 1200 gf/mm ² , for example, 530 to 1000 gf/mm ² . High compressive strength helps ensure reliability in wire bonding and effectively removes voids in EMC molding. When the compressive strength was measured, curing at 125 ° C for 30 minutes corresponds to curing at 150 ° C for 10 minutes.

The adhesive composition has a void (Vc) area ratio after one cycle of less than 15%, preferably less than 11%, and more preferably less than 6%.

Herein, the term "primary cycle curing" refers to a procedure in which a substrate/adhesive layer/substrate sample is placed on a hot plate and the adhesive layer is cured at 150 ° C for 30 minutes. 150 ° C and 30 minutes are the temperatures and times required for wire bonding after wafer bonding. At this time, the void generated in the program is defined as "the void after one cycle (hereinafter referred to as Vc)". The image area of the adhesive layer cured under the above conditions was collected by a microscope (magnification: × 25), and the void area was calculated by numerical value with respect to the measurement area to obtain a void area ratio (Vc area ratio) ((Vc area ratio = The void area/total area × 100. When the area ratio (Vc) of the void is more than 15%, the reliability is deteriorated.

Both samples can be made as follows.

The substrate/adhesive layer/substrate sample can be prepared by forming the adhesive film of the present invention to a thickness of 50 to 60 μm, followed by lamination between two 10 mm × 10 mm glass slides at 60 °C.

Alternatively, the PCB (or wafer) can be prepared by placing the ground wafer on a hot plate, removing impurities with isopropyl alcohol (IPA), and mounting the prepared adhesive film on the glossy side of the wafer. / Adhesive layer / wafer sample. At this time, the mounter sets the actual surface temperature at a temperature of 60 °C. The attached adhesive film and wafer were cut into 10 mm × 10 mm wafers, and the wafer (adhesive + wafer) on which the adhesive of the present invention was formed on one side was attached at 120 ° C and 1 kgf / sec. Pre-processed PCBs under the following conditions.

After a cycle of curing, and then EMC molding at 175 ° C for 60 seconds, a gap is created between the PCB (or wafer) and the adhesive layer. At this time, the void generated in the program is defined as "the void (Vm) after molding". The void (Vm) was measured after curing and molding under the above conditions. The sample was divided into individual units by a singulation saw, the PCB was removed to measure Vm, and ground with a grinder to expose the adhesive layer of the adhesive film. At this time, the solder resist (SR) layer polished to the PCB is only slightly left translucent to facilitate viewing of the voids.

After the grinding, an image of the exposed adhesive layer was collected with a microscope (magnification: × 25), and analysis was performed to determine whether or not voids were present, and Vm was numerically represented. In order to numerically represent the void (Vm), the total area was divided into 10 × 10 regions, and the region having the void was calculated and expressed as a percentage (Vm area ratio = void area / total area × 100). When the area ratio of Vm is less than 10%, the adhesive composition of the present invention is determined to be void elimination. When the area ratio of Vm is 10% or more, the adhesive composition of the present invention is determined not to eliminate voids. When the area ratio of Vm is less than 10%, excellent reliability can be obtained, and wafer creep does not occur.

The above adhesive composition for a semiconductor may include a binder resin, an epoxy resin, and an amine curing agent.

Adhesive resin

The binder resin may include only a (meth) acrylate copolymer or a combination of a (meth) acrylate copolymer and other polymer resins. In a specific embodiment, the binder resin can be a (meth) acrylate copolymer. Specifically, the (meth) acrylate copolymer may include an epoxy group.

In a specific embodiment, the (meth) acrylate copolymer may include a (meth) acrylate copolymer having an epoxy equivalent of 500 to 10,000. Within this range, high viscosity can be exhibited before heat curing, and high adhesion obtained after heat curing.

The (meth) acrylate copolymer may have a weight average molecular weight of 10,000 to 5,000,000 g/mol, preferably 50,000 to 1,000,000 g/mol. Within this range, excellent coating film formability can be obtained.

The above (meth) acrylate copolymer may be a copolymer of an alkyl (meth) acrylate monomer and a glycidyl (meth) acrylate monomer.

The (meth)acrylic acid alkyl ester monomer functions to impart viscosity to the film. The (meth)acrylic acid alkyl ester monomer may include, but is not limited to, 2-ethylhexyl methacrylate, isooctyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, n-butyl acrylate, Isobutyl acrylate, octadecyl methacrylate, and the like. The above (meth) acrylate copolymer may include 50 to 90% by weight, preferably 65 to 85% by weight, of an alkyl (meth) acrylate. Within this range, excellent adhesion and reliability are obtained.

Examples of the glycidyl (meth)acrylate monomer may include, but are not limited to, glycidyl methacrylate, glycidyl acrylate, and the like. Specifically, the (meth) acrylate copolymer may include 1 to 20% by weight, preferably 3 to 8% by weight, of glycidyl (meth) acrylate. Within this range, excellent adhesion and reliability are obtained. Meanwhile, in this range, the compressive strength after curing at 125 ° C for 60 minutes and at 150 ° C for 30 minutes may be 100 to 1500 gf / mm ² .

Alternatively, the (meth) acrylate copolymer may optionally include a hydroxyl group-containing (meth) acrylate monomer in addition to the above monomers. Examples of the hydroxyl group-containing (meth) acrylate monomer may include, but are not limited to, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, acrylic acid-3. - Hydroxypropyl ester, hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, N-(hydroxymethyl) acrylate, 3-chloro-2-hydroxypropyl methacrylate, and the like. The (meth) acrylate copolymer may include 5 to 35 wt%, preferably 10 to 30 wt% of a hydroxyl group-containing (meth) acrylate. Within this range, excellent adhesion and reliability are obtained.

The above binder resin may have a glass transition temperature of -55 to 80 ° C, preferably 5 to 60 ° C, and more preferably 5 to 35 ° C. Within this range, high fluidity is ensured to achieve excellent void elimination performance, and adhesion and reliability can be obtained.

The (meth) acrylate copolymer may have a viscosity of from 1000 to 300,000 cps at 25 °C. Within this range, excellent coating film formability can be obtained. Specifically, the viscosity may be from 3,000 to 100,000 cps.

The above binder resin may be contained in an amount of 25 to 70% by weight, preferably 36 to 60% by weight based on the total amount of the adhesive composition for the semiconductor. Within this range, excellent reliability and void elimination effects can be obtained.

Epoxy resin

The epoxy resin acts as a curing and adhesion and may include liquid epoxy resins, solid epoxy resins, and mixtures thereof.

Examples of liquid epoxy resins may include, but are not limited to, biphenyl epoxy resins, bisphenol A liquid epoxy resins, bisphenol F liquid epoxy resins, trifunctional or more functional liquid epoxy resins, rubber modified Liquid epoxy resin, polyurethane modified liquid epoxy resin, acrylic modified liquid epoxy resin and photosensitive liquid epoxy resin, which may be used singly or in combination thereof. Specifically, a biphenyl epoxy resin can be used.

The above liquid epoxy resin may have an epoxy equivalent weight of from about 100 to about 1500 g/eq, preferably from about 150 to about 800 g/eq, and more preferably from about 150 to about 400 g/eq. Within this range, the cured product exhibits excellent adhesion, maintains a glass transition temperature, and has excellent heat resistance.

Further, the liquid epoxy resin may have a weight average molecular weight of about 100 to 1000 g/mol. Within this range, the resin exhibits excellent fluidity.

The solid epoxy resin may include any epoxy resin having a solid phase or near a solid phase and having at least one functional group at room temperature. Specifically, an epoxy resin having a softening point (SP) of 30 to 100 ° C can be used. Examples of the solid epoxy resin may include a biphenyl epoxy resin, a bisphenol epoxy resin, a novolac epoxy resin, an o-cresol novolac epoxy resin, a polyfunctional epoxy resin, an amine epoxy resin, and a heterocyclic ring. Oxygen resins, substituted epoxy resins, naphthol epoxy resins, and derivatives thereof.

Commercially available products of solid epoxy resins include the following products. Examples of the bisphenol epoxy resin include: YD-017H, YD-020, YD020-L, YD-014, YD-014ER, YD-013K, YD-019K, YD-019, YD-017R, YD-017, YD -012, YD-011H, YD-011S, YD-011, YDF-2004, YDF-2001 (Kukdo Chemical Co., Ltd.) and the like. Examples of the novolac epoxy resin include: EPIKOTE 152 and EPIKOTE 154 (Yuka Shell Epoxy Co., Ltd.); EPPN-201 (Nippon Kayaku Co., Ltd.); DN-483 (Dow Chemical Co.); YDPN-641, YDPN-638A80, YDPN-638, YDPN-637, YDPN-644, YDPN-631 (Kukdo Chemical Co., Ltd.), and the like. Examples of the o-cresol novolac epoxy resin include: YDCN-500-1P, YDCN-500-2P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, YDCN-500-8P, YDCN-500- 10P, YDCN-500-80P, YDCN-500-80PCA60, YDCN-500-80PBC60, YDCN-500-90P, YDCN-500-90PA75 (Kukdo Chemical Co., Ltd.); EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027 (Nippon Kayaku Co., Ltd.); YDCN-701, YDCN-702, YDCN-703, YDCN-704 (Tohto Kagaku Co., Ltd.); Epiclon N-665-EXP ( Dainippon Ink and Chemicals) and so on. Examples of the bisphenol novolac epoxy resin include: KBPN-110, KBPN-120, KBPN-115 (Kukdo Chemical Co., Ltd.), and the like. Examples of polyfunctional epoxy resins include: Epon 1031S (Yuka Shell Epoxy Co., Ltd.); Araldite 0163 (Ciba Specialty Chemicals); Detachol EX-611, Detachol EX-614, Detachol EX-614B, Detachol EX-622, Detachol EX-512, Detachol EX-521, Detachol EX-421, Detachol EX-411, Detachol EX-321 (NAGA Celsius Temperature Kasei Co., Ltd.); EP-5200R, KD-1012, EP-5100R, KD-1011, KDT -4400A70, KDT-4400, YH-434L, YH-434, YH-300 (Kukdo Chemical Co., Ltd.) and the like. Examples of the amine epoxy resin include: EPIKOTE 604 (Yuka Shell Epoxy Co., Ltd.); YH-434 (Tohto Kagaku Co., Ltd.); TETRAD-X and TETRAD-C (Mitsubishi Gas Chemical Company); ELM-120 (Sumitomo Chemical Industry) Ltd.) and so on. Examples of heterocyclic epoxy resins include PT-810 Ciba Specialty Chemicals). Examples of the substituted epoxy resin include: ERL-4234, ERL-4299, ERL-4221, ERL-4206 (UCC Co., Ltd.) and the like. Examples of the naphthol epoxy resin include: Epiclon HP-4032, Epiclon HP-4032D, Epiclon HP-4700, and Epiclon HP-4701 (Dainippon Ink and Chemicals). These epoxy resins may be used singly or as a mixture.

Specifically, the epoxy resin may include 1 to 50% by weight, for example, 3 to 30% by weight of a biphenyl-containing epoxy resin. Within this range, the cured product exhibits excellent adhesion and excellent heat resistance.

Examples of the biphenyl epoxy resin include YX-4000H (Japan Epoxy Resin Co., Ltd.), YSLV-120TE, GK-3207 (Nippon Steel Chemical Co., Ltd.), and NC-3000 (Nippon Kayaku Co., Ltd.), which may be used alone or Used in combination of them.

The content of the epoxy resin may be from about 5 to 35 wt%, preferably from about 10 to 25 wt%, based on the total amount of the adhesive composition on the solid content. Within this range, excellent reliability can be ensured and void (Vc) elimination effect can be obtained.

Specifically, the amount of the above binder resin may be greater than the amount of the epoxy resin. In a specific embodiment, the ratio of binder resin to epoxy resin can range from 1.2:1 to 2:1.

Hardener

The amine curing agent can be two different types of amine curing agents having different reaction temperature ranges. That is, the first amine curing agent and the second amine curing agent.

The first amine curing agent may be an aromatic diamine represented by Formula 1:

Wherein A represents a C1 to C6 straight or branched alkylene group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent hydrogen. a C1 to C4 alkyl group, a C1 to C4 alkoxy group, or an amino group, and at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ Both include an amino group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may be the same or different substituents in the same ring. The first amine curing agent may have a symmetrical structure or an asymmetric structure, preferably a symmetrical structure.

Examples of the first amine curing agent include 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetra-n-propyl Diphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3',5,5'- Tetraisopropyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl 5-,5'-diethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-diisopropyldiphenylmethane, 4,4' -diamino-3,3'-diethyl-5,5'-diethyldiphenylmethane, 4,4'-diamino-3,5'-dimethyl-3',5'-di Ethyldiphenylmethane, 4,4'-diamino-3,5-dimethyl-3',5'-diisopropyldiphenylmethane, 4,4'-diamino-3,5- Diethyl-3',5'-dibutyldiphenylmethane, 4,4'-diamino-3,5-diisopropyl-3',5'-dibutyldiphenylmethane, 4 , 4'-diamino-3,3'-diisopropyl-5,5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5', 5'-di Diphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4, 4'-Diamino-3,3'-di-n-propyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyldiphenylmethane, 4,4'-diamino- 3,3'-dibutyldiphenylmethane, 4,4'-diamino-3,3',5-trimethyldiphenylmethane, 4,4'-diamino-3,3',5 -triethyldiphenylmethane, 4,4'-diamino-3,3',5-tri-n-propyldiphenylmethane, 4,4'-diamino-3,3',5-triiso Propyldiphenylmethane, 4,4'-diamino-3,3',5-tributyldiphenylmethane, 4,4'-diamino-3-methyl-3'-ethyldiphenyl Methane, 4,4'-diamino-3-methyl-3'-isopropyldiphenylmethane, 4,4'-diamino-3-methyl-3'-butyldiphenylmethane, 4,4'-diamino-3-isopropyl-3'-butyldiphenylmethane, 2,2-bis(4-amino-3,5-dimethylphenyl)propane, 2,2- Bis(4-amino-3,5-diethylphenyl)propane, 2,2-bis(4-amino-3,5-di-n-propylphenyl)propane, 2,2-bis(4-amino -3,5-diisopropylphenyl)propane, 2,2-bis(4-amino-3,5-dibutyl Phenyl) propane and the like. Among these first amine curing agents, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5 is preferably used. Tetramethyldiphenylmethane and 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane.

The second amine curing agent may be an aromatic diamine represented by Formula 2:

Wherein B represents -SO ₂ -, -NHCO- or -O-, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent hydrogen. a C1 to C4 alkyl group, a C1 to C4 alkoxy group, or an amino group, and at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ Both include an amino group.

Examples of the second amine curing agent may include 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'-diamino-3,3',5,5' -tetramethyldiphenylphosphonium, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylphosphonium, 4,4'-diamino-3,3',5, 5'-Tetra-n-propyldiphenylphosphonium, 4,4'-diamino-3,3',5,5'-tetraisopropyldiphenylphosphonium and the like. Specifically, 4,4'-diaminodiphenylanthracene can be used.

The above amine curing agent may include 0.5 to 50% by weight of the first amine curing agent and 50 to 99.5% by weight of the second amine curing agent.

In a specific embodiment, the weight ratio of the first amine curing agent to the second amine curing agent may be from 1:1 to 1:100. Within this range, excellent stability can be obtained. Specifically, the above ratio may be 1:1.5 to 1:85.

The content of the above amine curing agent may be from 1 to 15% by weight, preferably from 3 to 10% by weight, based on the total amount of the adhesive composition on the solid content. Within this range, a void (Vc) reduction effect can be obtained.

Decane coupling agent

The decane coupling agent serves as an adhesion enhancer for improving the bonding strength due to chemical bonding between an organic material and an inorganic material such as a filler.

Any decane coupling agent in the art can be used, for example, an epoxy-containing decane coupling agent such as 2-(3,4-epoxycyclohexyl)-ethyltrimethoxydecane, 3-glycidyloxyl Trimethoxy decane and 3-glycidoxypropyl triethoxy decane; amino-containing decane coupling agents such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Baseline, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethyl Oxydecane, 3-aminopropyltriethoxydecane, 3-triethoxymethylidene-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyl Trimethoxy decane; a mercapto group-containing decane coupling agent such as 3-mercaptopropylmethyldimethoxydecane and 3-mercaptopropyltriethoxydecane; and an isocyanate group-containing decane coupling agent such as 3 - Isocyanatopropyltriethoxydecane, which may be used singly or in combination of them.

The coupling agent may be included in an amount of from about 0.01 to 5% by weight, preferably from 0.1 to 3% by weight, and more preferably from about 0.5 to 2% by weight, based on the total amount of the adhesive composition on the solid content. Within this range, excellent bonding reliability can be obtained, and the bubble problem can be suppressed.

filler

The above adhesive composition may further include a filler.

Examples of the filler may include metals in powder form such as gold, silver, copper, and nickel; and non-metals such as alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, and oxidation. Calcium, magnesium oxide, aluminum nitride, ceria, boron nitride, titanium dioxide, glass, ferrite, ceramics, and the like. Specifically, cerium oxide can be used as the above filler.

Although the above filler is not particularly limited in shape and size, the filler is usually spherical ceria and amorphous ceria, and may have a size of 5 nm to 20 μm.

The content of the above filler may be from about 10 to 55 wt%, preferably from about 15 to 45 wt%, and more preferably from 20 to 40 wt%, based on the total amount of the adhesive composition on the solid content. Within this range, excellent fluidity, film formability, and adhesion can be obtained.

Solvent

The adhesive composition may further include a solvent. Solvents are used to reduce the viscosity of the adhesive composition for semiconductors and to promote film formation. Examples of the above solvent may include, but are not limited to, an organic solvent such as toluene, xylene, propylene glycol monomethyl ether acetate, benzene, acetone, methyl ethyl ketone, tetrahydrofuran, dimethyl hydrazine, cyclohexanone or the like.

Another aspect of the present invention provides an adhesive film for a semiconductor formed of the above-described adhesive composition. The use of the adhesive composition of the present invention for the manufacture of an adhesive film for semiconductor assembly requires no special equipment or equipment. The above adhesive film for semiconductor assembly can be formed by any method known in the art. For example, the components are dissolved in a solvent and thoroughly mixed with a ball mill, and then the mixture is applied to a release-treated polyethylene terephthalate (PET) film with an applicator at 100 ° C. The oven is thermally dried for 10 to 30 minutes to obtain an adhesive film having a suitable thickness.

In a specific embodiment, the adhesive film for a semiconductor may be composed of a base film, a pressure-sensitive adhesive layer, a bonding layer, and a protective film which are sequentially placed.

The above adhesive film may have a thickness of 5 to 200 μm, preferably 10 to 100 μm. Within this range, a balance between sufficient bond strength and cost efficiency can be obtained. Specifically, the thickness may be 15 to 60 μm.

The adhesive layer and the adhesive film produced by the adhesive composition according to the present invention can shorten or eliminate the semi-curing procedure after bonding the same type of wafer, and minimize the generation of voids (Vc and Vm).

Hereinafter, the present invention will be explained in more detail with reference to the following examples. These examples are provided for illustrative purposes only and are not to be construed as limiting the invention in any way.

Example

The details of the components used in the examples and comparative examples are explained below.

(A1) Adhesive Resin: SG-P3 (Nagase Chemtex)

(A2) Adhesive Resin: SBR 1000 (Emulsion Styrene Butadiene Rubber, Kumho Petrochemical)

(B1) Epoxy Resin: YDCN-500-1P (Kukdo Chemical)

(B2) Epoxy resin: NC-3000 (Nippon Kayaku)

(C1) Amine curing agent: C-300S (Nippon Kayaku, equivalent: 78)

(C2) Amine curing agent: DDS (Wako, equivalent: 67)

(D) decane coupling agent: KBM-403 (Shinetsu)

(E) Filler: SO-25H (ADMATECH)

(F) Solvent: cyclohexanone

Table 1 (solid content)

Table 2 (solid content)

Preparation of adhesive film

The components listed in Table 1 and Table 2 were added to cyclohexanone as the solvent (I), which had a solid content of 40%, and thoroughly mixed with a ball mill, and then the mixture was applied to the release type by an applicator. The treated PET film was thermally dried in an oven at 100 ° C for 10 to 30 minutes to prepare an adhesive film having a thickness of 60 μm.

The adhesive films produced in Examples 1 to 4 and Comparative Examples 1 to 7 were tested as follows, and the results are shown in Tables 5 and 6.

(1) Compressive strength

Each of the adhesive compositions was formed into a laminate having a thickness of 400 μm, which was placed between release-treated PET films and cured in an oven at 125 ° C for 30 minutes. Then, the product was pressed with ARES at 150 and 0.1 mm/sec, and the strength at a pressing distance of 0.05 mm was measured.

(2) Vm area ratio

The ground wafer was placed on a hot plate of a mounter, and impurities were removed with isopropyl alcohol (IPA), and the obtained adhesive films were mounted on the glossy surface of the wafer. At this time, the mounter sets the actual surface temperature at a temperature of 60 °C. Then, the adhesive film and the wafer were cut into a wafer of 10 mm × 10 mm, and the wafer (adhesive + wafer) on which the adhesive of the present invention was formed was attached at 120 ° C and 1 kgf / sec to Table 3 Prepare the sample by pre-treating the PCB under the conditions of the column.

The above sample was subjected to one cycle curing on a hot plate at 150 ° C for about 30 minutes, and then subjected to EMC molding under the conditions listed in Table 4, followed by measurement of voids.

Then, the above sample was divided into individual units by a split saw, the PCB was removed to measure Vm, and ground with a grinder to expose the adhesive layer of the adhesive film. At this time, only a small amount of the solder resist (SR) layer polished to the PCB remains translucent to facilitate observation of the void.

After the grinding, an image of the exposed adhesive layer was collected with a microscope (magnification: × 25), and analyzed to determine whether or not voids were present. In order to represent the gaps by numerical values, a grid counting method is used. That is, the total area is divided into 10 × 10 regions, and the region having the void is counted and expressed as a percentage (Vm area ratio). When the Vm ratio is less than 10%, it is determined to be void elimination. When the Vm ratio is 10% or more, it is determined that the void is not eliminated.

Vm area ratio = void area / total area × 100

(3) Vc area ratio

Each adhesive composition was formed to a thickness of 50 to 60 μm so that the solvent remained less than 1%, then laminated between two 10 mm × 10 mm glass slides at 60 ° C, and cured on a hot plate at 150 ° C. minute. An image of the adhesive layer was taken with a microscope (magnification: x 25) and analyzed to numerically represent the void area relative to the total measurement area.

Vc area ratio = void area / total area × 100

(4) Wafer creep after one cycle and molding

Each sample was produced in the same manner as the above measurement method (2), and subjected to EMC molding, followed by scanning ultrasonic microscope (SAT) to check whether creep occurred. When the sample was moved 10% or more from the initial attachment position, it was judged to be creep.

(5) Wafer shear strength

A 530 μm thick wafer coated with a dioxide film was cut into 5 mm × 5 mm wafers. These wafers were laminated with each adhesive film at 60 °C. Cutting the laminate leaves only the joint portion. By applying a force of 1 kgf on a hot plate at 120 ° C for 1 second, followed by curing by curing in an oven at 125 ° C for 60 minutes, on a hot plate at 150 ° C for 30 minutes, and then at 175 ° C for 2 hours. Procedure, a 5 mm x 5 mm upper wafer was attached to a 10 mm x 10 mm alloy 42 lead frame. The sample was incubated for 168 hours at 85 ° C / 85% RH and refluxed three times at the highest temperature of 260 ° C. Then, the wafer shear strength was measured at 250 ° C using a DSS apparatus (DAGE 4000).

(6) Reflow resistance test

Each sample was prepared in the same manner as in Test Step (2), and subjected to EMC molding and curing (in an oven at 175 ° C for 2 hours). The sample was blotted at 85 ° C / 85% RH for 168 hours and refluxed three times at the highest temperature of 260 ° C, and then the sample was observed to check for cracks.

* One cycle semi-curing: curing in a furnace at 150 ° C for 10 minutes and curing on a hot plate at 150 ° C for 30 minutes

As shown in Tables 5 and 6, the adhesive films according to Examples 1 to 4 had a compressive strength of 100 to 1500 gf/mm ² and voids were eliminated after molding. Meanwhile, the adhesive films according to Comparative Examples 1, 3 and 7 have a very high Vc area ratio, but the adhesive film according to Comparative Example 1 has a relatively low compressive strength, and the adhesive films according to Comparative Examples 6 and 7 Has a very high compressive strength. The voids in the adhesive film according to Comparative Examples 1, 2, 4, 6, and 7 were not eliminated after molding.

While the invention has been described with respect to the embodiments of the present invention, it is understood that Therefore, the scope of the invention should be limited only by the scope of the appended claims and their equivalents.

Claims (18)

Adhesive composition for semiconductor, the cured adhesive composition having a compressive strength after 30 minutes 100gf / mm at 150 ℃ ² to 1500gf / mm ² at 125 ℃. The adhesive composition for a semiconductor according to claim 1, comprising: a binder resin, an epoxy resin, and an amine curing agent. The adhesive composition for a semiconductor according to claim 2, wherein the binder resin comprises a (meth) acrylate copolymer. The adhesive composition for a semiconductor according to claim 2, wherein the amine curing agent comprises a first amine curing agent represented by Formula 1 and a second amine curing agent represented by Formula 2: Wherein A represents a C1 to C6 straight or branched alkylene group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent hydrogen. a C1 to C4 alkyl group, a C1 to C4 alkoxy group, or an amino group, and at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ Both include an amino group, and Wherein B represents -SO ₂ -, -NHCO- or -O-, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent hydrogen. a C1 to C4 alkyl group, a C1 to C4 alkoxy group, or an amino group, and at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ Both include an amino group. The adhesive composition for a semiconductor according to the above aspect of the invention, wherein the adhesive composition has a compressive strength of from 500 gf/mm ² to 1000 gf/mm ² . The adhesive composition for a semiconductor according to claim 1, wherein the adhesive composition for a semiconductor has less than 15% on the adhesive after one cycle of curing at 150 ° C for 30 minutes. The first void area ratio. The adhesive composition for a semiconductor according to claim 3, wherein the (meth) acrylate copolymer has a viscosity of from 1000 cps to 300,000 cps at 25 °C. The adhesive composition for a semiconductor according to claim 3, wherein the (meth) acrylate copolymer comprises 1 wt% to 20 wt% of glycidyl (meth)acrylate. The adhesive composition for a semiconductor according to claim 2, wherein the content of the binder resin is from 35 to 70% by weight based on the total amount of the adhesive composition on a solid content. An adhesive composition for a semiconductor according to claim 2, wherein the epoxy resin comprises a biphenyl group-containing epoxy resin. The adhesive composition for a semiconductor according to claim 10, wherein the epoxy resin comprises 3 wt% to 100 wt% of the biphenyl group-containing epoxy resin. The adhesive composition for a semiconductor according to claim 4, wherein the amine curing agent comprises 0.5% by weight to 50% by weight of the first amine curing agent and 50% by weight to 99.5% by weight of the Second amine curing agent. The adhesive composition for a semiconductor according to claim 12, wherein the weight ratio of the first amine curing agent to the second amine curing agent is from 1:1.1 to 1:100. The adhesive composition according to claim 1, wherein the adhesive composition is cured at 150 ° C for one cycle of 30 minutes and after EMC molding at 175 ° C for 60 seconds, has less than 10 on the adhesive. % of the second void area ratio. The adhesive composition for a semiconductor according to claim 2, wherein the content of the binder resin is greater than the total amount of the epoxy resin and the amine curing agent. The adhesive composition for a semiconductor according to claim 2, wherein the adhesive composition further comprises a decane coupling agent and a filler. The adhesive composition for a semiconductor according to claim 16, wherein the adhesive composition comprises 25 wt% to 70 wt% of the binder resin, and 5 wt% to 35 wt% of the epoxy resin. 1 wt% to 15 wt% of the amine curing agent, 0.01 wt% to 5 wt% of the decane coupling agent, and 10 wt% to 55 wt% of the filler. An adhesive film for a semiconductor, comprising the adhesive composition according to any one of claims 1 to 17.